JP2011241401A - Material having crosslinked polyrotaxane, and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a material in which 'settling' is improved, which is a material having crosslinked polyrotaxanes.SOLUTION: In this material having first polyrotaxane and second polyrotaxane, the first and second polyrotaxanes are crosslinked through first and second cyclic molecules, and the material is solvent free, and the material has at least on kind of characteristic selected from each group having: (X) a compression set of ≤10%; a tensile stress relaxation of ≤15%; and a hysteresis loss of ≤25%.

Description

  The present invention relates to a material having a crosslinked polyrotaxane, wherein the material has at least one of reduced compression set, stress relaxation resistance, and low hysteresis loss, and is solvent-free. . The present invention also relates to a method for producing the material.

Rubber is a typical viscoelastic material, but it is known that plastic flow occurs under a long-term load or deformation. This is a phenomenon called “sag” and can be observed as characteristics such as compression set, stress relaxation, and / or hysteresis loss.
Since rubber products are often used after being compressed due to their characteristics, these characteristics are closely related to the performance of the product. For example, in fields where low compression set is required, such as paper feed rolls for paper feeding used in seal materials typified by O-rings and copiers, various proposals have been made to achieve these characteristics. And a low value of about several percent is achieved (see Patent Documents 1 to 4).

  In addition, soft actuators that use elastomeric materials such as dielectric actuators require materials with little stress relaxation and hysteresis loss as elastomers to improve durability during repeated use. Research using various elastomeric materials (See Non-Patent Document 1).

  Furthermore, in order to achieve a material with less “sagging” (a material with low compression set, stress relaxation and / or hysteresis loss), it is necessary to approach a more ideal elastic body. However, in materials such as rubber and elastomer, since the cross-linking points are fixed, non-uniformity occurs in the distance between the cross-linking points, and there is a limit to approach an ideal elastic body. For this reason, it is difficult to completely eliminate the “sag” resulting from plastic flow.

  On the other hand, polyrotaxanes 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 clasped by linear molecules are relatively Various applications are expected from the characteristics derived from moving on linear molecules (see Patent Document 5).

  In the crosslinked polyrotaxane, a crosslinking point is formed by crosslinking a plurality of cyclic molecules on a linear molecule. Since the crosslinking point can move along the linear molecule, the stress can be uniformly dispersed. In the case where the movement of the crosslinking point is sufficiently fast, the polymer form is always isotropic even when an external force is applied, so that the entropy elasticity (rubber elasticity) based on the polymer shape change does not occur. Become. However, free cyclic molecules on linear molecules that are not involved in cross-linking points cannot pass through the cross-linking points, resulting in non-uniform distribution of free cyclic molecules and new entropy elasticity. (Non-patent document 2). Because of these movable cross-linking points and unique entropy elasticity, polyrotaxane cross-links have the potential to act as ideal elastic bodies, but the cross-linked polyrotaxanes have not yet been studied with respect to “sag”. There wasn't.

JP-A-8-85636. JP-A-2005-70574. JP2005-154545A. JP 2006-274146 A. Japanese Patent No. 3475252.

"Performance of dielectic elastomer actuators and materials", Smart Structures and Materials, Electroactive Polymer Actuators and Devices, Proc. SPIE Vol. 4695, pp. 158-166, 2002. March 10, 2011 11th Ring Tube Supramolecular Research Group Symposium “Sliding Mode of Ringing Polymer” Preliminary pp. 19-22.

Accordingly, an object of the present invention is to provide a material with improved “sag” resulting from plastic flow, particularly a material having a crosslinked polyrotaxane and having improved “sag”.
Specifically, an object of the present invention is to provide a material having at least one characteristic of reduced compression set, reduced stress relaxation characteristics, and low hysteresis loss and having a crosslinked polyrotaxane. There is.
Moreover, the objective of this invention is providing the manufacturing method of this material in addition to the said objective or in addition to the said objective.
Furthermore, the objective of this invention is providing the composition used as the raw material of the said material in addition to the said objective or in addition to the said objective.
Moreover, the objective of this invention is providing the manufacturing method of this composition in addition to the said objective or in addition to the said objective.

The inventors have found the following invention.
<1> A material having a first polyrotaxane and a second polyrotaxane,
The first polyrotaxane is such that the first cyclic molecule is not detached at both ends of the first pseudopolyrotaxane in which the opening of the first cyclic molecule is clasped by the first linear molecule. A first blocking group is arranged on
In the second polyrotaxane, the second cyclic molecule is prevented from being detached at both ends of the second pseudo-polyrotaxane in which the opening portion of the second cyclic molecule is clasped by the second linear molecule. A second blocking group is arranged on
The first and second polyrotaxanes are crosslinked via first and second cyclic molecules,
The material is solvent-free;
The material is
X) Compression set is 10% or less, preferably 5% or less, more preferably 1% or less;
Y) Tensile stress relaxation is 15% or less, preferably 10% or less, more preferably 5% or less; and Z) Hysteresis loss is 25% or less, preferably 15% or less, more preferably 10% or less;
The above material having at least one characteristic selected from the group consisting of:

  The properties are: X) a combination of compression set and Y) tensile stress relaxation, Y) a combination of tensile stress relaxation and Z) hysteresis loss, Z) a combination of hysteresis loss and X) compression set, and X) compression set. A combination of strain, Y) tensile stress relaxation, and Z) hysteresis loss. In addition, the numerical value of each characteristic is said arbitrary value, and a characteristic should be those arbitrary combinations.

<2> In the cross-linking of the above <1>, it is preferable to have a polymer portion having 3 or more repeating units between the first and second cyclic molecules.
<3> In the above item <2>, the repeating unit of the polymer site may be a polyether, polyester, polysiloxane, polycarbonate, poly (meth) acrylate or polyene, or a copolymer thereof. Preferably, the repeating unit is a polyether or a polycarbonate, or a copolymer thereof.
<4> In the above item <2> or <3>, the polymer site may have a number average molecular weight of 300 or more and 10,000 or less, preferably 400 to 5000, more preferably 500 to 3000.

<5> In the cross-linking of <1> above, a polymer moiety having a number average molecular weight of 300 to 10,000, preferably 400 to 5000, more preferably 500 to 3000 is provided between the first and second cyclic molecules. Is good. The polymer site preferably has 3 or more repeating units. The repeating unit of the polymer site may be polyether, polyester, polysiloxane, polycarbonate, poly (meth) acrylate or polyene, or a copolymer thereof. Preferably, the repeating unit is a polyether or a polycarbonate, or a copolymer thereof.
<6> In any one of the above items <2> to <5>, the first and second cyclic molecules have first and second active groups, respectively.
Having first and second reactive groups at each end of the polymer site;
It is preferable that a bond is formed from the first active group and the first reactive group, a bond is formed from the second active group and the second reactive group, and a bridge is formed.

<7> A material having a first polyrotaxane and a second polyrotaxane, the first and second polyrotaxanes being crosslinked and solvent-free, wherein the material comprises:
X) Compression set is 10% or less, preferably 5% or less, more preferably 1% or less;
Y) Tensile stress relaxation is 15% or less, preferably 10% or less, more preferably 5% or less; and Z) Hysteresis loss is 25% or less, preferably 15% or less, more preferably 10% or less;
A method for producing a material having at least one characteristic selected from the group consisting of:
a) First blocking so that the first cyclic molecule is not detached at both ends of the first pseudopolyrotaxane in which the opening of the first cyclic molecule is clasped by the first linear molecule. Providing a first polyrotaxane having a group disposed thereon;
b) Second blocking so that the second cyclic molecule is not detached at both ends of the second pseudopolyrotaxane in which the opening of the second cyclic molecule is clasped by the second linear molecule. Providing a second polyrotaxane having a group disposed thereon;
c) preparing a first crosslinking compound having a polymer moiety; and d) reacting the first and second polyrotaxanes and a crosslinking precursor having the first crosslinking compound to react the first and second Cross-linking the polyrotaxane through the polymer site;
A method as described above, wherein a material is obtained by having

  The characteristics of X) to Z) are as follows: X) Combination of compression set and Y) Tensile stress relaxation, Y) Combination of tensile stress relaxation and Z) Hysteresis loss, Z) Hysteresis loss and X) Compression A combination of permanent set, X) compression set, Y) tensile stress relaxation, and Z) hysteresis loss. In addition, the numerical value of each characteristic is said arbitrary value, and a characteristic should be those arbitrary combinations.

<8> In the above item <7>, the polymer portion may have 3 or more repeating units.
<9> In the above item <8>, the repeating unit may be polyether, polyester, polysiloxane, polycarbonate, poly (meth) acrylate, polyene, or a copolymer thereof. Preferably, the repeating unit is a polyether or a polycarbonate, or a copolymer thereof.

  <10> In the above item <7>, the polymer portion may have a number average molecular weight of 300 or more and 10,000 or less, preferably 400 to 5000, more preferably 500 to 3000. The polymer site preferably has 3 or more repeating units. The repeating unit of the polymer site may be polyether, polyester, polysiloxane, polycarbonate, poly (meth) acrylate or polyene, or a copolymer thereof. Preferably, the repeating unit is a polyether or a polycarbonate, or a copolymer thereof.

<11> In any one of the above items <7> to <10>, the first crosslinking compound preferably has first and second reactive groups at both ends of the polymer site. The first cross-linking compound is
c) -1) a step of obtaining a polymer site; and c) -2) a step of providing first and second reactive groups on both ends of the polymer site, respectively;
It is good to be obtained.
The first and second cyclic molecules have first and second active groups, respectively;
It is preferable that a bond is formed from the first active group and the first reactive group, a bond is formed from the second active group and the second reactive group, and a bridge is formed.

<12> In any one of the above items <7> to <11>, the cross-linking precursor preferably includes a second cross-linking compound having at least a third and a fourth reactive group.
The first and second cyclic molecules have first and second active groups, respectively;
The first cross-linking compound has first and second reactive groups at both ends of the polymer site,
A bond is formed from the first active group and the first reactive group, a bond is formed from the second active group and the second reactive group, and the first and second polyrotaxanes pass through the polymer site. And a bond is formed from the first active group and the third reactive group, a bond is formed from the second active group and the fourth reactive group, and the first and second polyrotaxanes are: It may be crosslinked via a second crosslinking compound.

<13> In any one of the above <7> to <12>, the first cross-linking compound has first and second reactive groups at both ends of the polymer site, respectively, and the first and second reactive groups Are preferably protected by first and second protecting groups, respectively. The first cross-linking compound is
c) -1) obtaining a polymer moiety having 3 or more repeating units;
c) -2) providing first and second reactive groups at both ends of the polymer site; and c) -3) first and second protecting the first and second reactive groups, respectively. Providing a protecting group;
Obtained with
The first and second cyclic molecules have first and second active groups, respectively;
During the reaction of the crosslinking precursor, the first and second protecting groups are deprotected,
A bond is formed from the first active group and the first reactive group, a bond is formed from the second active group and the second reactive group, and the first and second polyrotaxanes pass through the polymer site. It should be crosslinked.

<14> In any one of the above items <7> to <13>, the crosslinking precursor has at least third and fourth reactive groups, and the third and fourth reactive groups are third and fourth, respectively. It may be protected by 4 protecting groups.
The second cross-linking compound is
e) providing a third and fourth protecting group for protecting the third and fourth reactive groups, respectively;
Obtained with
During the reaction of the crosslinking precursor, the third and fourth protecting groups are deprotected,
A bond is formed from the first active group and the first reactive group, a bond is formed from the second active group and the second reactive group, and the first and second polyrotaxanes pass through the polymer site. And a bond is formed from the first active group and the third reactive group, a bond is formed from the second active group and the fourth reactive group, and the first and second polyrotaxanes are: It may be crosslinked via a second crosslinking compound.

<15> In any one of the above items <6> and <11> to <14>, the first and second reactive groups may each have two or more functional groups.
<16> In any one of the above items <2> to <15>, the polymer portion may include a plurality of polymers and a linker portion that connects the polymers.
<17> In any one of the above items <2> to <16>, the polymer portion may have a branched chain.

<18> In the above item <17>, any of the plurality of polymers may have a branched chain, and / or the linker portion may have a branched chain.
<19> In any one of the above items <6> and <11> to <18>, the first and second active groups are each independently —OH, —SH, —NH ₂ , —COOH, —SO _3. It may be derived from a group selected from the group consisting of H and —PO ₄ H.
<20> In any one of the above items <6> and <11> to <19>, the first and second reactive groups, and the third and fourth reactive groups are each independently an isocyanate group or a thioisocyanate group. , An oxirane group, an oxetane group, a carbodiimide group, a silanol group, an oxazoline group, and an aziridine group. An isocyanate group or a thioisocyanate group is preferable, and an isocyanate group is more preferable.

<21> In any one of the above items <6> and <11> to <20>, the first and second protective groups, and the third and fourth protective groups are each independently ε-caprolactam, 1, 2-pyrazole, butanone oxime, 1,2,4-triazole, diisopropylamine, 3,5-dimethylpyrazole, diethyl malonate, dimethyl malonate, methyl acetoacetate, ethyl acetoacetate, N, N'-diphenylformamidine compound Preferably selected from the group consisting of protecting groups by reaction with. Preferred is ε-caprolactam, 3,5-dimethylpyrazole or butanone oxime, and more preferred is ε-caprolactam or 3,5-dimethylpyrazole.
<22> In any one of the above items <15> to <21>, the two or more functional groups include an isocyanate group, a thioisocyanate group, an oxirane group, an oxetane group, a carbodiimide group, a silanol group, an oxazoline group, and an aziridine group. It may be two or more groups selected from the group. An isocyanate group or a thioisocyanate group is preferable, and an isocyanate group is more preferable.
<23> In any one of the above <6> and <11> to <22>, the first and second active groups are derived from —OH groups, and the first and second reactive groups or functional groups are isocyanate groups. And the polymer portion may be polyether, polyester, polycarbonate, polysiloxane, or a copolymer thereof.

<24> I) A polyrotaxane in which blocking groups are arranged so that the cyclic molecule is not detached at both ends of a pseudopolyrotaxane in which openings of the cyclic molecule are skewered by linear molecules; and II) A first cross-linking compound having a first polymer moiety, the first and second reactive groups having both first and second reactive groups at both ends of the first polymer moiety. A first bridging compound having first and second protecting groups that protects;
A composition having

  <25> The composition according to <24>, further comprising: III) a third and a fourth protective group having at least a third and a fourth reactive group and protecting the third and the fourth reactive group A second cross-linking compound.

<26> A) I) A polyrotaxane in which a blocking group is arranged at both ends of a pseudopolyrotaxane in which the opening of a cyclic molecule is skewered by a linear molecule so that the cyclic molecule is not detached. The step of:
B) II) A first cross-linking compound having a first polymer moiety, having first and second reactive groups at both ends of the first polymer moiety, and the first and second A first crosslinking compound having first and second protecting groups that protect two reactive groups; and C) I) a polyrotaxane; and II) a first crosslinking compound;
A method for producing a composition, wherein the composition is obtained.

<27> In the above <26>,
D) III) providing a second bridging compound having at least a third and a fourth reactive group and having a third and a fourth protective group that protects the third and fourth reactive groups;
Further comprising
In step C), I) polyrotaxane; II) first cross-linking compound; and III) second cross-linking compound may be mixed.

<28> In any one of the above items <1> to <27>, the first and second cyclic molecules are each independently selected from the group consisting of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin. It is better.
<29> In any one of the above items <1> to <28>, the first and second linear molecules are each independently polyvinyl alcohol, polyvinylpyrrolidone, poly (meth) acrylic acid, cellulose resin (carboxy Methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.), polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl acetal resin, polyvinyl methyl ether, polyamine, polyethyleneimine, casein, gelatin, starch, etc. and / or their co-polymerization Polyolefin resins such as coalesced polymers, polyethylene, polypropylene, and other copolymer resins with olefin monomers, polyester resins, polyvinyl chloride resins, polystyrene and acrylo Polystyrene resins such as nitrile-styrene copolymer resins, acrylic resins such as polymethyl methacrylate and (meth) acrylate copolymers, acrylonitrile-methyl acrylate copolymer resins, polycarbonate resins, polyurethane resins, vinyl chloride-vinyl acetate Copolymer resins, polyvinyl butyral resins, etc .; and derivatives or modified products thereof, polyisobutylene, polytetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyamides such as nylon, polyimides, polyisoprene, Polydienes such as polybutadiene, polysiloxanes such as polydimethylsiloxane, polysulfones, polyimines, polyacetic anhydrides, polyureas, polysulfides, polyphosphazenes Preferably selected from the group consisting of polyketones, polyphenylenes, polyhaloolefins, and derivatives thereof, such as polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene. , Polyvinyl alcohol and polyvinyl methyl ether, preferably polyethylene glycol.

<30> In any one of the above items <1> to <29>, the first and second linear molecules each independently have a weight average molecular weight of 3,000 or more, preferably 5,000 to 100, 000, more preferably 10,000 to 50,000.
<31> In any one of the above items <1> to <30>, the first and second blocking groups are each independently dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, Silsesquioxanes, pyrenes, substituted benzenes (substituents include, but are not limited to, alkyl, alkyloxy, hydroxy, halogen, cyano, sulfonyl, carboxyl, amino, phenyl, etc. One or more may be present), polynuclear aromatics that may be substituted (substituents may include, but are not limited to, the same as above. One or more substituents may be present) And may be selected from the 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.

<32> In any one of the above items <1> to <31>, the first and second cyclic molecules are each independently derived from α-cyclodextrin, and the first and second linear molecules are polyethylene. Preferably it is glycol.
<33> In any one of the above items <1> to <32>, the first and second cyclic molecules are included in a skewered manner by the first and second linear molecules. When the amount of the cyclic molecules included is maximally included, the first and second cyclic molecules are each independently 0.001 to 0.6, preferably 0.01 to 0.5, More preferably, the first and second linear molecules are included in a skewered manner in an amount of 0.05 to 0.4.

According to the present invention, it is possible to provide a material having improved sag caused by plastic flow.
The present invention can provide a material having at least one characteristic of reduced compression set, reduced stress relaxation characteristics, and low hysteresis loss.
In addition to the above effects, or in addition to the above effects, the present invention can provide a method for producing the material.
Furthermore, according to the present invention, in addition to the above effects or in addition to the above effects, a composition as a raw material for the above materials can be provided.
Moreover, according to this invention, the manufacturing method of this composition can be provided in addition to the said effect or in addition to the said effect.

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 illustrates typically 1 aspect 1 of the bridge | crosslinking polyrotaxane in the material of this invention.

Hereinafter, the invention described in the present application will be described in detail.
The present application is a material having first and second polyrotaxanes,
The first and second polyrotaxanes are crosslinked via respective cyclic molecules,
The material is solvent-free;
X) Compression set is 10% or less, preferably 5% or less, more preferably 1% or less;
Y) Tensile stress relaxation is 15% or less, preferably 10% or less, more preferably 5% or less; and Z) Hysteresis loss is 25% or less, preferably 15% or less, more preferably 10% or less;
A material having at least one property selected from the group consisting of:

  The material having the first and second polyrotaxanes of the present invention can provide at least one characteristic selected from the above-mentioned X) to Z) while being solvent-free. By having this characteristic, “sagging” can be improved.

  In the present application, “solvent-free” means that there is preferably no solvent, but may contain a very small amount, that is, 3 wt% of the solvent (when the entire material is 100 wt%), preferably 1 wt% or less. In addition, when the material of the present invention is produced under normal conditions, or when it is processed or processed, it may contain a solvent, but it means that the final amount of the solvent is within the above range. .

The material of the present invention has a X) compression set of 10% or less, preferably 5% or less, more preferably 1% or less;
Y) Tensile stress relaxation is 15% or less, preferably 10% or less, more preferably 5% or less; and Z) Hysteresis loss is 25% or less, preferably 15% or less, more preferably 10% or less;
Having at least one characteristic selected from the group consisting of
In particular, the properties are: X) a combination of compression set and Y) tensile stress relaxation, Y) a combination of tensile stress relaxation and Z) hysteresis loss, Z) a combination of hysteresis loss and X) compression set, X) It may be a combination of compression set, Y) tensile stress relaxation and Z) hysteresis loss. In these combinations, the numerical value of each characteristic is preferably the above arbitrary value.
More particularly, in the combination of X) compression set, Y) tensile stress relaxation, and Z) hysteresis loss, compression set is 1% or less, tensile stress relaxation is 5% or less, and hysteresis loss is 10% or less. Good.

In the present specification, the compression set means that measured in accordance with JIS K6301.
Moreover, in this specification, tensile stress relaxation means what is measured based on JISK6263.

Furthermore, in this specification, the hysteresis loss refers to the mechanical energy loss rate (hysteresis loss) in one cycle of deformation and recovery in accordance with JIS K6400, using the strain due to the tensile test of the material instead of the deformation of the material. Say what you were.
Specifically, a sample of dumbbell No. 7 (dumbbell No. 7 conforms to JIS K-6251) is subjected to a tensile test, and a stress-strain curve is measured. After stretching to 100% of the effective length, it shrinks to 0% at the same rate as stretching. This cycle is repeated 10 times and the hysteresis loss is calculated. Specifically, the area is measured and calculated by the method shown in FIG. The area at the time of extension in each cycle (area in FIG. 1: obedo) and the area at the time of contraction (area in FIG. 1: dcbed) are calculated. The reduction rate of the area at the time of contraction with respect to the area at the time of expansion in each cycle is calculated, and an average value of 2 to 10 cycles is defined as a hysteresis loss in the present application.

Hysteresis loss (%) =
{(Area: oobedo) − (area: dcbed)} × 100 / (area: oobedo).

The material of the present invention having such characteristics can realize an elastomer having excellent restorability in applications that are used repeatedly or used after being deformed for a long period of time. Therefore, in the existing elastomers such as urethane elastomers and rubber elastomers, the present invention can be applied to a field in which “sagging” of a material becomes a problem after long-term use or repeated use.
From these facts, the material of the present invention can be applied to applications requiring a material with little “sagging” for repeated use over a long period of time. For example, hoses such as rubber hoses, seal parts such as O-rings and gaskets, power transmission belts such as toothed belts, conveyor belts for conveyance, vibration-proof rubber for industrial machinery, industrial rolls such as paper rolls, OA Examples include various equipment rolls such as equipment rolls and soft actuators such as dielectric actuators.
In addition, the material of the present invention can reduce compression set, stress relaxation characteristics and hysteresis loss by combining with other polymers, and can improve sag as a material.

The material of the present invention will be described in more detail.
Each of the first or second polyrotaxane has the following configuration. That is, the first (second) polyrotaxane includes a first (second) cyclic molecule in which the opening of the first (second) cyclic molecule is included in a skewered manner by the first (second) linear molecule. ), A first (second) blocking group is arranged at both ends of the pseudopolyrotaxane so that the first (second) cyclic molecule is not eliminated.
The first and second polyrotaxanes may be the same or different. In short, in the present invention, it is necessary that two or more polyrotaxane molecules exist and two or more molecules are crosslinked.
Regarding the elements constituting the first (second) polyrotaxane, ie, the first (second) cyclic molecule, the first (second) linear molecule, and the first (second) blocking group This will be described later.

The material of the present invention is obtained by crosslinking the first and second polyrotaxanes via respective cyclic molecules.
Specifically, a cross-link is preferably formed between the first and second cyclic molecules so as to have a polymer site. The polymer site may have 3 or more repeating units and / or the number average molecular weight of the polymer site is 300 or more and 10,000 or less, preferably 400 to 5000, more preferably 500 to 3000.

More specifically, the first and second cyclic molecules have first and second active groups, respectively, and have first and second reactive groups at both ends of the polymer site, respectively. The active group and the first reactive group, and the second active group and the second reactive group may be directly chemically bonded to form a bridge. The repeating unit of the “polymer part” may be divided in the middle of the polymer part by some spacer, but the repeating unit between the first and second reactive groups is in the above range. It is good. In addition, regarding the molecular weight of the “polymer part”, the polymer part may be divided by some spacer in the middle, but the molecular weight between the first and second reactive groups is in the above range. Is good.
The polymer portion may have, for example, a plurality of polymers and a linker portion that connects the polymers. Even in this case, the repeating unit and / or molecular weight between the first and second reactive groups may be in the above-mentioned range.
The polymer site may have a branched chain. In this case, the branched chain may be included in any of the plurality of polymers and / or in the linker portion.
The polymer site may be derived from one monomer or from two or more monomers.

Examples of polymer sites or polymer sites having first and second reactive groups at both ends include polyethers, polyesters, polysiloxanes, polycarbonates, poly (meth) acrylates or polyenes, or copolymers thereof. Or a mixture thereof may be mentioned.
More specifically, polyethylene glycol diol, polyethylene glycol dicarboxylic acid terminal, polyethylene glycol dithiolic acid terminal, polypropylene diol, polytetrahydrofuran, poly (tetrahydrofuran) bis (3-aminopropyl) terminal, polypropylene glycol bis (2-aminopropyl ether) ), Glycerol propoxylate, glycerol tris [poly (propylene glycol) amino terminal], polyethers such as pentaerythritol ethoxylate, pentaerythritol propoxylate; poly (ethylene adipate), poly (1,3-propylene adipate) diol terminal Polyesters such as poly (1,4-butylene adipate) diol end, polylactone; modified polybutadiene, modified poly Polyenes such as isoprene; polydimethylsiloxane disilanol end, polydimethylsiloxane hydrogenated end, polydimethylsiloxane bis (aminopropyl) end, polydimethylsiloxane diglycidyl ether end, polydimethylsiloxane dicarbinol end, polydimethylsiloxane di Examples thereof include, but are not limited to, siloxanes such as vinyl terminals and polydimethylsiloxane dicarboxylic acid terminals; polyalkylene carbonate diols containing 1,5-pentanediol, 1,6-hexanediol, and the like as components. In particular, the polymer sites may be polyethers or polycarbonates.

  The polymer part can also have a reactive group at both ends thereof by reacting a group of the polymer part with a certain group. For example, as the provision of a “reactive group” by the “certain group”, hexamethylene diisocyanate, hexamethylene diisocyanate biuret type, isocyanurate type, adduct type, tolylene 2,4-diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, Giving isocyanate groups with polyfunctional isocyanates such as xylylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, (4,4'-methylenedicyclohexyl) diisocyanate; oxirane compounds such as epichlorohydrin and epibromohydrin Giving an oxirane group with oxetane group with an oxetane compound such as 3- (chloromethyl) -3-methyloxetane; That oxazoline group imparting; grant of a polyfunctional aziridine PZ-33, DZ-22E (manufactured by Nippon Shokubai) aziridine group due; may be mentioned, without limitation.

The reactive group is included in the above-mentioned groups, but is preferably selected from the group consisting of an isocyanate group, a thioisocyanate group, an oxirane group, an oxetane group, a carbodiimide group, a silanol group, an oxazoline group, and an aziridine group. An isocyanate group or a thioisocyanate group is preferable, and an isocyanate group is more preferable.
Each of the first and second reactive groups may have two or more functional groups.
Two or more functional groups may be two or more groups selected from the group consisting of isocyanate groups, thioisocyanate groups, oxirane groups, oxetane groups, carbodiimide groups, silanol groups, oxazoline groups, and aziridine groups. An isocyanate group or a thioisocyanate group is preferable, and an isocyanate group is more preferable.

Hereinafter, each of the elements constituting the first (second) polyrotaxane will be described. Hereinafter, “first” or “second” will be described without distinction unless otherwise specified.
<< Cyclic molecule >>
The cyclic molecule is a molecule in which a linear molecule is included in a skewered manner in the opening, and is not particularly limited as long as it has an active group.
The active group may be derived from a group selected from the group consisting of —OH, —SH, —NH ₂ , —COOH, —SO ₃ H, and —PO ₄ H.
For example, the cyclic molecule may be selected from the group consisting of α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin. A part of —OH group such as α-cyclodextrin may be substituted with other groups, for example, the above-mentioned groups. The cyclic molecule may have a group other than the active group described above.

  Examples of groups other than active groups include acetyl, propionyl, hexanoyl, methyl, ethyl, propyl, 2-hydroxypropyl, 1,2-dihydroxypropyl, cyclohexyl, butylcarbamoyl, hexylcarbamoyl Group, phenyl group, polycaprolactone group, alkoxysilane group, acryloyl group, methacryloyl group or cinnamoyl group, polymer chain (polycaprolactone group, polycarbonate group, etc.), or derivatives thereof. The active group may be directly bonded to the cyclic molecule or may be bonded to the cyclic molecule via a group other than the active group. By providing these groups in the cyclic molecule, for example, improving the solubility of the polyrotaxane in the solvent in the step of producing a crosslinked product, improving the compatibility with the polymer site, and imparting specific functionality ( For example, a water / oil repellent function, a friction control function, a photocuring function, a surface adhesion improving function, etc.) can be achieved.

<< 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 It may be 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. Particularly preferred is polyethylene glycol.

The linear molecule should have a weight average molecular weight of 3,000 or more, preferably 5,000 to 100,000, more preferably 10,000 to 50,000.
In the first (second) polyrotaxane of the present invention, the first (second) 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.

The above-described material of the present invention, that is, a material having a crosslinked polyrotaxane will be described with reference to the drawings.
FIG. 2 is a diagram schematically illustrating an embodiment 1 of a crosslinked polyrotaxane in the material of the present invention.
In the figure, the left side is derived from the first polyrotaxane 2, the right side is derived from the second polyrotaxane 4, and both are crosslinked.
The first polyrotaxane 2 has an opening of the first cyclic molecules 5 a, 5 b, and 5 c that is included in a skewered manner by the first linear molecules 6, and both ends of the first linear molecules 6 The first blocking groups 7a and 7b are arranged so that the first cyclic molecules 5a, 5b and 5c are not detached.
The first cyclic molecule 5a has a graft chain 8a as a group other than the active group, the first cyclic molecule 5b has a graft chain 8b and 8c as a group other than the active group, and the first cyclic molecule 5c. Has graft chains 8d and 8e as groups other than the active group.

Similarly, the second polyrotaxane 4 also includes the second linear molecules 16 in which the openings of the second first cyclic molecules 15a, 15b, and 15c are clasped in a skewered manner. Second blocking groups 17a and 17b are arranged at both ends of the chain molecule 16 so that the second cyclic molecules 15a, 15b and 15c are not detached.
The second cyclic molecule 15a has graft chains 18a and 18b as groups other than the active group, and the second cyclic molecule 15b has graft chains 18c and 18d as groups other than the active group in the second cyclic group. The molecule 15c has graft chains 18e and 18f as groups other than the active group.

The first polyrotaxane 2 and the second polyrotaxane 4 are more specifically, the first cyclic molecule 5a, the graft chain 8a, and the polymer via the first cyclic molecule 5a and the second cyclic molecule 15b. Cross-linking is performed via the site 21a, the graft chain 18d, and the second cyclic molecule 15b.
In addition, a bridge is also formed through the first cyclic molecule 5b and the second cyclic molecule 15b, and more specifically, the first cyclic molecule 5b, the graft chain 8c, the polymer portion 21b, and the second cyclic molecule 5b. Crosslinks are formed through the cyclic molecules 15b.
Furthermore, a bridge is also formed through the first cyclic molecule 5c and the second cyclic molecule 15c, and more specifically, the first cyclic molecule 5c, the polymer portion 21c, and the second cyclic molecule 15c. Crosslinks are formed via

  By using a polyrotaxane, the material of the present invention can realize an elastomer having low compression set, stress relaxation characteristics and / or hysteresis loss. Thereby, it is possible to realize an elastomer having excellent resilience in applications that are used repeatedly or used after being deformed for a long period of time. Therefore, it can be applied to a use requiring a member with less “sag” especially for long-term use and repeated use. For example, hoses such as rubber hoses, seal parts such as O-rings and gaskets, power transmission belts such as toothed belts, conveyor belts for conveyance, vibration-proof rubber for industrial machinery, industrial rolls such as paper rolls, OA Examples include various equipment rolls such as equipment rolls and soft actuators such as dielectric actuators.

<Method for producing material of the present invention>
The material of the present invention described above can be obtained, for example, by the following method.
That is,
a) First blocking so that the first cyclic molecule is not detached at both ends of the first pseudopolyrotaxane in which the opening of the first cyclic molecule is clasped by the first linear molecule. Providing a first polyrotaxane having a group disposed thereon;
b) Second blocking so that the second cyclic molecule is not detached at both ends of the second pseudopolyrotaxane in which the opening of the second cyclic molecule is clasped by the second linear molecule. Providing a second polyrotaxane having a group disposed thereon;
c) preparing a first cross-linking compound having a polymer moiety; and d) mixing and reacting the first polyrotaxane, the second polyrotaxane, and the first cross-linking compound to produce a first polyrotaxane and a second polyrotaxane. Cross-linking via a polymer site;
By having this, the material of the present invention can be obtained.

  Steps a) and b) are steps for preparing a so-called polyrotaxane. The polyrotaxane can be obtained by referring to documents published prior to the filing of the present application (for example, WO 2005-080469 and WO 2005-108464, the entire contents of which are incorporated herein by reference). . If the first and second polyrotaxanes are the same, steps a) and b) can be performed in one step. The first and second polyrotaxanes are the same as described above.

  Step c) is a step of preparing the first cross-linking compound. Here, the polymer site is the same as described above, and has 3 or more repeating units, and / or the number average molecular weight of the polymer site is 300 or more and 10,000 or less, preferably 400 to 5000, more preferably It is good that it is 500-3000. The polymer part is the same in other respects.

  As step c), the first cross-linking compound is obtained by adding a reactive group to the above-mentioned “polymer part” or “polymer part having the first and second reactive groups”. Obtainable. That is, c) -1) a step of obtaining a polymer site; and c) -2) a step of providing first and second reactive groups at both ends of the polymer site, respectively, thereby providing the first crosslinking compound. Obtainable. And c) -3) providing first and second protecting groups for protecting the first and second reactive groups, respectively. In this case, the first and second protective groups can provide a stabilized first cross-linking compound, which can be useful for long-term storage of the first cross-linking compound. In addition, when using the 1st bridge | crosslinking compound which has a 1st and 2nd protective group, the process of deprotecting this 1st and 2nd protective group in subsequent process d) or before process d). It is good to have.

The first and second protecting groups are each independently ε-caprolactam, 1,2-pyrazole, butanone oxime, 1,2,4-triazole, diisopropylamine, 3,5-dimethylpyrazole, diethyl malonate, dimethyl It may be selected from the group consisting of malonate, methyl acetoacetate, ethyl acetoacetate, and a protecting group by reaction with N, N′-diphenylformamidine compound. Preferred is ε-caprolactam, 3,5-dimethylpyrazole or butanone oxime, and more preferred is ε-caprolactam or 3,5-dimethylpyrazole.
The deprotecting step can be performed mainly by heating. Further, a deprotection catalyst that promotes deprotection may be added to the system.

  The catalyst for deprotection depends on the compound present in the system, the first and second protecting groups, etc., but dibutyltin dilaurate, dioctyltin dilaurate, tri (acetate) butyltin, di (acetate) dibutyltin , Acetate tributyltin, methoxytributyltin, tri (2-ethylhexanoate) butyltin, bis (2-ethylhexanoate) dibutyltin, tri (laurate) butyltin, di (octanoate) dibutyltin, tri (octanoate) ) Tin-based catalysts such as butyltin, dibutyltin oxide, monobutyltin hydroxide oxide, stannous octoate; triethylenediamine, triethylamine, N, N, N ', N'-tetramethylpropylenediamine, N, N, N' , N'-Tetrakis (2-hydroxypropyl) ethylenediamine, N-methylmorpholine, 1,2-dimethyl Imidazole, 1,5-diazabicyclo (4,3,0) nonene-5, 1,8-diazabicyclo (5,4,0) -undecene-7 (hereinafter abbreviated as DBU), borane salts of these amine catalysts, Various amine salt catalysts such as DBU phenol salt, DBU octylate, DBU carbonate; carboxylates such as magnesium naphthenate, lead naphthenate and potassium acetate; trialkylphosphines such as triethylphosphine and tribenzylphosphine; sodium Examples include, but are not limited to, alkali metal alkoxides such as methoxide; zinc-based organometallic catalysts, and the like.

  In steps c) -1) and c) -2), i) a method of obtaining a cross-linked compound by reacting a polymer having a portion capable of imparting a reactive group with a compound having two or more reactive groups; ii) monomer Can be exemplified by, but not limited to, a method of polymerizing by a general method, producing a polymer site, and adding a compound serving as a reactive group in the production process. The monomer here may be a monomer having a repeating unit.

In the above method i), a compound having two or more reactive groups is generally reacted with a polymer in excess, and then the reaction product may be used as it is, or may be used after purification. . Examples of the compound having two or more reactive groups include, but are not limited to, the compounds described above as the “reactive group” imparted by “a certain group”.
As a specific example of the above ii), a crosslinking compound obtained by adding glycidyl methacrylate to the polymerization of methyl (meth) acrylate, and α-methacryloyloxy-γ-butyrolactone is added to the polymerization of methyl (meth) acrylate. Cross-linked compounds obtained by the above, cross-linked compounds obtained by having terminal carboxylic acid groups by condensation polymerization of ethylene glycol and adipic acid, cross-linked compounds having an isocyanate terminal obtained by polyaddition of triethylene glycol and hexamethylene diisocyanate, etc. For example, but not limited to.
These reactions depend on the polymer site to be used, the “certain group” to be used, and the reactive group to be used, but in a solvent of toluene, xylene, and butyl acetate under normal pressure and a reaction temperature of room temperature to 120 ° C. It can be carried out.

Step d) is a step in which the first and second polyrotaxanes and the first cross-linking compound are mixed and reacted to cross-link the first and second polyrotaxanes through the polymer sites.
Step d) depends on the polyrotaxane to be used, the polymer site to be used, etc., but it is generally preferable to react in a solvent. Depending on the first and second polyrotaxanes and the crosslinking compound as solvents, dimethylacetamide, dimethylformamide, tetrahydrofuran, ethyl acetate, butyl acetate, toluene, xylene, acetonitrile, cyclohexanone, methyl ethyl ketone or acetone, or a mixed solvent thereof Although not limited to these, it is not limited to these. The reaction depends on the reactive group, the active group, and the solvent, and examples include, but are not limited to, conditions from room temperature to 150 ° C., 5 minutes to 24 hours, in the presence of a catalyst.

In step d), a second cross-linking compound different from the first cross-linking compound may be included.
The second cross-linking compound preferably has third and fourth reactive groups at both ends thereof. Further, the second crosslinking compound may further have a fifth reactive group.
The third, fourth, and fifth reactive groups are each independently selected from the group consisting of isocyanate groups, thioisocyanate groups, oxirane groups, oxetane groups, carbodiimide groups, silanol groups, oxazoline groups, and aziridine groups. Is good. An isocyanate group or a thioisocyanate group is preferable, and an isocyanate group is more preferable.

In addition, the second cross-linking compound may include the third and fourth reactive groups, and the fifth reactive group, if present, protected by the third, fourth, and fifth protective groups, respectively. Good. The protecting group may be deprotected in step d) or before step d).
The third, fourth and fifth protecting groups are each independently ε-caprolactam, 1,2-pyrazole, butanone oxime, 1,2,4-triazole, diisopropylamine, 3,5-dimethylpyrazole, diethyl It may be selected from the group consisting of malonate, dimethyl malonate, methyl acetoacetate, ethyl acetoacetate, and a protecting group by reaction with N, N'-diphenylformamidine compound. Preferred is ε-caprolactam, 3,5-dimethylpyrazole or butanone oxime, and more preferred is ε-caprolactam or 3,5-dimethylpyrazole.
Deprotection of the protecting group can be performed mainly by heating. Further, a deprotection catalyst that promotes deprotection may be added to the system.

  The deprotection catalyst depends on the compounds present in the system, such as the first and second polyrotaxanes; and the first and second protecting groups, but dibutyltin dilaurate, dioctyltin dilaurate, tri ( Acetate) butyltin, di (acetate) dibutyltin, acetate tributyltin, methoxytributyltin, tri (2-ethylhexanoate) butyltin, bis (2-ethylhexanoate) dibutyltin, tri (laurate) butyltin , Tin catalysts such as di (octanoate) dibutyltin, tri (octanoate) butyltin, dibutyltin oxide, monobutyltin hydroxide oxide, stannous octoate; triethylenediamine, triethylamine, N, N, N ', N'- Tetramethylpropylenediamine, N, N, N ', N'-tetrakis (2-hydroxypropyl) ethyl Range amine, N-methylmorpholine, 1,2-dimethylimidazole, 1,5-diazabicyclo (4,3,0) nonene-5, 1,8-diazabicyclo (5,4,0) -undecene-7 (hereinafter, Abbreviated as DBU), various amine salt catalysts such as borane salts, DBU phenol salts, DBU octylates and DBU carbonates of these amine catalysts; carboxylates such as magnesium naphthenate, lead naphthenate and potassium acetate; triethyl Examples thereof include, but are not limited to, trialkylphosphines such as phosphine and tribenzylphosphine; alkali metal alkoxides such as sodium methoxide; and zinc-based organometallic catalysts.

When the method of the present application uses a solvent, various drying steps may be provided after step d) or simultaneously with step d) in order to make the obtained material containing the crosslinked product solvent-free. Further, in step d), drying may be performed in a mold or on a substrate. Furthermore, in order to perform a drying process efficiently, you may provide a solvent substitution process before a drying process.
Examples of the drying process include, but are not limited to, a drying process by standing at room temperature, natural drying, a drying process by normal pressure heating, a drying process by heating under reduced pressure, a freeze drying process, and the like.

  In addition to steps a), b), c), and d), other steps may be provided. For example, the above-described drying step after step d), step d) and / or after step d), the step of including other components in the material, the step d) the washing step with the solvent, the first and the first steps A deprotecting step of the protecting group in the case of having the second, third, fourth and fifth protecting groups. Other components include other polymers or oligomers, plasticizers, low molecular weight crosslinking agents, surfactants, UV absorbers, antibacterial agents, viscosity modifiers, inorganic fine particles, antioxidants, silane coupling agents, antifoaming agents, etc. It can mention, but it is not limited to these.

  Among other components, as other polymers or oligomers, polyethylene glycol monomethyl ether, polyethylene glycol monobutyl ether, polyethylene glycol dimethyl ether, polypropylene glycol monobutyl ether, one-end hydroxylated polycaprolactone, polycaprolactone, polydimethylsiloxane, one-end hydroxylated poly Examples thereof include, but are not limited to, dimethylsiloxane, polycarbonate, one-end hydroxylated polycarbonate, polyester, and one-end hydroxylated polyester. In addition, you may have only one location which can provide a reactive group to this other polymer or oligomer, and it is not necessary to have it. By adding these polymers or oligomers, the viscoelastic properties of the material can be moderately adjusted.

  Among other ingredients, plasticizers include dibutyl phthalate, di-2-ethylhexyl phthalate, butyl benzyl phthalate, dihexyl phthalate, dioctyl adipate, bis (2-ethylhexyl) adipate, tris trimellitic acid (2 -Ethylhexyl), tricresyl phosphate, and the like, but are not limited thereto.

  Among other ingredients, low molecular weight crosslinking agents include cyanuric chloride, trimesoyl chloride, terephthaloyl chloride, epichlorohydrin, dibromobenzene, glutaraldehyde, aliphatic polyfunctional isocyanate, aromatic polyfunctional isocyanate, diisocyanic acid Acid anhydrides such as trilein, hexamethylene diisocyanate, divinyl sulfone, 1,1′-carbonyldiimidazole, ethylenediaminetetraacetic acid dianhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, Examples thereof include, but are not limited to, polyfunctional acid hydrazines, polyfunctional carboimides, alkoxysilanes, and derivatives thereof.

  Among other components, as surfactants, nonionic surfactants such as polyoxyethylene (8) octylphenyl ether, sorbitan polyoxyethylene trioleate, sorbitan polyoxyethylene monostearate; sodium dodecyl sulfate, dodecyl sulfate Examples include, but are not limited to, ionic surfactants such as sodium sulfonate, triethanolamine dodecyl sulfate, dodecyltrimethylammonium salt, and dodecylpyridinium chloride.

  Among other ingredients, as UV absorbers, 2-dimethylhexyl paradimethylaminobenzoate, 2-ethylhexyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octylbenzophenone, 2- (2′-hydroxy) -5'-t-butylphenyl) benzotriazole, bis (2,2,6,6-tetramethyl-4-piperidyl) -sebacate, 2-ethylhexyl paramethoxycinnamate, isopropyl paramethoxycinnamate, ethylhexyl methoxycinnamate , Octyl methoxycinnamate, and the like, but are not limited thereto.

Among other components, antibacterial agents include, but are not limited to, silver, zinc, copper compounds or complexes and ions thereof; organosilicon compounds; organophosphorus compounds.
Among other components, examples of the viscosity modifier include, but are not limited to, carboxyvinyl polymer, propylene glycol alginate, ethyl cellulose, sodium carboxymethyl cellulose, sodium polyacrylate, and the like.
Among the other components, examples of the inorganic fine particles include silica, alumina, titanium oxide, and silicon carbide, but are not limited thereto.

Among the other components, examples of the antioxidant include, but are not limited to, a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant.
Among other components, examples of the silane coupling agent include vinyl silane, epoxy silane, and amino silane, but are not limited thereto.

The present application provides a composition for obtaining a material having the above-mentioned crosslinked polyrotaxane.
The composition comprises
I) a polyrotaxane in which blocking groups are arranged so that the cyclic molecule is not detached at both ends of the pseudopolyrotaxane in which the opening of the cyclic molecule is clasped with a linear molecule; and II) the first A first cross-linking compound having a polymer moiety, having first and second reactive groups at both ends of the first polymer moiety and protecting the first and second reactive groups A first bridging compound having first and second protecting groups;
Have

Here, I) polyrotaxane has the same definition as the first and second polyrotaxanes described above. In addition, I) The polyrotaxane may be one type of polyrotaxane or may have two or more types of polyrotaxane.
II) The first cross-linking compound also has the same definition as the first cross-linking compound described above. However, in the above description, the first and second protecting groups are arbitrary, but here, the point of having the first and second protecting groups is different. As described above, II) the first cross-linking compound has the first and second protecting groups, so that I) polyrotaxane in the composition and II) the first cross-linking compound do not react with each other stably. Can exist. When crosslinking is performed, the first and second protecting groups are preferably deprotected before crosslinking. Deprotection is as described above. The first and second reactive groups and the first and second protecting groups have the same definitions as described above.

The composition further comprises III) a second cross-linking compound having at least a third and a fourth reactive group and having a third and a fourth protective group that protects the third and fourth reactive groups; It is good to have.
The second cross-linking compound has the same definition as above. The third and fourth reactive groups and the third and fourth protecting groups also have the same definition as described above.

  The composition of the present invention may have other components other than the above I) to III). Other components include other polymers or oligomers, plasticizers, low molecular weight crosslinking agents, surfactants, UV absorbers, antibacterial agents, viscosity modifiers, inorganic fine particles, antioxidants, silane coupling agents, antifoaming agents, etc. It can mention, but it is not limited to these. Other components than the antifoaming agent have the same definition as described above. The antifoaming agent will be described later.

The composition of this application can be manufactured as follows.
That is, A) I) a polyrotaxane in which a blocking group is arranged at both ends of a pseudopolyrotaxane in which the opening of a cyclic molecule is skewered by a linear molecule so that the cyclic molecule is not detached is prepared. Process;
B) II) A first cross-linking compound having a first polymer moiety, having first and second reactive groups at both ends of the first polymer moiety, and the first and second A first crosslinking compound having first and second protecting groups that protect two reactive groups; and C) I) a polyrotaxane; and II) a first crosslinking compound;
The composition can be obtained.

Here, the step A) is the same as the above-described steps a) and b), that is, the steps of preparing the first and second polyrotaxanes.
Step B) is the same as having step c) above, in particular step c) -3).
Step C) is a step of mixing I) a polyrotaxane; and II) a first crosslinking compound. The mixing may be dry mixing without a solvent or may be mixing using a solvent.
When a solvent is used, examples of the solvent include, but are not limited to, dimethylacetamide, dimethylformamide, tetrahydrofuran, ethyl acetate, butyl acetate, toluene, xylene, acetonitrile, cyclohexanone, methyl ethyl ketone or acetone, or a mixed solvent thereof. .

Examples of the mixing method include, but are not limited to, a magnetic stirrer, mechanical stirring, a homodisper machine, a high-pressure emulsifier, and an ultrasonic emulsifier / disperser.
After mixing uniformly, a defoaming step may be provided by a method such as vacuum defoaming or centrifugal defoaming.
An antifoaming agent may be added during mixing. Examples of the antifoaming agent include, but are not limited to, silicone antifoaming agents; organic antifoaming agents such as surfactants, polyethers, and higher alcohols.

  When the composition of this invention has other components other than said I) -III), it is good to mix this other component at the said C) process.

  The said manufacturing method may have another process other than the said process A) -C). For example, you may have the process of shape | molding a composition after process C). A conventionally well-known process can be used for a shaping | molding process. For example, the process used for the molding method of a thermosetting resin can be used. More specifically, methods such as injection molding, mold molding, film forming by a coater and / or a coating machine can be exemplified, but the method is not limited thereto.

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

(Synthesis Example A-1)
<Preparation of polyrotaxane having hydroxypropyl group>
A linear molecule: polyethylene glycol (weight average molecular weight: 35,000), a cyclic molecule: α-cyclodextrin (hereinafter sometimes simply referred to as “α-CD”), a blocking group: a polyrotaxane comprising an adamantaneamine group A compound obtained by further hydroxypropylating a part of the OH group of α-CD (hereinafter, hydroxypropylated polyrotaxane is abbreviated as “HAPR35”) is disclosed in WO 2005-080469 (the contents of this document are all referred to in this specification). Prepared in the same manner as described above.
^{By 1} H-NMR analysis, α-CD inclusion rate: 25% and introduction rate of hydroxypropyl group: 48% were confirmed. Moreover, average weight molecular weight Mw: 150,000 was confirmed by GPC.

The molecular weight and molecular weight distribution of the synthesized polyrotaxane 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 (DMSO) /0.01 M LiBr, column oven: 50 ° C., flow rate: 0.5 ml / min, sample The concentration was measured under the conditions of about 0.2 wt / vol%, injection amount: 20 μl, pretreatment: filtration through a 0.2 μm filter, standard molecular weight: PEO (the same applies to Synthesis Examples B-2 and B-3). is there). ¹ H-NMR analysis was performed with 400 MHz JEOL JNM-AL400 (manufactured by JEOL Ltd.).

(Synthesis Example A-2)
<Preparation of polyrotaxane having hydroxypropyl group and polycaprolactone group>
20 g of HAPR35 obtained in Synthesis Example A-1 was placed in a three-necked flask, and 90 g of ε-caprolactone was introduced while slowly flowing nitrogen. After uniformly stirring with a mechanical stirrer at 100 ° C. for 60 minutes, 6 g of tin 2-ethylhexanoate (50 wt% solution) previously diluted with toluene was added, reacted for 5 hours, the solvent was removed, and the reaction product ( 113 g was obtained in which polycaprolactone group was introduced into HAPR35, and “in which polycaprolactone was introduced into HAPR35” may be generally abbreviated as “HAPR35-g-PCL”. As a result of measuring IR, a peak derived from an ester of 1736 cm ⁻¹ was observed. Moreover, the weight average molecular weight Mw was 586,800 and molecular weight distribution Mw / Mn was 1.7 by GPC.

<Synthesis Example B Synthesis of a cross-linking agent having a polymerization site>
<< Synthesis Example B-1 Preparation of Crosslinking Agent B-1 >>
2.80 kg of 1,3-bis (isocyanatomethyl) cyclohexane (Mitsui Chemicals Takenate 600) was placed in a 20 L reactor, and the temperature was raised to 80 ° C. with stirring under a nitrogen stream.
Polycarbonate diol (polyalkylene carbonate diol (polyalkylene polycarbonate having 1,5-pentanediol and / or 1,6-hexanediol as a repeating unit) 96 wt% or more, 1,5-pentanediol 2 wt% or less, 1,6- Polycarbonate having a composition of hexanediol of 2 wt% or less), DURANOL (registered trademark) T-5650J (manufactured by Asahi Kasei Chemicals Corporation, Mn: 800; 1,5-pentanediol and / or 1,6-hexanediol as repeating units) In this case, the repeating unit is 6 to 7. Hereinafter, 4.98 kg of simply abbreviated as “polycarbonate diol Duranol (registered trademark) T5650J”) was warmed to 70 ° C. and slowly dropped into the reaction vessel over 4 hours. After further stirring for 3 hours, polyisocyanate modified at both ends with isocyanate groups A crosslinking agent B-1 (7.78 kg) having carbonate diol and 1,3-bis (isocyanatomethyl) cyclohexane was obtained.

<< Synthesis Example B-2 Preparation of Crosslinking Agent B-2 >>
In a 20 L reaction vessel, 3.00 kg of 1,3-bis (isocyanatomethyl) cyclohexane (Mitsui Chemicals Takenate 600) was added, and the temperature was raised to 80 ° C. with stirring under a nitrogen stream.
Polycarbonate diol (polyalkylene carbonate diol having a repeating unit of 1,5-pentanediol and / or 1,6-hexanediol of 96 wt% or more, 1,5-pentanediol 2 wt% or less, 1,6-hexanediol 2 wt% or less Polycarbonate), Duranol (registered trademark) T-5650E (manufactured by Asahi Kasei Chemicals Corporation, Mn: 500; when 1,5-pentanediol and / or 1,6-hexanediol is used as a repeating unit, the repeating unit The unit is 4 to 5. Hereinafter, 3.32 kg of simply abbreviated as “polycarbonate diol DURANOL (registered trademark) T5650E”) is warmed to 70 ° C., slowly dropped into the reaction vessel over 2 hours, and further 3 hours With stirring, polycarbonate diol and 1,3-bis ( To obtain a cross-linking agent B-2 (6.32kg) with Socia isocyanatomethyl) cyclohexane.

<< Synthesis Example B-3 Preparation of Crosslinking Agent B-3 >>
Under nitrogen atmosphere, at 80 ° C., 198 ml of 1,3-bis (isocyanatomethyl) cyclohexane (Mitsui Chemicals Takenate 600) was vigorously stirred.
Separately, a solution in which 300 g of polycarbonate diol Duranol (registered trademark) T5650J was dissolved in 300 ml of toluene was prepared. This solution was slowly added dropwise to Takenate 600 and stirred for 2 hours. After the reaction, the solvent was removed under reduced pressure to obtain a crosslinking agent B-3 (517 g) having an isocyanate group-modified polycarbonate diol and 1,3-bis (isocyanatomethyl) cyclohexane at both ends.

<< Synthesis Example B-4 Preparation of Crosslinking Agent B-4 >>
168 ml of 1,3-bis (isocyanatomethyl) cyclohexane (Mitsui Chemicals Takenate 600) was vigorously stirred at 80 ° C. in a nitrogen atmosphere.
Separately, a solution in which 150 g of triol type polypropylene glycol (Mn: 700, Wako Pure Chemical Industries, Ltd., propylene glycol repeating units 12 to 13) was dissolved in 450 ml of toluene was prepared. This solution was slowly added dropwise to Takenate 600 and stirred for 2 hours. After the reaction, the solvent was removed under reduced pressure to obtain a crosslinking agent B-4 (334 g) having three modified ends of polypropylene modified with an isocyanate group and 1,3-bis (isocyanatomethyl) cyclohexane.

<Synthesis Example C Preparation of Blocked Crosslinking Agent>
<< Synthesis Example C-1 Preparation of Crosslinking Agent C-1 >>
The crosslinking agent B-1 (77.78 kg) was placed in a 200 L reaction tank, and the temperature was raised to 100 ° C. while stirring under a nitrogen stream. Ε-Caprolactam (20.38 kg) was added thereto and stirred for 6 hours to obtain a crosslinking agent C-1 in which isocyanate groups at both ends of the polycarbonate were protected with ε-caprolactam. As a result of measurement by FT-IR, it was confirmed that the isocyanate group was protected from the disappearance of the peak derived from the isocyanate group in the vicinity of 2250 cm ⁻¹ .

<< Synthesis Example C-2 Preparation of Crosslinking Agent C-2 >>
The crosslinking agent B-2 (6.32 kg) was placed in a 20 L reaction vessel, and the temperature was raised to 100 ° C. while stirring under a nitrogen stream. Ε-Caprolactam (1.99 kg) was added thereto and stirred for 6 hours to obtain a crosslinking agent C-2 in which the isocyanate groups at both ends of the polycarbonate were protected with ε-caprolactam. As a result of measurement by FT-IR, it was confirmed that the isocyanate group was protected from the disappearance of the peak derived from the isocyanate group in the vicinity of 2250 cm ⁻¹ .

<Synthesis Example D Preparation of Sample for One-Pack Crosslinking>
<< Synthesis Example D-1 Preparation of Sample D-1 for One-Part Crosslinking >>
Crosslinking agent C-1 (4.6 kg), polycarbonate diol Duranol (registered trademark) T5650J (2.94 kg), HAPR-g-PCL (3.22 kg) obtained in Synthesis Example A-2, catalyst for deprotection: Dibutyltin dilaurate (1.1 g) and 2,4-bis (dodecylthiomethyl) -6-methylphenol (BASF, Irganox 1726) (211 g) were placed in a reaction vessel, heated to 80 ° C. and stirred. And a uniform solution, and then degassed under reduced pressure to obtain a one-component crosslinking sample D-1.
The obtained one-pack crosslinking sample D-1 was stably present for 90 days or more at room temperature.

<< Synthesis Example D-2 Preparation of Sample D-2 for One-Part Crosslinking >>
Crosslinking agent C-2 (8.31 kg), polycarbonate diol Duranol (registered trademark) T5650E (6.69 kg), HAPR-g-PCL (3 kg) obtained in Synthesis Example A-2, catalyst for deprotection: dilauric acid Dibutyltin (5.2 g), 2,4-bis (dodecylthiomethyl) -6-methylphenol (BASF, Irganox 1726) (180 g) was placed in a reaction vessel, heated to 80 ° C., and stirred uniformly. After preparing the solution, degassing was performed under reduced pressure to obtain a one-component crosslinking sample D-2.
The obtained one-pack crosslinking sample D-2 was stably present for 90 days or more at room temperature.

<Synthesis Example E Preparation of crosslinked product>
<< Synthesis Example E-1 Preparation of Crosslinked Product E-1 >>
After degassing the one-component crosslinking sample D-1 at 80 ° C., the sample was put in a Teflon (registered trademark) mold and reacted in an oven at 150 ° C. for 5 hours to obtain a crosslinked product E-1.
The obtained cross-linked product E-1 was obtained by reducing the peak near 3450 cm ⁻¹ derived from the OH group of HAPR35-g-PCL by infrared spectroscopy, from the cross-linking agent B-1 and / or 1,3- It was confirmed that the isocyanate group of bis (isocyanatomethyl) cyclohexane and the OH group of HAPR35-g-PCL reacted to form a crosslink.

<< Synthesis Example E-2 Preparation of Cross-linked Product E-2 >>
After defoaming the one-component crosslinking sample D-2 at 80 ° C., it was placed in a Teflon (registered trademark) mold and reacted in an oven at 150 ° C. for 5 hours to obtain a crosslinked product E-2.
The obtained cross-linked product E-2 was subjected to infrared spectroscopy as in the case of the cross-linked product E-1, and the cross-linking agent B-2 and / or 1,3-bis (isocyanatomethyl) cyclohexane isocyanate group and HAPR35- It confirmed that the OH group of g-PCL reacted and the bridge | crosslinking was formed.

<< Synthesis Example E-3 Preparation of Cross-linked Product E-3 >>
HAPR-g-PCL (10 g) obtained in Synthesis Example A-2, polycarbonate diol Duranol (registered trademark) T5650J (5.35 g), crosslinking agent B-3 (4.63 g), crosslinking agent B-4 (3 .55 g), toluene (25 g), and dibutyltin dilaurate (8 mg) to make a homogeneous solution, then defoamed and placed in a Teflon mold for 20 hours in an oven at 40 ° C. The obtained reaction product was dried under reduced pressure to obtain a crosslinked product E-3.
The obtained cross-linked product E-3 was subjected to cross-linking agent B-3 and / or B-4 and / or 1,3-bis (isocyanate) by infrared spectroscopy in the same manner as the cross-linked products E-1 and E-2. It was confirmed that the isocyanate group of natomethyl) cyclohexane and the OH group of HAPR35-g-PCL reacted to form a crosslink.

For the crosslinked products E-1 to E-3, compression set, stress relaxation, and hysteresis loss were measured. The results are shown in Table 1. Each measurement was performed as follows.
<Measurement of compression set>
As described above, in accordance with JIS K6301, measurement was performed at 70 ° C. × 24 hours and at a compression rate of 25%.
<Measurement of stress relaxation>
As described above, in accordance with JIS K6263, measurement was performed at 40 ° C. for 72 hours using a JIS strip No. 3 test piece.
<Measurement of hysteresis loss>
Using a JIS dumbbell-shaped No. 7 test piece, 10 cycles were measured at a tensile speed of 0.2 mm / s, and the average of 2 to 10 hysteresis loss was calculated. Each hysteresis loss value was measured as described above.

From Table 1, it can be seen that any one of compression set, stress relaxation, and hysteresis loss shows a low value in the crosslinked product of the present application.
In particular, it can be seen that the cross-linked product E-1 shows a low value in all three types of compression set, stress relaxation, and hysteresis loss.
Moreover, it turns out that the crosslinked material E-2 shows a low value in two types, compression set and hysteresis loss.
Furthermore, it turns out that crosslinked material E-3 shows a low value in 2 types, stress relaxation and hysteresis loss.

Claims (18)

A material having a first polyrotaxane and a second polyrotaxane,
In the first polyrotaxane, the first cyclic molecule is not detached at both ends of the first pseudo-polyrotaxane in which the opening of the first cyclic molecule is clasped by the first linear molecule. The first blocking group is arranged as follows,
In the second polyrotaxane, the second cyclic molecule is not detached at both ends of the second pseudo-polyrotaxane in which the opening of the second cyclic molecule is clasped by the second linear molecule. A second blocking group is arranged as follows,
The first and second polyrotaxanes are crosslinked via the first and second cyclic molecules,
The material is solvent-free;
The material is
X) Compression set is 10% or less;
Y) Tensile stress relaxation is 15% or less; and Z) Hysteresis loss is 25% or less;
The above material having at least one characteristic selected from the group consisting of:   2. The material according to claim 1, wherein the cross-linking has a polymer portion having 3 or more repeating units between the first and second cyclic molecules.   The material according to claim 2, wherein the repeating unit of the polymer site is polyether, polyester, polysiloxane, polycarbonate, poly (meth) acrylate or polyene, or a copolymer thereof.   The material according to claim 2 or 3, wherein the polymer portion has a number average molecular weight of 300 or more and 10,000 or less.   The material according to any one of claims 1 to 3, wherein in the crosslinking, a polymer part having a number average molecular weight of 300 or more and 10,000 or less is provided between the first and second cyclic molecules. The first and second cyclic molecules have first and second active groups, respectively;
Having first and second reactive groups at both ends of the polymer site, respectively;
The bond is formed from the first active group and the first reactive group, the bond is formed from the second active group and the second reactive group, and the bridge is formed. The material according to any one of 5. A material having a first polyrotaxane and a second polyrotaxane, the first and second polyrotaxanes being crosslinked and solvent-free, wherein the material comprises:
X) Compression set is 10% or less;
Y) Tensile stress relaxation is 15% or less; and Z) Hysteresis loss is 25% or less;
A method for producing a material having at least one characteristic selected from the group consisting of:
a) The first cyclic molecule is formed so that the first cyclic molecule is not detached at both ends of the first pseudopolyrotaxane in which the opening of the first cyclic molecule is skewered by the first linear molecule. Preparing the first polyrotaxane having a blocking group disposed thereon;
b) The second cyclic molecule is formed so that the second cyclic molecule is not detached at both ends of the second pseudopolyrotaxane in which the opening of the second cyclic molecule is skewered by the second linear molecule. Preparing the second polyrotaxane having a blocking group disposed thereon;
c) preparing a first cross-linking compound having a polymer moiety; and d) reacting the first and second polyrotaxanes and a cross-linking precursor having the first cross-linking compound to react the first and second polyrotaxanes. Cross-linking the second polyrotaxane through the polymer site;
The method as described above, wherein the material is obtained.   The method according to claim 7, wherein the polymer portion has 3 or more repeating units.   The method according to claim 8, wherein the repeating unit is polyether, polyester, polysiloxane, polycarbonate, poly (meth) acrylate or polyene, or a copolymer thereof.   The method according to claim 7, wherein the polymer site has a number average molecular weight of 300 to 10,000. The first cross-linking compound is
c) -1) a step of obtaining the polymer portion; and c) -2) a step of providing first and second reactive groups at both ends of the polymer portion, respectively.
Obtained with
The first and second cyclic molecules have first and second active groups, respectively;
The bond is formed from the first active group and the first reactive group, the bond is formed from the second active group and the second reactive group, and the bridge is formed. 11. The method according to any one of items 10. The cross-linking precursor has a second cross-linking compound having at least third and fourth reactive groups;
The first cross-linking compound has first and second reactive groups at both ends of the polymer site, respectively.
The first and second cyclic molecules have first and second active groups, respectively;
A bond is formed from the first active group and the first reactive group, a bond is formed from the second active group and the second reactive group, and the first and second polyrotaxanes are: Cross-linked through the polymer site, and a bond is formed from the first active group and the third reactive group, and a bond is formed from the second active group and the fourth reactive group. The method according to any one of claims 7 to 11, wherein the first and second polyrotaxanes are crosslinked via the second crosslinking compound. The first cross-linking compound is
c) -1) obtaining a polymer moiety having 3 or more repeating units;
c) -2) providing first and second reactive groups at both ends of the polymer site; and c) -3) first and second protecting the first and second reactive groups, respectively. Providing a protecting group;
Obtained with
The first and second cyclic molecules have first and second active groups, respectively;
During the reaction of the cross-linking precursor, the first and second protecting groups are deprotected,
A bond is formed from the first active group and the first reactive group, a bond is formed from the second active group and the second reactive group, and the first and second polyrotaxanes are: The method according to any one of claims 7 to 12, which is cross-linked through the polymer site. The second crosslinking compound is
e) providing a third and fourth protecting group for protecting the third and fourth reactive groups, respectively;
Obtained with
During the reaction of the cross-linking precursor, the third and fourth protecting groups are deprotected,
A bond is formed from the first active group and the first reactive group, a bond is formed from the second active group and the second reactive group, and the first and second polyrotaxanes are: Cross-linked through the polymer site, and a bond is formed from the first active group and the third reactive group, and a bond is formed from the second active group and the fourth reactive group. The method according to claim 12 or 13, wherein the first and second polyrotaxanes are crosslinked via the second crosslinking compound. I) a polyrotaxane in which blocking groups are arranged so that the cyclic molecule is not detached at both ends of the pseudopolyrotaxane in which the opening of the cyclic molecule is clasped with a linear molecule; and II) the first A first cross-linking compound having a polymer moiety, having first and second reactive groups at both ends of the first polymer moiety and protecting the first and second reactive groups A first bridging compound having first and second protecting groups;
A composition having further,
III) a second bridging compound having at least a third and a fourth reactive group and having a third and a fourth protective group that protects the third and fourth reactive groups;
16. The composition of claim 15 having: A) I) A step of preparing a polyrotaxane in which a blocking group is arranged so that the cyclic molecule is not detached at both ends of a pseudopolyrotaxane in which the opening of the cyclic molecule is skewered by a linear molecule. ;
B) II) A first cross-linking compound having a first polymer moiety, having first and second reactive groups at both ends of the first polymer moiety, and the first and second Preparing a first cross-linking compound having first and second protecting groups protecting two reactive groups; and C) mixing I) polyrotaxane; and II) first cross-linking compound. ;
A method for producing a composition, wherein the composition is obtained. further,
D) III) providing a second bridging compound having at least a third and a fourth reactive group and having a third and a fourth protective group that protects the third and fourth reactive groups;
Have
18. The method of claim 17, wherein in step C), I) polyrotaxane; II) first cross-linking compound; and III) second cross-linking compound are mixed.

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