CN106164119A - Injection heat curable polyurethane elastomer - Google Patents

Abstract

The present invention is at least to make polycarbonate polyol (A), polyisocyanates (B) and polyrotaxane (C) react the injection heat curable polyurethane elastomer obtained, need relative to polycarbonate polyol (A) according to and, polyisocyanates (B), the quality summation of polyrotaxane (C) and inorganic material (D) can be containing the inorganic material (D) of 0～30 mass %, the quality adding rate of described polyrotaxane (C) is relative to polycarbonate polyol (A), polyisocyanates (B), the quality summation of polyrotaxane (C) and inorganic material (D) is 1～10 mass %, or the viscosity of polyrotaxane (C) is below 5000cP at 120 DEG C, or polyisocyanates (B) be can dilution ratio be less than 0.4 injection heat curable polyurethane elastomer.

Description

Injection molding thermosetting polyurethane elastomer

technical field

The present invention relates to thermosetting polyurethane elastomers obtained by injection molding.

Background technique

We are developing a linear molecule that has a circular molecule, a linear molecule that runs through the circular molecule, and a cap that is placed at both ends of the linear molecule and prevents the separation of the circular molecule and the linear molecule. based polyrotaxanes. This polyrotaxane is used as a raw material for a paint that provides a cured product excellent in scratch resistance, and as a raw material for an elastomer characterized by low compression set (see JP-A-2011-046917).

In particular, a flexible and thermally conductive urethane material using polycarbonate polyol, polyrotaxane, and a thermally conductive filler has been proposed (see International Publication No. 2012/165401).

In addition, it is known that a charging member using a polyrotaxane can provide an electrophotographic process cartridge capable of stably forming high-quality electronic photographs (see International Publication No. 2013/094129).

In addition, it is known that an electrophotographic photoreceptor having a polyrotaxane in its outermost layer has excellent mechanical and electrical durability against repeated use over a long period of time (see JP-A-2012-181244).

In addition, it is known that a developed polyrotaxane-containing transparent plastic for automobiles has excellent scratch resistance and chipping resistance (see Japanese Patent Application Laid-Open No. 2007-106861).

In addition, it is known that urethane materials using polycarbonate polyols and polyrotaxanes are free from solvents and softeners and have desired flexibility and expandability (see International Publication No. 2011/108515). .

In addition, polyurethane elastomers and the like have begun to be used as members of paper feed rollers used in printing devices (see JP-A-2011-037564). In recent years, people have been seeking higher image quality of printing devices, and along with this, characteristics such as no roll marks and no sticking to paper are required. In order to suppress the adhesion of roll marks and adhesion to paper, it has been reported that the purpose is achieved by reducing the swelling ratio of rolls to toluene (see JP-A-2008-280144). Therefore, it is necessary to reduce the toluene swelling rate of the elastomer in order to manufacture a paper feed roller free from sticking to roll marks and sticking to paper.

Urethane materials using polycarbonate polyols and polyrotaxanes are characterized by excellent flexibility (see International Publication No. 2012/165401).

prior art literature

patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2011-046917

Patent Document 2: International Publication No. 2012/165401

Patent Document 3: International Publication No. 2013/094129

Patent Document 4: Japanese Patent Laid-Open No. 2012-181244

Patent Document 5: Japanese Patent Laid-Open No. 2007-106861

Patent Document 6: International Publication No. 2011/108515

Patent Document 7: Japanese Patent Laid-Open No. 2011-037564

Patent Document 8: Japanese Patent Laid-Open No. 2008-280144

Contents of the invention

The problem to be solved by the invention

However, the urethane material described in International Publication No. 2012/165401 has problems of high viscosity at high temperature and sticky surface after injection molding. Since the urethane material described in International Publication No. 2013/094129 uses polyether polyol, there is a problem that weather resistance is poor. In addition, due to poor compatibility between polyether materials and polyrotaxanes, crosslinking reactions between polyether materials and polyrotaxanes are difficult to occur, and crosslinking reactions between polyether materials occur preferentially. As a result, gels of the obtained elastomers exist. There are problems such as low efficiency and low mechanical strength. The material described in Japanese Patent Application Laid-Open No. 2012-181244 contains a solvent, so molding other than the solution casting method (film-forming method) and coating method cannot be performed. In the case of molding by injection molding, etc., a large number of bubbles are formed in the cured product. such a problem. The urethane material described in Japanese Patent Application Laid-Open No. 2007-106861 does not form a cross-linked structure and has a low gel fraction, and thus has a problem of poor mechanical properties as an elastomer. The mixed solution of the urethane material described in International Publication No. 2011/108515 has a problem that the viscosity of the mixed solution of the urethane material is very high, and the mixed solution has almost no fluidity, so that injection molding cannot be performed. The urethane material described in International Publication No. 2012/165401 has a problem that the toluene swelling rate is low.

Therefore, in the first to third aspects of the present invention, it is an object to provide an injection molding thermosetting polyurethane elastomer having a low viscosity of the liquid mixture and no bubbles in the cured product of injection molding. An object of the present invention according to the first and second aspects is to provide an injection molding thermosetting polyurethane elastomer having a high gel fraction. In addition, the present invention according to the first aspect also has an object of providing an injection molding thermosetting polyurethane elastomer having a low surface viscosity at 60°C. In addition, the third aspect of the present invention has an object of providing an injection molding thermosetting polyurethane elastomer having a low toluene swelling rate.

means to solve the problem

Specifically, the present invention has the following constitutions.

The present invention according to the first aspect has the constitutions of [1] to [6].

[1] An injection molding thermosetting polyurethane elastomer obtained by reacting at least polycarbonate polyol (A), polyisocyanate (B) and polyrotaxane (C) in the absence of a solvent, and optional An injection molding thermosetting polyurethane elastomer containing an inorganic material (D), wherein,

The polyrotaxane (C) has a cyclic molecule (Ca), a linear molecule (Cb) that penetrates the opening of the cyclic molecule (Ca) in a string, and is arranged on the linear molecule (Cb). A capping group (Cc) that prevents separation of the cyclic molecule (Ca) from the linear molecule (Cb), and a modifying group (Cd) that modifies the cyclic molecule (Ca),

The mass addition rate of the polyrotaxane (C) is 1 to 10% by mass relative to the mass sum of the polycarbonate polyol (A), polyisocyanate (B), polyrotaxane (C) and inorganic material (D) The mass addition rate of the inorganic material (D) is 0 to 30% by mass relative to the mass sum of the polycarbonate polyol (A), polyisocyanate (B), polyrotaxane (C) and the inorganic material (D).

[2] The injection molding thermosetting polyurethane elastomer according to the above [1], wherein the mass addition rate of the inorganic material (D) is The mass total of (C) and the inorganic material (D) contained as needed is 0-9 mass %.

[3] The injection molding thermosetting polyurethane elastomer according to the above [1] or [2], wherein the mass addition rate of the polyrotaxane (C) is ), the polyrotaxane (C), and the mass total of the inorganic material (D) contained if necessary is 3 to 10 mass%.

[4] The injection molding thermosetting polyurethane elastomer according to any one of the above [1] to [3], wherein the hydroxyl groups of the polycarbonate polyol (A) and the polyrotaxane (C) are The molar ratio of the isocyanate group which the isocyanate (B) has is NCO/OH=1/1-5/1.

[5] The injection molding thermosetting polyurethane elastomer according to any one of the above [1] to [4], wherein the polycarbonate polyol (A) has a number average molecular weight of 500 to 1500.

[6] The injection molding thermosetting polyurethane elastomer according to any one of the above [1] to [5], wherein the polycarbonate polyol (A) has an alicyclic ring content of 10% or less.

The present invention according to the second aspect has the constitutions of [7] to [10].

[7] An injection molding thermosetting polyurethane elastomer, which is an injection molding thermosetting polyurethane obtained by reacting at least polycarbonate polyol (A), polyisocyanate (B) and polyrotaxane (C) without solvent Elastomer, where,

The polyrotaxane (C) has a cyclic molecule (Ca), a linear molecule (Cb) that penetrates the opening of the cyclic molecule (Ca) in a string, and is arranged on the linear molecule (Cb). A capping group (Cc) that prevents separation of the cyclic molecule (Ca) from the linear molecule (Cb), and a modifying group (Cd) that modifies the cyclic molecule (Ca),

The polyrotaxane (C) has a viscosity of 5000 cP or less at 120°C.

[8] The injection molding thermosetting polyurethane elastomer according to the above [7], wherein the mass addition rate of the polyrotaxane (C) is The mass sum of alkanes (C) is 3-10 mass%.

[9] The injection molding thermosetting polyurethane elastomer according to the above [7] or [8], wherein the polycarbonate polyol (A) and polyrotaxane (C) have hydroxyl groups and polyisocyanate (B) The molar ratio of the isocyano group to have is NCO/OH=1/1 to 10/1.

[10] The injection molding thermosetting polyurethane elastomer according to any one of the above [7] to [9], wherein the mass ratio of the modifying group (Cd) to the cyclic molecule (Ca) and linear molecule The mass sum of (Cb), capping group (Cc) and modification group (Cd) is 80% or less.

A third aspect of the present invention has the constitutions of [11] to [14].

[11] An injection molding thermosetting polyurethane elastomer, which is an injection molding thermosetting polyurethane obtained by reacting at least polycarbonate polyol (A), polyisocyanate (B) and polyrotaxane (C) without solvent elastic body, which

The polyrotaxane (C) has a cyclic molecule (Ca), a linear molecule (Cb) that penetrates the opening of the cyclic molecule (Ca) in a string, and is arranged on the linear molecule (Cb). A capping group (Cc) that prevents the separation of the cyclic molecule (Ca) from the linear molecule (Cb), and a modifying group (Cd) that modifies the cyclic molecule (Ca) ,

The dilutable ratio of the polyisocyanate (B) is 0.4 or less.

[12] The injection molding thermosetting polyurethane elastomer according to the above [1], wherein the mass addition rate of the polyrotaxane (C) is The sum of the mass of alkanes (C) is 2-10 mass %.

[13] The injection molding thermosetting polyurethane elastomer according to the above [11] or [12], wherein the average number of functional groups in one molecule of polyisocyanate (B) is 2.5 to 5.0.

[14] The injection molding thermosetting polyurethane elastomer according to any one of the above [11] to [13], wherein the dilutable ratio of the polyisocyanate (B) is 0.2 or less.

Invention effect

According to the present inventions of the first to third aspects, it is possible to provide an injection-molded thermosetting polyurethane elastomer having a low viscosity of the liquid mixture and no bubbles in the injection-molded cured product. According to the present inventions of the first and second aspects, it is possible to provide an injection molding thermosetting polyurethane elastomer having a high gel ratio. Also, according to the first aspect of the present invention, it is possible to provide an injection-molded thermosetting polyurethane elastomer having a low surface viscosity at 60°C. In addition, according to the third aspect of the present invention, it is possible to provide an injection molding thermosetting polyurethane elastomer having a low toluene swelling rate.

[The present invention of the first aspect]

Hereinafter, the present invention according to the first aspect will be specifically described.

The present invention of the first aspect is an injection molding thermosetting polyurethane elastomer, which is obtained by at least reacting polycarbonate polyol (A), polyisocyanate (B) and polyrotaxane (C) without solvent, and An injection-molded thermosetting polyurethane elastomer optionally containing an inorganic material (D), wherein,

The polyrotaxane (C) has a cyclic molecule (Ca), a linear molecule (Cb) that penetrates the opening of the cyclic molecule (Ca) in a string, and is arranged on the linear molecule (Cb). A capping group (Cc) that prevents separation of the cyclic molecule (Ca) from the linear molecule (Cb), and a modifying group (Cd) that modifies the cyclic molecule (Ca),

The mass addition rate of the polyrotaxane (C) is 1 to 10% by mass relative to the mass sum of the polycarbonate polyol (A), polyisocyanate (B), polyrotaxane (C) and inorganic material (D) The mass addition rate of the inorganic material (D) is 0 to 30% by mass relative to the mass sum of the polycarbonate polyol (A), polyisocyanate (B), polyrotaxane (C) and the inorganic material (D).

＜Polycarbonate polyol (A)＞

The polycarbonate polyol (A) is obtained by reacting one or more polyol monomers with carbonate and phosgene. From the viewpoints of ease of production and absence of terminal chloride by-products, polycarbonate diols obtained by reacting one or more polyol monomers with carbonate esters are preferred.

The polyol monomer is not particularly limited, and examples thereof include aliphatic polyol monomers, polyol monomers having an alicyclic structure, and aromatic polyol monomers.

From the viewpoint that the viscosity of the mixture containing polycarbonate polyol (A), polyisocyanate (B) and polyrotaxane (C) becomes low, polycarbonate polyol (A) is preferably It is the aliphatic polycarbonate polyol of raw material, more preferably is aliphatic polycarbonate diol, especially preferably is the aliphatic polycarbonate diol that 1,6-hexanediol and carbonic ester transesterify .

In addition, the polycarbonate polyol (A) may be a polycarbonate polyol modified with polyester polyol, polyether polyol, cyclic ester, or the like.

The modified polycarbonate polyol can be obtained by transesterifying polycarbonate polyol with polyester polyol, polyether polyol, cyclic ester, etc., or by making carbonate or phosgene, and It is obtained by reacting polyol monomer with polyester polyol or polyether polyol, cyclic ester, etc.

The aliphatic polyhydric alcohol monomer is not particularly limited, and examples thereof include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, Alcohol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol and other linear aliphatic diols; 2-methyl-1,3-propanediol, 2 -Methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,9-nonanediol and other branched aliphatic diols; trihydroxy Trifunctional or higher polyhydric alcohols such as methylpropane and pentaerythritol, etc.

The polyhydric alcohol monomer having an alicyclic structure is not particularly limited, and examples thereof include 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclopentanediol, 1,4-cycloheptanediol, 2,7-norbornanediol, 1,4-bis(hydroxyethoxy)cyclohexane, etc. Cyclic diols, etc.

The aromatic polyhydric alcohol monomer is not particularly limited, and examples thereof include 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, 4,4'-naphthalene dimethanol, 3,4'-Naphthalene dimethanol, etc.

The polyester polyol is not particularly limited, and examples thereof include polyester polyols such as 6-hydroxycaproic acid and hexanediol, polyester polyols such as hydroxycarboxylic acids and diols, adipic acid and hexanediol, etc. Polyester polyols such as dicarboxylic acids and diols such as polyester polyols of alcohols.

The polyether polyol is not particularly limited, and examples thereof include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

The cyclic ester is not particularly limited, and examples thereof include lactones such as valerolactone, caprolactone, and laurolactone.

The carbonate is not particularly limited, and examples thereof include aliphatic carbonates such as dimethyl carbonate and diethyl carbonate, aromatic carbonates such as diphenyl carbonate, and cyclic carbonates such as ethylene carbonate. Moreover, phosgene etc. which can produce polycarbonate polyol can also be used. In particular, from the viewpoint of easiness of production of polycarbonate polyol, aliphatic carbonates are preferred, and dimethyl carbonate is particularly preferred.

The number average molecular weight of the polycarbonate polyol (A) is preferably 500-3000, more preferably 500-1500. When the number average molecular weight is 500 or more, the pot life tends to be longer. When the number average molecular weight is 3000 or less, the gel fraction tends to be higher.

The number average molecular weight is set as the number average molecular weight calculated based on the hydroxyl value measured based on JISK1577. Specifically, the hydroxyl value was measured, and calculated by (56.1×1000×valent number)/hydroxyl value [mgKOH/g] by the terminal group quantification method. In the formula, the valency is the number of hydroxyl groups in one molecule.

The hydroxyl value of the above mixture is measured by the method described in JIS K 0070.

The polycarbonate polyol (A) may be used alone or in combination.

It is preferable that the average number of functional groups of polycarbonate polyol (A) is 2-5. When the average number of functional groups is within this range, a polyurethane elastomer having a higher gel fraction can be obtained, and the pot life also tends to be longer.

In the present invention, when the polycarbonate polyol (A) has an alicyclic structure, the alicyclic content is preferably 10% by mass or less. When the alicyclic ring content is 10% by mass or less, the strength of the cured product tends to be sufficiently high, and the residual strain of the cured product also tends to be small.

Here, the alicyclic content rate in the polyhydric alcohol means the portion (alicyclic hydrocarbon residue) in which two hydrogen atoms are removed from the alicyclic hydrocarbon, for example, when the alicyclic structure is a cyclohexane ring, it is the fraction from cyclohexane How many parts (cyclohexane residues) except two hydrogen atoms exist in the polyol in mass percent. In addition, the alicyclic content rate in a polyurethane resin shows how many alicyclic hydrocarbon residues exist in a polyurethane resin by mass percentage.

Specifically, the alicyclic ring content can be derived from the following formula.

[Alicyclic content ratio] = [Molecular weight of alicyclic structure in polycarbonate polyol]/[Molecular weight of polycarbonate polyol]

The mass addition rate of polycarbonate polyol (A) is preferably with respect to the mass summation of polycarbonate polyol (A), polyisocyanate (B), polyrotaxane (C) and the inorganic material (D) that can contain arbitrarily 40 to 90% by mass, more preferably 45 to 85% by mass. In addition, it is preferably 45 to 80% by mass. With such a ratio of raw materials, a polyurethane elastomer having a higher gel fraction can be obtained.

＜Polyisocyanate (B)＞

It does not specifically limit as polyisocyanate (B), For example, aromatic isocyanate, aliphatic isocyanate, alicyclic isocyanate etc. are mentioned.

The aromatic isocyanate is not particularly limited, and examples thereof include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate (TDI), 2,6-toluene Diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,4-diphenylmethane diisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4 , 4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthalene diisocyanate, 4,4',4 "-Triphenylmethane triisocyanate, m-isocyanatophenylsulfonyl isocyanate, p-isocyanatophenylsulfonyl isocyanate, etc.

The aliphatic isocyanate is not particularly limited, and examples thereof include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11 -Undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylhexanoate, bis(2-isocyanate Acetoethyl)fumarate, bis(2-isocyanatoethyl)carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, and the like.

The alicyclic isocyanate is not particularly limited, and examples thereof include isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexene diisocyanate, methylcyclo Hexene diisocyanate (hydrogenated TDI), bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6- Norbornane diisocyanate, hydrogenated xylylene diisocyanate (H6XDI), etc.

As for the polyisocyanate (B), it is preferable to use an alicyclic isocyanate from the viewpoint of increasing the strength of the cured product and improving the light resistance of the cured product. From the viewpoint of workability and reactivity, hydrogenated xylylene diisocyanate (H6XDI) is preferably used. In addition, the polyisocyanate (B) may be used alone or in combination.

It is preferable that the average number of functional groups (average number of NCO groups) of polyisocyanate (B) is 2-5. More preferably, it is 2.0-5.0, More preferably, it is 2.5-5.0. By using a polyisocyanate having such an average number of functional groups, the pot life can be relatively extended, and a polyurethane elastomer having a higher gel fraction can be obtained.

The mass addition rate of polyisocyanate (B) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. When the mass addition rate of the polyisocyanate (B) is in such a range, the pot life can be relatively extended, and a polyurethane elastomer having a higher gel ratio can be obtained.

＜Polyrotaxane (C)＞

The polyrotaxane (C) used in the present invention has a cyclic molecule (Ca) arranged thereon, and a straight chain molecule (Cb) that penetrates the opening of the cyclic molecule (Ca) in a string, and is arranged in the straight chain a capping group (Cc) that prevents separation of the cyclic molecule (Ca) from the linear molecule (Cb) at both ends of the chain molecule (Cb), and a capping group (Cc) that modifies the cyclic molecule (Ca) Inclusion compound composed of modifying group (Cd). As the polyrotaxane, a polyrotaxane specified by CAS No. 928045-45-8 is preferable.

＜(Ca)cyclic molecule＞

The cyclic molecule (Ca) is not particularly limited as long as its opening can be penetrated by the linear molecule (Cb) to form a string. This cyclic molecule (Ca) may be used in the production of the polyrotaxane (C) only by one type or in multiple types.

The cyclic molecule (Ca) usually has a hydroxyl group, at least a part of which is bonded with the isocyanate group of the prepolymer comprising the polycarbonate polyol (A) and the polyisocyanate (B), or the isocyanate group of the polyisocyanate (B). Modified by a modifying group (Cd) that undergoes a cross-linking reaction.

From the viewpoint that the modifying group (Cd) can be introduced, as the above-mentioned cyclic molecule (Ca), cyclodextrins such as α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin are preferable.

The modifying group (Cd) can make the polyrotaxane hydrophilic or hydrophobic while imparting good crosslinkability to the polyrotaxane.

The modifying group (Cd) particularly preferably has a hydrophobic group that makes the polyrotaxane hydrophobic. The hydrophobic group modifies at least a part of the hydroxyl group of the cyclic molecule (Ca).

Examples of the hydrophobic group include: an alkylene group which may have a substituent having 1 to 50 carbons, an arylene group which may have a substituent having 6 to 50 carbons, and an arylene group which may have a substituent having 4 to 50 carbons. A heteroarylene group as a substituent, a divalent polyether group derived from a diol having 3 to 12 carbons or an oxyalkylene group, a divalent polyester derived from a hydroxycarboxylic acid or a cyclic ester having 3 to 12 carbons group, a divalent polyamide group derived from a lactam having 3 to 8 carbon atoms, and the like.

Examples of the substituent include halogen atoms (for example, fluorine atoms, chlorine atoms, bromine atoms), alkyl groups having 1 to 20 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, butyl, base, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, 2-ethylhexyl, octyl, dodecyl, dodecyl octyl (dodecyl octyl)), aryl (such as , phenyl, naphthyl), aralkyl (eg, benzyl, phenethyl), alkoxy (eg, methoxy, ethoxy) and the like.

It should be noted that the carbons in these substituents are not included in the carbon numbers of the alkylene, arylene and heteroarylene groups.

In addition, examples of the heteroarylene group include: furylylene, thienylene, pyridylylene, pyridazinylene, pyrimidinylene, pyrazinylene, triazinylene, imidazolinylene, Pyrazolinyl, thiazolinylene, quinazolinylene, phthalazinylene, etc.

In addition, the reactive group bonded to the other end of the hydrophobic group that modifies the cyclic molecule (Ca) is a group that can react with each other, or has a reaction with polyisocyanate (B). The reactive group of the isocyanate group, as its example, photoreactive groups such as hydroxyl group, amino group, thiol group, carboxyl group, (meth)acryloyl group, vinyl group and allyl group, isocyanate group, Block isocyanato, keto, aldehyde, epoxy, oxetanyl and carbodiimide groups.

From the viewpoint of ease of introduction into the hydrophobic group, the reactive group is particularly preferably a hydroxyl group of polycaprolactone or an amino group of polycaprolactam. The "poly" means that the repeating unit is 2 or more. In addition, in polycaprolactone or polycaprolactam, the part other than the part corresponding to the group mentioned as an example of a reactive group will comprise a part of the said hydrophobic group.

In addition, as the method for introducing the modifying group (Cd) into the cyclic molecule (Ca) described above, for example, the following method can be employed. Cyclodextrin is used as the cyclic molecule (Ca), and the hydroxyl group of the cyclodextrin is hydroxypropylated with propylene oxide (the hydroxyl group of the cyclodextrin is modified with a hydrophobic group), and then ε-hexane lactone, and tin 2-ethylhexanoate was added as a catalyst. Thus, a modifying group (Cd) having a carboxyl group as a reactive group is introduced into the cyclic molecule (Ca).

The degree of modification can be arbitrarily controlled by changing the addition ratio of propylene oxide and ε-caprolactone to cyclodextrin at this time. Here, when the maximum number of hydroxyl groups that can be modified is 1, the cyclodextrin is preferably modified with a modification degree of 0.02 or more. It should be noted that the degree of modification is: when one molecule of polyrotaxane is observed, the modified hydroxyl group is relative to the total number of hydroxyl groups in the multiple cyclodextrin molecules contained in the polyrotaxane (including the hydroxyl groups modified by hydrophobic groups). )proportion.

Various modifying groups (Cd) can be introduced into the cyclic molecule (Ca) by the same method as described above or by a known method utilizing a reaction with another hydroxyl group.

If the crosslinking point is introduced at a position slightly away from the main body of the polyrotaxane (C) molecule by the modifier (Cd) in this way, the crosslinking reaction with the polyisocyanate (B) becomes easier due to reasons such as a reduction in steric hindrance. .

＜(Cb) Linear Molecule＞

The linear molecule (Cb) used in the present invention is not particularly limited as long as the opening of the cyclic molecule (Ca) is penetrated in a string and can be included by the cyclic molecule (Ca). It should be noted that both ends of the linear molecule (Cb) have functional groups that serve as reactive sites when a capping group (Cc) described later is introduced. Examples of the functional group include hydroxyl group, carboxyl group, amino group, mercapto group, sulfonyl group and the like.

In the production of the polyrotaxane (C), only one type of the linear molecule (Cb) may be used, or a plurality of types may be used.

Examples of the linear molecule (Cb) include polyvinyl alcohol, polycaprolactone, polyvinylpyrrolidone, poly(meth)acrylic acid, cellulose-based resins (carboxymethyl cellulose, hydroxyethyl cellulose, etc.) cellulose, hydroxypropyl cellulose, etc.), polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl acetal resin, polyvinyl methyl ether, polyamine, polyethylene Imine, casein, gelatin, starch, polyester resin, poly(meth)acrylic acid, polycarbonate resin, polyurethane resin, etc., polytetrahydrofuran, polyaniline, polyamide resin, polyimide resin, polyisoprene Polydiene such as olefin and polybutadiene, polysiloxane such as polydimethylsiloxane, polysulfone, polyimide, polyanhydrous acetic acid, polyurea, polysulfide, Polyphosphazenes, polyketones, polyphenylenes, polyhalogenated olefins, and their derivatives and copolymers.

Of these, polycaprolactone, polyethylene glycol, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyvinyl alcohol, and polyvinylmethyl ether are preferred.

Among these, polycaprolactone, polyethylene glycol, polypropylene glycol, polytetrahydrofuran, and polydimethylsiloxane are more preferred, polycaprolactone and polyethylene glycol are further preferred, and particularly preferred from the viewpoint of being water-soluble. polyethylene glycol.

The weight average molecular weight of the linear molecule (Cb) is 1,000 or more, preferably 2,000 or more from the viewpoint of further improving the gel fraction of the injection molding thermosetting polyurethane elastomer of the present invention. The weight average molecular weight is 100,000 or less, preferably 80,000 or less. More preferably, it is 30,000 or less.

In addition, the said weight average molecular weight is the value of polystyrene conversion measured by gel filtration chromatography (GPC).

In addition, when a linear molecule (Cb) is included by a cyclic molecule (Ca), when the maximum inclusion amount (maximum inclusion amount) of the linear molecule (Cb) is set to 1, the average The inclusion amount is usually 0.001 to 0.6, preferably 0.01 to 0.5, more preferably 0.05 to 0.4.

It should be noted that the maximum inclusion capacity of the cyclic molecule (Ca) can be determined by the length of the linear molecule (Cb) and the thickness of the cyclic molecule (Ca) in the chain direction of the linear molecule (Cb) . For example, when the linear molecule (Cb) is polyethylene glycol and the cyclic molecule (Ca) is α-cyclodextrin, the maximum inclusion amount is as described in Macromolecules 1993, 26, 5698-5703, using Experiment to find out.

＜(Cc)capping group＞

The capping group (Cc) of the polyrotaxane (C) used in the present invention is provided at both ends of the linear molecule (Cb) so as to connect the cyclic molecule (Ca) and the linear molecule (Cb). ) is not particularly limited to groups that do not have the effect of separation. Such a capping group (Cc) may use only 1 type, and may use multiple types.

Examples of the terminal capping group (Cc) include dinitrophenyl groups, cyclodextrin-derived groups, adamantyl groups, trityl groups, fluorenyl groups, pyrenyl groups, Substituted phenyl (as the substituent of the phenyl group, alkyl, alkoxy, hydroxyl, halogen, cyano, sulfonyl, carboxyl, amino and phenyl can be mentioned, but not limited thereto. Substituents can exist 1 one or more.), a polycyclic aromatic group that may be substituted (as the substituent of the polycyclic aromatic group, the same groups as mentioned above can be mentioned, but not limited thereto. There may be one substituent or more.) and steroids.

Among these, dinitrophenyl groups, groups derived from cyclodextrins, adamantyl groups, trityl groups, fluorenyl groups, and pyrenyl groups are preferable from the viewpoint of easy introduction of a capping group (Cc). , more preferably adamantyl and trityl.

Arranging the end-capping group (Cc) at both ends of the linear molecule (Cb) can be carried out as follows: by making a group that reacts with the functional group present at the two ends, and having a group that becomes the It is carried out by reacting the compound at the position of the capping group (Cc) with the linear molecule (Cb).

In the first aspect of the present invention, the mass addition rate of polyrotaxane (C) is relative to polycarbonate polyol (A), polyisocyanate (B), polyrotaxane (C), and inorganic materials that can be used as needed The total mass of (D) is 1-10 mass %, Preferably it is 3-10 mass %. When the mass addition rate of the polyrotaxane (C) is in such a range, a polyurethane elastomer having a higher gel fraction can be obtained, and the pot life at the time of production can be relatively extended.

＜Inorganic material (D)＞

The inorganic material (D) is not particularly limited, and examples thereof include metals, metal oxides, metal nitrides, metal carbides, alloys, and the like.

It does not specifically limit as a metal, For example, aluminum, copper, nickel etc. are mentioned.

It does not specifically limit as a metal oxide, For example, aluminum oxide, magnesium oxide, beryllium oxide, chromium oxide, titanium oxide etc. are mentioned.

It does not specifically limit as a metal nitride, For example, boron nitride, aluminum nitride, etc. are mentioned.

It does not specifically limit as a metal carbide, For example, boron carbide, titanium carbide, silicon carbide etc. are mentioned.

The alloy is not particularly limited, and examples thereof include Fe-Si alloys, Fe-Al alloys, Fe-Si-Al alloys, Fe-Si-Cr alloys, Fe-Ni alloys, Fe-Ni-Co alloys, Fe-Ni alloys, and Fe-Ni alloys. - Mo alloy, Fe-Co alloy, Fe-Si-Al-Cr alloy, Fe-Si-B alloy, Fe-Si-Co-B alloy, etc.

The mass addition rate of the inorganic material (D) is 0 to 30% by mass relative to the mass sum of the polycarbonate polyol (A), polyisocyanate (B), polyrotaxane (C) and the inorganic material (D), preferably 0 to 9% by mass. When the added amount of the inorganic material (D) is 30% by mass or less, the gel fraction tends to be higher.

＜Composition for polyurethane resin＞

The composition for polyurethane resins (hereinafter sometimes simply referred to as "composition") contains polycarbonate polyol (A), polyisocyanate (B), polyrotaxane (C), and inorganic materials ( The mixed solution of D) is the mass addition rate of the polyrotaxane (C) relative to the quality of polycarbonate polyol (A), polyisocyanate (B), polyrotaxane (C) and inorganic material (D) The sum is 1 to 10% by mass, and the mass addition rate of the inorganic material (D) is 0 to 30% by mass of the mixed solution. The composition for polyurethane resins may contain catalysts, antioxidants, air release agents, ultraviolet absorbers, reaction regulators, plasticizers, release agents, reinforcing agents, fillers (inorganic fillers, organic fillers), stabilizers Various substances used in conventionally known compositions for forming polyurethane resin compositions, such as additives, colorants (pigments and dyes), flame retardants, and light stabilizers, are optional components.

The catalyst is not particularly limited, and examples thereof include salts of metals such as tin (sz)-based catalysts (trimethyltin laurate, dibutyltin dilaurate, etc.), lead-based catalysts (lead octoate, etc.), and organic and inorganic acids, And organometallic derivatives, amine catalysts (triethylamine, N-ethylmorpholine, triethylenediamine, etc.), diazabicycloundecene catalysts, etc. In particular, from the viewpoint of reactivity, dibutyltin dilaurate and dioctyltin dilaurate are preferable. The amount of the catalyst used is not particularly limited, and an appropriate amount known to those skilled in the art can be used.

The antioxidant is not particularly limited, and examples thereof include IRGANOX 1726 (BASF Japan), IRGANOX 1010 (BASF Japan), IRGANOX 1076 (BASF Japan), IRGANOX 245 (BASF Japan), and VANOX 830 (phenolic compounds, alkylated diphenylamines and triphenylamines) Alkyl phosphite mixture) (R.T Vanderbilt company) and the like.

The mass addition rate of the antioxidant is preferably 0.01 to 10% by mass relative to the total of the polycarbonate polyol (A), polyisocyanate (B), polyrotaxane (C), and inorganic material (D) that can be used if necessary. , more preferably 0.1 to 5% by mass. When the addition rate of the antioxidant falls within such a range, yellowing can be suppressed without greatly affecting the physical properties of the polyurethane elastomer.

Regarding defoaming agents, ultraviolet absorbers, reaction modifiers, plasticizers, mold release agents, reinforcing agents, fillers (inorganic fillers, organic fillers), stabilizers, colorants (pigments, dyes), flame retardants There are no particular limitations on the types and amounts of other components such as agents and photostabilizers, and appropriate amounts known to those skilled in the art can be used.

In the polyurethane resin composition of the present invention, the molar ratio of the hydroxyl group (OH) of the polycarbonate polyol (A) and the polyrotaxane (C) to the isocyanate group (NCO) of the polyisocyanate (B) , NCO/OH is preferably 0.1/1 to 10/1, NCO/OH is more preferably 0.5/1 to 5/1, and NCO/OH is still more preferably 1/1 to 5/1. When the value of NCO/OH is within such a range, the pot life tends to be longer.

＜Manufacturing method of injection molding thermosetting polyurethane elastomer＞

Next, the method for producing the injection-molded thermosetting polyurethane elastomer of the present invention will be described.

The injection-molded thermosetting polyurethane elastomer of the present invention is produced, for example, through the following first to third steps.

The first step: a step of mixing polycarbonate polyol (A), polyisocyanate (B), polyrotaxane (C), and an inorganic material (D) that may be used if necessary.

The second process: the process of applying the mixed liquid to the model.

The third process: the process of making the mixed solution react and heat-cure in the mold.

＜<First step: Step of mixing polycarbonate polyol (A), polyisocyanate (B), polyrotaxane (C), and optional inorganic material (D)>>

In the step of mixing polycarbonate polyol (A), polyisocyanate (B) and polyrotaxane (C) for producing the injection molding thermosetting polyurethane elastomer of the present invention, an inorganic material (D) can be used. Through this step, a composition for a polyurethane resin is obtained.

＜＜＜Case where no inorganic material (D) is used＞＞＞

As the mixing method of the components used to produce the injection molding thermosetting polyurethane elastomer of the present invention, when the inorganic material (D) is not used, the mixing method and operation sequence are not particularly limited, and examples include: mixing polycarbonate A so-called one-shot method in which ester polyol (A), polyisocyanate (B) and polyrotaxane (C) are mixed; polycarbonate polyol (A) and polyisocyanate (B) are reacted in advance to A synthetic prepolymer having an isocyanate group at a molecular terminal, a so-called prepolymer method in which polyrotaxane (C) is mixed, and the like.

＜<<<In the case of one-time method>>>>

In the case of the so-called one-time method of mixing polycarbonate polyol (A), polyisocyanate (B) and polyrotaxane (C), the mixing method and operation sequence are not particularly limited, and examples include mixing all The method of mixing the ingredients; and the product obtained by mixing the two ingredients in advance, the method of mixing with the remaining ingredients, etc. The order of mixing the ingredients and the combination of previously mixed ingredients can be in any order and combination.

＜<<<In case of prepolymer method>>>>

In the case of the so-called prepolymer method in which a prepolymer synthesized by reacting polycarbonate polyol (A) and polyisocyanate (B) in advance is mixed with polyrotaxane (C), its mixing method and operation procedure It is not particularly limited, and examples thereof include: a method of mixing a prepolymer synthesized by reacting polycarbonate polyol (A) and polyisocyanate (B) in advance with polyrotaxane (C); In (C), a method of mixing a prepolymer having an isocyanate group at a molecular terminal, which is synthesized by reacting a polycarbonate polyol (A) and a polyisocyanate (B) in advance, or the like.

A part of the polycarbonate polyol (A) may be reacted with the polyisocyanate (B) in advance to synthesize a prepolymer, and the remaining polycarbonate polyol (A) may be mixed with the polyrotaxane (C). The mixing order of the prepolymer and other components is not particularly limited, and examples thereof include a method of mixing all the components at once, a method of mixing two components in advance, and a method of mixing with the remaining components. The order of the ingredients to be mixed and the combination of the previously mixed ingredients can be any order and combination.

＜＜＜In case of using inorganic material (D)＞＞＞

When the inorganic material (D) is used as the mixing method of the components for the production of the injection molding thermosetting polyurethane elastomer of the present invention, the mixing method and operation sequence are not particularly limited, and examples thereof include mixing polycarbonate The so-called one-time method of mixing polyol (A), polyisocyanate (B), polyrotaxane (C) and inorganic material (D); and the polycarbonate polyol (A) and polyisocyanate (B) will be reacted in advance On the other hand, a synthetic prepolymer, a so-called prepolymer method in which a polyrotaxane (C) or an inorganic material (D) is mixed, and the like.

＜<<<In the case of one-time method>>>>

In the case of the so-called one-step method of mixing polycarbonate polyol (A), polyisocyanate (B), polyrotaxane (C) and inorganic material (D), the mixing method and operation sequence are not particularly limited, and examples include For example: a method of mixing all the ingredients at once; a method of mixing a product obtained by mixing two ingredients in advance with the remaining ingredients; a method of mixing a product obtained by mixing two ingredients in advance with the remaining two ingredients The method of mixing the product obtained; and the method of mixing the product obtained by mixing the three components in advance with the remaining components. The order of the components to be mixed and the combination of the components to be mixed in advance may be any order or combination.

＜<<<In case of prepolymer method>>>>

In the case of the so-called prepolymer method in which a prepolymer synthesized by reacting polycarbonate polyol (A) and polyisocyanate (B) in advance is mixed with polyrotaxane (C) and inorganic material (D), the The mixing method and operation order are not particularly limited, and examples include: a method of mixing the prepolymer and other components at once; a method of mixing the prepolymer and other components sequentially, and the like.

A process of mixing polycarbonate polyol (A), polyisocyanate (B) and polyrotaxane (C), or mixing polycarbonate polyol (A), polyisocyanate (B), polyrotaxane (C) and The step of the inorganic material (D) can be performed at 0 to 150°C, preferably at 20 to 100°C. By mixing in such a temperature range, more efficient mixing and injection molding can be performed.

A process of mixing polycarbonate polyol (A), polyisocyanate (B) and polyrotaxane (C), or mixing polycarbonate polyol (A), polyisocyanate (B), polyrotaxane (C) and The mixing time of the step of the inorganic material (D) can be performed within 5 seconds to 5 hours. Preferably it is 10 seconds to 1 hour. By setting such a mixing time, a polyurethane elastomer can be manufactured more efficiently.

A process of mixing polycarbonate polyol (A), polyisocyanate (B) and polyrotaxane (C), or mixing polycarbonate polyol (A), polyisocyanate (B), polyrotaxane (C) and In the step of the inorganic material (D), known stirring devices such as an autorotation-revolving stirrer, a mixer, and a stirring mixer can be used.

＜<The second process: the process of applying the mixed solution to the model＞＞

A mixed solution, which is a composition of polycarbonate polyol (A), polyisocyanate (B), polyrotaxane (C), and if necessary, an inorganic material (D), is injected into the mold.

Put polyisocyanate with isocyanate group, polyurethane prepolymer, polycarbonate polyol and polyrotaxane with substituent reactive with isocyanate group into different tanks, and perform heat preservation, defoaming, Dehydration etc. Catalysts, additives, chain extenders and the like are preferably mixed in the same tank as polycarbonate polyol and the like.

Injection molding is performed by discharging each liquid as a raw material from the injection molding machine into a mold that is kept warm at a predetermined ratio.

Examples of the material of the model include metal, plastic, inorganic substances, wood, and the like. As the shape of the model, shapes known to those skilled in the art can be used. If necessary, before injecting the composition, a mold release agent may be applied in advance in the mold.

In addition, when the curing speed of the composition is slow, after applying the composition, the pressure may be reduced to further defoam. At this time, when an open mold is used as a mold, defoaming may be performed in a vacuum oven.

The temperature during the degassing is preferably 20-100°C, more preferably 50-80°C. By performing degassing at such a temperature, degassing can be performed more efficiently. Depending on the temperature at which defoaming is performed, the step of defoaming and thermal curing described later may be performed simultaneously.

The degassing time is preferably carried out within 1 to 60 minutes, more preferably 5 to 30 minutes. By performing defoaming in such a time, the polyurethane elastomer can be produced more efficiently.

＜<Third process: The process of making the mixed liquid react in the mold and heat curing it＞＞

Polycarbonate polyol (A) and polyrotaxane (C) have hydroxyl groups, and polyisocyanate (B) has the isocyanate group react, can make polycarbonate polyol (A), polyisocyanate A liquid mixture of (B), polyrotaxane (C) and, if necessary, an inorganic material (D) is solidified. Thus, an injection-molded thermosetting polyurethane elastomer was obtained as a cured product of the composition.

Examples of the heating method include a heating method using its own heat of reaction, a heating method using both the reaction heat and active heating of a mold, and the like.

Regarding the active heating of the model, there is a method of heating the model together with a hot air drying oven, an electric furnace, or an infrared induction heating furnace.

The heating temperature is preferably 40-200°C, more preferably 60-160°C. By heating at such a temperature, the urethanization reaction can be advanced more efficiently.

The heating time is preferably 0.5 to 20 hours, more preferably 1 to 10 hours. By setting such a heating time, a polyurethane elastomer with higher hardness can be obtained.

In addition, the cured product can be peeled off from the substrate to obtain an injection molding thermosetting polyurethane elastomer.

<The present invention according to the second aspect>

Next, the present invention of the second aspect will be described.

The present invention of the second aspect is an injection molding thermosetting polyurethane elastomer, which is an injection molding obtained by reacting at least polycarbonate polyol (A), polyisocyanate (B) and polyrotaxane (C) without solvent. Thermosetting polyurethane elastomer, wherein,

The polyrotaxane (C) has a cyclic molecule (Ca), a linear molecule (Cb) that penetrates the opening of the cyclic molecule (Ca) in a string, and is arranged on the linear molecule (Cb). A capping group (Cc) that prevents separation of the cyclic molecule (Ca) from the linear molecule (Cb), and a modifying group (Cd) that modifies the cyclic molecule (Ca),

The polyrotaxane (C) has a viscosity of 5000 cP or less at 120°C.

In the present invention of the second aspect, examples of the polycarbonate polyol (A) and the polyisocyanate (B) are as described in the present invention of the first aspect.

＜Polyrotaxane (C)＞

In the second aspect of the present invention, the viscosity of the polyrotaxane (C) at 120° C. is 5000 cP or less, preferably 3500 cP or less. When the viscosity of the polyrotaxane (C) is within this range, the pot life tends to be longer.

In addition, the viscosity of polyrotaxane (C) was set as the value measured at 120 degreeC using the B-type viscometer (Brookfield company make: LV2+Pro: rotor SC4-34: rotation speed 0.5 rpm).

In the present invention of the second aspect, the mass ratio of the modifying group (Cd) of the polyrotaxane (C) is relative to the cyclic molecule (Ca), the linear molecule (Cb), the capping group (Cc) and the modifying group ( The total mass of Cd) is 90% by mass or less, preferably 80% by mass or less. The cyclic molecule (Ca), linear molecule (Cb), capping group (Cc) and modification group (Cd) of the polyrotaxane (C) are as described in the first aspect of the present invention.

In the present invention of the second aspect, the mass addition rate of polyrotaxane (C) is preferably 1 to 10 mass with respect to the mass sum of polycarbonate polyol (A), polyisocyanate (B), and polyrotaxane (C). %, more preferably 3 to 10% by mass. When the addition rate of the polyrotaxane (C) is in such a range, a polyurethane elastomer having a higher gel fraction can be obtained, and the pot life at the time of production can be relatively extended.

In the second aspect of the present invention, the polyurethane resin composition contains at least polycarbonate polyol (A), polyisocyanate (B) and polyrotaxane (C), and the viscosity of the polyrotaxane (C) is 120 Compositions below 5000cP at °C. The arbitrary components contained in the composition such as a catalyst and an antioxidant, the value of NCO/OH, and the like are as described in the first aspect of the present invention.

In the present invention of the second aspect, the manufacturing method of the injection molding thermosetting polyurethane elastomer is as described in the present invention of the first aspect.

[The present invention of the third aspect]

Next, the present invention according to the third aspect will be described.

The present invention of the third aspect is an injection molding thermosetting polyurethane elastomer, which is an injection molding obtained by reacting at least polycarbonate polyol (A), polyisocyanate (B) and polyrotaxane (C) without solvent. Thermosetting polyurethane elastomer, wherein,

The polyrotaxane (C) has a cyclic molecule (Ca), a linear molecule (Cb) that penetrates the opening of the cyclic molecule (Ca) in a string, and is arranged on the linear molecule (Cb). A capping group (Cc) that prevents separation of the cyclic molecule (Ca) from the linear molecule (Cb), and a modifying group (Cd) that modifies the cyclic molecule (Ca),

The dilutable ratio of the polyisocyanate (B) is 0.4 or less.

In the present invention of the third aspect, the polycarbonate polyol (A) is as described in the present invention of the first aspect.

＜Polyisocyanate (B)＞

Regarding the polyisocyanate (B) of the present invention according to the third aspect, the dilutable ratio thereof is 0.4 or less. The dilutable ratio of the polyisocyanate (B) is more preferably from 0.1 to 0.4, and still more preferably from 0.1 to 0.2, from the viewpoint that the swelling ratio of the resulting elastomer with respect to toluene is low.

In the present invention, the dilutable ratio is as follows: 1 ml of an organic solvent ("Pegasol 3040" manufactured by Mobil Oil Co., Ltd.) is gradually added to 10 ml of isocyanate heated to 40° C. The magnification calculated by the formula.

[mathematical formula 1]

Dilutable ratio = A2/Al

In the above formula, Al represents the volume (ml) of isocyanate, and A2 represents the dropwise amount (ml) of the organic solvent at the point where cloudiness occurs.

In the present invention of the third aspect, the polyisocyanate (B) is not particularly limited except for the dilutable ratio described above, and examples thereof include aromatic isocyanate, aliphatic isocyanate, and alicyclic isocyanate. Specific examples of the polyisocyanate (B) are as described in the first aspect of the present invention as long as it is within the range of the aforementioned dilutable ratio.

In the present invention of the third aspect, it is preferable that the average number of functional groups (average number of NCO groups) in one molecule of the polyisocyanate (B) is 2.5 to 5.0. By using a polyisocyanate having such an average number of functional groups, the pot life can be relatively extended, and a polyurethane elastomer having a higher gel fraction can be obtained.

For example, when using two types of polyisocyanate, isocyanate A and isocyanate B, it is preferable that the average number of functional groups of two types of isocyanate is 2.5-5.0.

＜Polyrotaxane (C)＞

In the present invention of the third aspect, regarding the cyclic molecule (Ca), the linear molecule (Cb), the capping group (Cc) and the modification group (Cd) of the polyrotaxane (C), as in the present invention of the first aspect Invention is recorded. In the third aspect of the present invention, the mass addition rate of polyrotaxane (C) is preferably 1 to 10 mass with respect to the mass sum of polycarbonate polyol (A), polyisocyanate (B), and polyrotaxane (C). %, more preferably 2 to 10 mass%, even more preferably 3 to 10 mass%. When the addition rate of the polyrotaxane (C) is in such a range, a polyurethane elastomer having a higher gel fraction can be obtained, and the pot life at the time of production can be relatively extended.

In the third aspect of the present invention, the polyurethane resin composition contains at least polycarbonate polyol (A), polyisocyanate (B) and polyrotaxane (C), and the dilutable ratio of the polyisocyanate (B) is Composition below 0.4. The arbitrary components contained in the composition such as catalyst and antioxidant, the value of NCO/OH, etc. are as described in the first aspect of the present invention.

In the present invention of the third aspect, the method for producing the injection-molded thermosetting polyurethane elastomer is as described in the present invention of the first aspect.

Example

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

[example 1]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 0.20 g (1 mass %) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super Polymer SH3400P" manufactured by Advanced Softmaterials Co., Ltd.), 16.6 g (80 mass %) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and the polycarbonate diol that dimethyl carbonate reaction obtains), the mixed solution of 0.11g dibutyltin dilaurate/defoamer , and 0.21 g of an antioxidant ("IRGANOX 1726" manufactured by BASF Japan Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. 3.92 g (19% by mass) of hydrogenated xylylene diisocyanate (H6XDI) was uniformly mixed with the prepared polyrotaxane liquid mixture with a rotary revolution mixer. The obtained mixture was poured into a rubber mold made of Teflon (registered trademark), and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a gel fraction measurement test.

[Example 2]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 0.61g (3% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH3400P" manufactured by Advanced Softmaterials Co., Ltd.), 16.1g (78% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and the polycarbonate diol that dimethyl carbonate reaction obtains), the mixed solution of 0.13g dibutyltin dilaurate/defoamer , and 0.21 g of an antioxidant ("IRGANOX 1726" manufactured by BASF Japan Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. 3.91 g (19% by mass) of hydrogenated xylylene diisocyanate (H6XDI) and the prepared polyrotaxane mixed liquid were uniformly mixed with a rotary revolution mixer. The obtained mixture was poured into a rubber mold made of Teflon (registered trademark), and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a gel fraction measurement test.

[Example 3]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 1.00 g (5 mass %) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super Polymer SH3400P" manufactured by Advanced Softmaterials Co., Ltd.), 15.4 g (76 mass %) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and the polycarbonate diol that dimethyl carbonate reaction obtains), the mixed solution of 0.12g dibutyltin dilaurate/defoamer , and 0.20 g of an antioxidant ("IRGANOX 1726" manufactured by BASF Japan Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. 3.81 g (19% by mass) of hydrogenated xylylene diisocyanate (H6XDI) and the prepared polyrotaxane mixed liquid were uniformly mixed with a rotary revolution mixer. The obtained mixture was poured into a rubber mold made of Teflon (registered trademark), and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a gel fraction measurement test.

[Example 4]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 5.77g (10% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH3400P" manufactured by Advanced Softmaterials Co., Ltd.), 42.3g (73% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and the polycarbonate diol that dimethyl carbonate reaction obtains), the mixed solution of 0.29g dibutyltin dilaurate/defoamer , and 0.58 g of an antioxidant ("IRGANOX 1726" manufactured by BASF Japan Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. 9.99 g (17% by mass) of hydrogenated xylylene diisocyanate (H6XDI) and the prepared polyrotaxane mixed liquid were uniformly mixed with a rotary revolution mixer. The obtained mixture was poured into a rubber mold made of Teflon (registered trademark), and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a gel fraction measurement test.

[Example 5]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 0.96g (5% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH3400P" manufactured by Advanced Softmaterials Co., Ltd.), 15.0g (77% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and polycarbonate diol obtained by the reaction of dimethyl carbonate), the mixed solution of 0.10g dibutyltin dilaurate/defoamer , and 0.19 g of an antioxidant ("IRGANOX 1726" manufactured by BASF Japan Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. 3.48 g (18% by mass) of hydrogenated xylylene diisocyanate (H6XDI) and the prepared polyrotaxane mixed liquid were uniformly mixed with a rotary revolution mixer. The obtained mixture was poured into a rubber mold made of Teflon (registered trademark), and heated at 160° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a gel fraction measurement test.

[Example 6]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 0.93g (5% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "SuperPolymer SH3400P" manufactured by Advanced Softmaterials Co., Ltd.), 14.6g (78% by mass) of ETERNACOLL (registered trademark) UM90 (1/3) (manufactured by Ube Industries; number average molecular weight 893; hydroxyl value 126mgKOH/g; polyol component is a polyol with a molar ratio of 1,4-cyclohexanedimethanol:1,6-hexanediol=1:3 Polycarbonate diol obtained by reacting the mixture with carbonate), 0.09 g of dibutyltin dilaurate/defoamer mixed liquid, and 0.19 g of antioxidant (BASF Japan Co., Ltd. "IRGANOX1726") were mixed to obtain a polyrotaxane mixture liquid. 3.28 g (17% by mass) of hydrogenated xylylene diisocyanate (H6XDI) was uniformly mixed with the prepared polyrotaxane liquid mixture with a rotary revolution mixer. The obtained mixture was poured into a rubber mold made of Teflon (registered trademark), and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a gel fraction measurement test.

[Example 7]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 0.55g (3% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH3400P" manufactured by Advanced Softmaterials Co., Ltd.), 15.1g (81% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and polycarbonate diol obtained by the reaction of dimethyl carbonate), the mixed solution of 0.10g dibutyltin dilaurate/defoamer , and 0.18 g of an antioxidant ("IRGANOX 1726" manufactured by BASF Japan Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. 3.01 g (16% by mass) of hydrogenated xylylene diisocyanate (H6XDI) and the prepared polyrotaxane mixed liquid were uniformly mixed with a rotary revolution mixer. The obtained mixture was poured into a rubber mold made of Teflon (registered trademark), and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a gel fraction measurement test.

[Example 8]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 0.98g (5% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH3400P" manufactured by Advanced Softmaterials Co., Ltd.), 15.6g (79% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and the polycarbonate diol that dimethyl carbonate reaction obtains), the mixed solution of 0.12g dibutyltin dilaurate/defoamer , and 0.21 g of an antioxidant ("IRGANOX 1726" manufactured by BASF Japan Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. 3.06 g (16% by mass) of hydrogenated xylylene diisocyanate (H6XDI) and the prepared polyrotaxane mixed liquid were uniformly mixed with a rotary revolution mixer. The obtained mixture was poured into a rubber mold made of Teflon (registered trademark), and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a gel fraction measurement test.

[Example 9]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 0.98g (5% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH3400P" manufactured by Advanced Softmaterials Co., Ltd.), 16.7g (84% by mass) of ETERNACOLL (registered trademark) UH200 (Ube Industries, Ltd. Number average molecular weight 2028; Hydroxyl value 55mgKOH/g; 1,6-hexanediol and polycarbonate diol obtained by the reaction of dimethyl carbonate), the mixed solution of 0.10g dibutyltin dilaurate/defoamer , and 0.20 g of an antioxidant ("IRGANOX 1726" manufactured by BASF Japan Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. 2.11 g (11% by mass) of hydrogenated xylylene diisocyanate (H6XDI) and the prepared polyrotaxane mixed liquid were uniformly mixed with a rotary revolution mixer. The obtained mixture was poured into a rubber mold made of Teflon (registered trademark), and cured by heating at 160° C. for 7 hours to obtain an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a gel fraction measurement test.

[Example 10]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 1.08g (3% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH3400P" manufactured by Advanced Softmaterials Co., Ltd.), 29.7g (83% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and the polycarbonate diol that dimethyl carbonate reaction obtains), the mixed solution of 0.19g dibutyltin dilaurate/defoamer , and 0.37 g of an antioxidant ("IRGANOX 1726" manufactured by BASF Japan Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. 5.11 g (14% by mass) of hydrogenated xylylene diisocyanate (H6XDI) and the prepared polyrotaxane mixed liquid were uniformly mixed with a rotary revolution mixer. The obtained mixture was poured into a rubber mold made of Teflon (registered trademark), and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a gel fraction measurement test.

[Example 11]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 2.99g (3% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH3400P" manufactured by Advanced Softmaterials Co., Ltd.), 80.0g (74% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and the polycarbonate diol that dimethyl carbonate reaction obtains), the mixed solution of 0.50g dibutyltin dilaurate/defoamer , and 1.00 g of an antioxidant ("IRGANOX 1726" manufactured by BASF Japan Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. 3.71g (14% by mass) of hydrogenated xylylene diisocyanate (H6XDI), 21.1g of prepared polyrotaxane mixed solution, and 2.53g (9% by mass) of alumina (manufactured by Nippon Light Metal Co., Ltd. lowsoda aluminuma LS-242") and mix evenly. The obtained mixture was poured into a rubber mold made of Teflon (registered trademark), and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a gel fraction measurement test.

[Example 12]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 2.99g (3% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH3400P" manufactured by Advanced Softmaterials Co., Ltd.), 80.0g (79% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and the polycarbonate diol that dimethyl carbonate reaction obtains), the mixed solution of 0.50g dibutyltin dilaurate/defoamer , and 1.00 g of an antioxidant ("IRGANOX 1726" manufactured by BASF Japan Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. 3.76g (17% by mass) of hydrogenated xylylene diisocyanate (H6XDI), 18.7g of prepared polyrotaxane mixed solution, and 0.22g (1% by mass) of aluminum oxide (manufactured by Nippon Light Metal Co., Ltd. lowsoda aluminuma LS-242") and mix evenly. The obtained mixture was poured into a rubber mold made of Teflon (registered trademark), and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a gel fraction measurement test.

[Comparative example 1]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 0.50 g (3% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super Polymer SH3400P" manufactured by Advanced Softmaterials), 13.2 g (79% by mass) of polyether diol (manufactured by Aldrich; Average molecular weight 966; hydroxyl value 116 mgKOH/g), 0.08 g of dibutyltin dilaurate/defoamer mixed solution, and 0.17 g of antioxidant (BASF Japan Co., Ltd. "IRGANOX 1726") were mixed to obtain a polyrotaxane mixed solution. 2.92 g (18% by mass) of hydrogenated xylylene diisocyanate (H6XDI) was uniformly mixed with the prepared polyrotaxane liquid mixture with a rotary revolution mixer. The obtained mixture was poured into a rubber mold made of Teflon (registered trademark), and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a gel fraction measurement test.

[Comparative example 2]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 7.26g (15% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH3400P" manufactured by Advanced Softmaterials Co., Ltd.), 33.1g (65% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and the polycarbonate diol that dimethyl carbonate reaction obtains), the mixed solution of 0.24g dibutyltin dilaurate/defoamer , and 0.59 g of an antioxidant ("IRGANOX 1726" manufactured by BASF Japan Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. 9.99 g (20% by mass) of hydrogenated xylylene diisocyanate (H6XDI) and the prepared polyrotaxane mixed liquid were uniformly mixed with a rotary revolution mixer. The obtained mixture was poured into a rubber mold made of Teflon (registered trademark), and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a gel fraction measurement test.

[Comparative example 3]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 0.67g (3% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH3400P" manufactured by Advanced Softmaterials Co., Ltd.), 21.6g (97% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and the polycarbonate diol that dimethyl carbonate reaction obtains), the mixed solution of 0.11g dibutyltin dilaurate/defoamer , and 0.22 g of an antioxidant ("IRGANOX 1726" manufactured by BASF Japan Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. The polyrotaxane mixture was poured into a Teflon (registered trademark) rubber mold and cured by heating at 120° C. for 7 hours to obtain an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a gel fraction measurement test.

[Comparative example 4]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 0.79g (3% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH3400P" manufactured by Advanced Softmaterials Co., Ltd.), 21.3g (80% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and the polycarbonate diol that dimethyl carbonate reaction obtains), the mixed solution of 0.14g dibutyltin dilaurate/defoamer , and 0.27 g of an antioxidant (“IRGANOX 1726” manufactured by BASF Japan Co., Ltd.), and 2.67 g of dimethylacetamide as a solvent were mixed to obtain a polyrotaxane liquid mixture. 4.54 g (17% by mass) of hydrogenated xylylene diisocyanate (H6XDI) and the prepared polyrotaxane mixed liquid were uniformly mixed with a rotary revolution mixer. The obtained mixture was poured into a rubber mold made of Teflon (registered trademark), and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a gel fraction measurement test.

[Comparative Example 5]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 2.91g (2% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH3400P" manufactured by Advanced Softmaterials Co., Ltd.), 58.2g (40% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and the polycarbonate diol that dimethyl carbonate reaction obtains), the mixed solution of 0.50g dibutyltin dilaurate/defoamer , 1.11 g of an antioxidant ("IRGANOX 1726" manufactured by BASF Japan Co., Ltd.), and 72.3 g (50% by mass) of alumina ("low soda aluminum LS-242" manufactured by Nippon Light Metal Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. 11.6 g (8% by mass) of hydrogenated xylylene diisocyanate (H6XDI) and the prepared polyrotaxane mixed liquid were uniformly mixed with a rotary revolution mixer. The obtained mixture was poured into a rubber mold made of Teflon (registered trademark), and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a gel fraction measurement test.

(polyrotaxane)

"Super Polymer SH3400P" manufactured by Advanced Softmaterials Co., Ltd. used in each experimental example is a polyrotaxane specified by CAS No. 928045-45-8, and has a weight average molecular weight of 700,000. In addition, the polystyrene-equivalent weight-average molecular weight of the polyethylene glycol serving as the shaft was 35,000.

(Evaluation of Gel Rate)

After toluene immersion (100 degreeC, 22 hours), the gel fraction was calculated|required by the following formula from the mass after drying (180 degreeC, 3 hours) in a vacuum oven.

Gel rate=W2/W1×100(%)

In the above formula, W1 represents the mass (g) before immersion, and W2 represents the mass (g) after drying.

(evaluation of liquidity)

The surface of the cured product after heating was observed visually and evaluated on the basis of the following criteria.

○: The surface is smooth

×: The surface is convex and concave

(evaluation of the presence or absence of air bubbles)

The surface and inside of the cured product after heating were observed visually, and the following criteria were used for evaluation.

○: There are almost no air bubbles on the surface and inside of the cured product

×: There are many bubbles on the surface and inside of the cured product

(evaluation of stickiness)

The cured product after heating was heated to 60° C., and the surface was touched with a finger, and the following criteria were used for evaluation.

○: Almost no stickiness on the surface

×: Much stickiness on the surface

In Examples 1 to 12, good results were obtained for fluidity, presence or absence of air bubbles, gel fraction, and viscosity. On the other hand, in Comparative Examples 1 and 3 which did not contain polycarbonate polyol (A) or polyisocyanate (B), the result that the gel fraction was low was obtained. In addition, in Comparative Example 2 in which the amount of polyrotaxane was large, good fluidity could not be obtained. In Comparative Example 4 containing a solvent, bubbles were generated. In Comparative Example 5 in which the amount of the inorganic material was large, good viscosity could not be obtained.

[Example 13]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 0.19g (1% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH2400P" manufactured by Advanced Softmaterials Co., Ltd.), 15.4g (82% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and polycarbonate diol obtained by the reaction of dimethyl carbonate), the mixed solution of 0.10g dibutyltin dilaurate/defoamer , and 0.20 g of an antioxidant ("IRGANOX 1726" manufactured by BASF Japan Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. 3.16 g (17% by mass) of hydrogenated xylylene diisocyanate (H6XDI) and the prepared polyrotaxane mixed liquid were uniformly mixed with a rotary revolution mixer. The obtained mixture was poured into a rubber mold made of Teflon (registered trademark), and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a gel fraction measurement test.

[Example 14]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 0.21g (1% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH2300P" manufactured by Advanced Softmaterials Co., Ltd.), 17.5g (82% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and the polycarbonate diol that dimethyl carbonate reaction obtains), the mixed solution of 0.11g dibutyltin dilaurate/defoamer , and 0.22 g of an antioxidant ("IRGANOX 1726" manufactured by BASF Japan Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. 3.73 g (17% by mass) of hydrogenated xylylene diisocyanate (H6XDI) was uniformly mixed with the prepared polyrotaxane liquid mixture with a rotary revolution mixer. The obtained mixture was poured into a rubber mold made of Teflon (registered trademark), and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a gel fraction measurement test.

[Example 15]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 0.59g (3% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH2300P" manufactured by Advanced Softmaterials Co., Ltd.), 15.7g (80% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and polycarbonate diol obtained by the reaction of dimethyl carbonate), the mixed solution of 0.10g dibutyltin dilaurate/defoamer , and 0.22 g of an antioxidant ("IRGANOX 1726" manufactured by BASF Japan Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. 3.46 g (17% by mass) of hydrogenated xylylene diisocyanate (H6XDI) and the prepared polyrotaxane mixed liquid were uniformly mixed with a rotary revolution mixer. The obtained mixture was poured into a rubber mold made of Teflon (registered trademark), and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a gel fraction measurement test.

[Example 16]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 0.93g (5% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH2400P" manufactured by Advanced Softmaterials Co., Ltd.), 14.5g (78% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and the polycarbonate diol that dimethyl carbonate reaction obtains), the mixed solution of 0.11g dibutyltin dilaurate/defoamer , and 0.23 g of an antioxidant ("IRGANOX 1726" manufactured by BASF Japan Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. 3.14 g (17% by mass) of hydrogenated xylylene diisocyanate (H6XDI) and the prepared polyrotaxane mixed liquid were uniformly mixed with a rotary revolution mixer. The obtained mixture was poured into a rubber mold made of Teflon (registered trademark), and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a gel fraction measurement test.

[Example 17]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 1.05 g (5% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH2400P" manufactured by Advanced Softmaterials Co., Ltd.), 16.8 g (80% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and the polycarbonate diol that dimethyl carbonate reaction obtains), the mixed solution of 0.13g dibutyltin dilaurate/defoamer , and 0.23 g of an antioxidant ("IRGANOX 1726" manufactured by BASF Japan Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. 3.28 g (15% by mass) of hydrogenated xylylene diisocyanate (H6XDI) was uniformly mixed with the prepared polyrotaxane liquid mixture with a rotary revolution mixer. The obtained mixture was poured into a rubber mold made of Teflon (registered trademark), and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a gel fraction measurement test.

[Comparative Example 6]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 1.05g (3% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH2300P" manufactured by Advanced Softmaterials Co., Ltd.), 28.1g (80% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol reacts with dimethyl carbonate to obtain the polycarbonate diol), the mixed solution of 0.18g dibutyltin dilaurate/defoamer , 0.35 g of an antioxidant ("IRGANOX 1726" manufactured by BASF Japan Co., Ltd.), and 3.52 g of dimethylacetamide as a solvent were mixed to obtain a polyrotaxane liquid mixture. 6.00 g (17% by mass) of hydrogenated xylylene diisocyanate (H6XDI) and the prepared polyrotaxane mixed liquid were uniformly mixed with a rotary revolution mixer. The obtained mixture was poured into a rubber mold made of Teflon (registered trademark), and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a gel fraction measurement test.

[Comparative Example 7]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 1.04g (3% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH2300P" manufactured by Advanced Softmaterials Co., Ltd.), 33.6g (97% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and the polycarbonate diol that dimethyl carbonate reaction obtains), the mixed solution of 0.17g dibutyltin dilaurate/defoamer , and 0.38 g of an antioxidant ("IRGANOX 1726" manufactured by BASF Japan Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. The polyrotaxane mixture was poured into a Teflon (registered trademark) rubber mold and cured by heating at 120° C. for 7 hours to obtain an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a gel fraction measurement test.

[Comparative Example 8]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 0.57 g (3% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super Polymer SH2300P" manufactured by Advanced Softmaterials), 15.0 g (78% by mass) of polytetramethylene glycol (manufactured by Aldrich; Average molecular weight 966; hydroxyl value 116 mgKOH/g), 0.09 g of dibutyltin dilaurate/defoamer mixed solution, and 0.19 g of antioxidant (BASF Japan Co., Ltd. "IRGANOX 1726") were mixed to obtain a polyrotaxane mixed solution. 3.56 g (19% by mass) of hydrogenated xylylene diisocyanate (H6XDI) was uniformly mixed with the prepared polyrotaxane liquid mixture with a rotary revolution mixer. The obtained mixture was poured into a rubber mold made of Teflon (registered trademark), and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a gel fraction measurement test.

(polyrotaxane)

"Super Polymer SH3400P", "Super Polymer SH2400P", "Super Polymer SH2300P", and "Super Polymer SH1300P" manufactured by Advanced Softmaterials Co., Ltd. used in each experiment example are polyrotaxanes specified by CAS No. 928045-45-8.

Super Polymer SH3400P: The weight average molecular weight is 700,000. In addition, the polystyrene-equivalent number average molecular weight of the polyethylene glycol serving as the axis was 35,000. The viscosity at 120°C is 5600cP. In addition, the mass ratio of the modification group of the polyrotaxane was 82%.

Super Polymer SH2400P: The weight average molecular weight is 400,000. In addition, the polystyrene-equivalent number average molecular weight of the polyethylene glycol serving as the axis was 20,000. The viscosity at 120°C is 2700cP. In addition, the mass ratio of the modification group of the polyrotaxane was 82%.

Super Polymer SH2300P: The weight average molecular weight is 300,000. In addition, the polystyrene-equivalent number average molecular weight of the polyethylene glycol serving as the axis was 20,000. The viscosity at 120°C is 3000cP. In addition, the mass ratio of the modification group of the polyrotaxane was 77%.

Evaluations of the gel fraction, fluidity, and presence or absence of air bubbles were as described above.

[table 3]

[Table 4]

In Example 1 of Table 1, compared with the examples in Table 3, by using a polyrotaxane (C) with a lower viscosity, the fluidity, the presence or absence of bubbles, and the viscosity were not changed, and the gel ratio could be further increased. In addition, in Comparative Example 6 using a solvent, bubbles were generated, and in Comparative Examples 7 and 8 that did not contain polycarbonate polyol (A) or polyisocyanate (B), both of Comparative Examples 7 and 8 showed a result that the gel fraction was low.

[Example 18]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 0.94g (1% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH2300P" manufactured by Advanced Softmaterials Co., Ltd.), 64.2g (68% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and the polycarbonate diol that dimethyl carbonate reaction obtains), the mixed solution of 0.47g dibutyltin dilaurate/defoamer , and 1.04 g of an antioxidant (“IRGANOX 1726” manufactured by Toyotsu Chemiplas Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. 29.2 g (31% by mass) of DURANATED 101 and the prepared polyrotaxane liquid mixture were uniformly mixed with a rotary revolution mixer. The resulting mixture was poured into a polytetrafluoroethylene rubber mold and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a toluene swelling rate measurement test.

[Example 19]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 2.86g (3% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH2300P" manufactured by Advanced Softmaterials Co., Ltd.), 63.2g (66% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and the polycarbonate diol that dimethyl carbonate reaction obtains), the mixed solution of 0.49g dibutyltin dilaurate/defoamer , and 0.98 g of an antioxidant ("IRGANOX 1726" manufactured by Toyotsu Chemiplas Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. 30.0 g (31% by mass) of DURANATED 101 and the prepared polyrotaxane liquid mixture were uniformly mixed with a rotary revolution mixer. The resulting mixture was poured into a polytetrafluoroethylene rubber mold and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a toluene swelling rate measurement test.

[Example 20]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 4.70g (5% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH2300P" manufactured by Advanced Softmaterials Co., Ltd.), 60.4g (64% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number-average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and polycarbonate diol obtained by the reaction of dimethyl carbonate), the mixed solution of 0.48g dibutyltin dilaurate/defoamer , and 0.96 g of an antioxidant (“IRGANOX 1726” manufactured by Toyotsu Chemiplas Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. 29.4 g (31% by mass) of DURANATED 101 and the prepared polyrotaxane liquid mixture were uniformly mixed with a rotary revolution mixer. The resulting mixture was poured into a polytetrafluoroethylene rubber mold and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a toluene swelling rate measurement test.

[Example 21]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 2.90g (3% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH2300P" manufactured by Advanced Softmaterials Co., Ltd.), 59.2g (59% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and the polycarbonate diol that dimethyl carbonate reaction obtains), the mixed solution of 0.49g dibutyltin dilaurate/defoamer , and 0.98 g of an antioxidant ("IRGANOX 1726" manufactured by Toyotsu Chemiplas Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. 35.7 g (36% by mass) of DURANATE D201 and the prepared polyrotaxane liquid mixture were uniformly mixed with a rotary revolution mixer. The resulting mixture was poured into a polytetrafluoroethylene rubber mold and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a toluene swelling rate measurement test.

[Example 22]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 2.29g (3% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH2300P" manufactured by Advanced Softmaterials Co., Ltd.), 58.6g (76% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and the polycarbonate diol that dimethyl carbonate reaction obtains), the mixed solution of 0.39g dibutyltin dilaurate/defoamer , and 0.78 g of an antioxidant (“IRGANOX 1726” manufactured by Toyotsu Chemiplas Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. 16.4 g (21% by mass) of DURANATE TPA-100 and the prepared polyrotaxane liquid mixture were uniformly mixed with a rotary revolution mixer. The resulting mixture was poured into a polytetrafluoroethylene rubber mold and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a toluene swelling rate measurement test.

[Example 23]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 2.85g (3% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH2300P" manufactured by Advanced Softmaterials Co., Ltd.), 63.2g (66% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and the polycarbonate diol that dimethyl carbonate reaction obtains), the mixed solution of 0.46g dibutyltin dilaurate/defoamer , and 0.94 g of an antioxidant ("IRGANOX 1726" manufactured by Toyotsu Chemiplas Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. 29.2 g (31% by mass) of Desmodur XP2580 and the prepared polyrotaxane liquid mixture were uniformly mixed with a rotary revolution mixer. The resulting mixture was poured into a polytetrafluoroethylene rubber mold and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a toluene swelling rate measurement test.

[Example 24]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 2.53g (3% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH2300P" manufactured by Advanced Softmaterials Co., Ltd.), 57.7g (68% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and the polycarbonate diol that dimethyl carbonate reaction obtains), the mixed solution of 0.44g dibutyltin dilaurate/defoamer , and 0.85 g of an antioxidant ("IRGANOX 1726" manufactured by Toyotsu Chemiplas Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. 24.3 g (29% by mass) of Sumidur N3300 and the prepared polyrotaxane liquid mixture were uniformly mixed with a rotary revolution mixer. The resulting mixture was poured into a polytetrafluoroethylene rubber mold and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a toluene swelling rate measurement test.

[Example 25]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 2.70 g (3% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; “Super PolymerSH2300P” manufactured by Advanced Softmaterials Co., Ltd.), 61.0 g (67% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and the polycarbonate diol that dimethyl carbonate reaction obtains), the mixed solution of 0.45g dibutyltin dilaurate/defoamer , and 0.91 g of an antioxidant (“IRGANOX 1726” manufactured by Toyotsu Chemiplas Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. 27.0 g (30% by mass) of CoronateHX was uniformly mixed with the prepared polyrotaxane liquid mixture with a rotary revolution mixer. The resulting mixture was poured into a polytetrafluoroethylene rubber mold and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a toluene swelling rate measurement test.

[Example 26]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 2.62g (3% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH2300P" manufactured by Advanced Softmaterials Co., Ltd.), 55.7g (64% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and the polycarbonate diol that dimethyl carbonate reaction obtains), the mixed solution of 0.44g dibutyltin dilaurate/defoamer , and 0.88 g of an antioxidant ("IRGANOX 1726" manufactured by Toyotsu Chemiplas Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. 7.32 g (8% by mass) of DURANATE TPA-100, 22.0 g (25% by mass) of DURANATE D201 and the prepared polyrotaxane liquid mixture were uniformly mixed with a self-rotating revolution mixer. The resulting mixture was poured into a polytetrafluoroethylene rubber mold and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a toluene swelling rate measurement test.

[Example 27]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 2.97g (3% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH2300P" manufactured by Advanced Softmaterials Co., Ltd.), 61.3g (61% by mass) of ETERNACOLL (registered trademark) UM90 (1/1 ) (manufactured by Ube Industries; number average molecular weight 914; hydroxyl value 123 mgKOH/g; polyol component is 1,4-cyclohexanedimethanol:1,6-hexanediol=1:1 molar ratio polyol Polycarbonate diol obtained by reacting the mixture with carbonate), 0.50 g of dibutyltin dilaurate/defoamer mixture, and 1.00 g of antioxidant (Toyotsu Chemiplas Co., Ltd. "IRGANOX1726") were mixed to obtain a polywheel alkane mixture. 9.05g (9% by mass) of DURANATE TPA-100, 27.2g (27% by mass) of DURANATE D201 were uniformly mixed with the prepared polyrotaxane liquid mixture with a rotary revolution mixer. The resulting mixture was poured into a polytetrafluoroethylene rubber mold and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a toluene swelling rate measurement test.

[Example 28]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 4.72g (5% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH2300P" manufactured by Advanced Softmaterials Co., Ltd.), 57.1g (60% by mass) of ETERNACOLL (registered trademark) UM90 (3/1 ) (manufactured by Ube Industries; number average molecular weight 917; hydroxyl value 122 mgKOH/g; polyol composition is 1,4-cyclohexanedimethanol:1,6-hexanediol=3:1 molar ratio polyol polycarbonate diol obtained by reacting the mixture with carbonate), 0.48 g of dibutyltin dilaurate/defoamer mixture, and 0.95 g of antioxidant ("IRGANOX 1726" manufactured by Toyotsu Chemiplas Co., Ltd.) were mixed to obtain a polywheel alkane mixture. 4.19 g (4% by mass) of DURANATE TLA-100 and 29.3 g (31% by mass) of DURANATE D201 were uniformly mixed with the prepared polyrotaxane liquid mixture using a self-rotating revolution mixer. The resulting mixture was poured into a polytetrafluoroethylene rubber mold and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a toluene swelling rate measurement test.

[Example 29]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 2.93g (3% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH2300P" manufactured by Advanced Softmaterials Co., Ltd.), 56.8g (57% by mass) of ETERNACOLL (registered trademark) UM90 (3/1 ) (manufactured by Ube Industries; number average molecular weight 917; hydroxyl value 122 mgKOH/g; polyol composition is 1,4-cyclohexanedimethanol:1,6-hexanediol=3:1 molar ratio polyol Polycarbonate diol obtained by reacting the mixture with carbonate), 0.49 g of dibutyltin dilaurate/defoamer mixture, and 0.99 g of antioxidant ("IRGANOX 1726" manufactured by Toyotsu Chemiplas Co., Ltd.) were mixed to obtain a polywheel alkane mixture. 39.9 g (40% by mass) of DURANATE D201 and the prepared polyrotaxane liquid mixture were uniformly mixed with a rotary revolution mixer. The resulting mixture was poured into a polytetrafluoroethylene rubber mold and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a toluene swelling rate measurement test.

[Example 30]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 4.5g (5% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH2300P" manufactured by Advanced Softmaterials), 47.7g (53% by mass) of ETERNACOLL (registered trademark) UM90 (3/1 ) (manufactured by Ube Industries; number average molecular weight 917; hydroxyl value 122 mgKOH/g; polyol composition is 1,4-cyclohexanedimethanol:1,6-hexanediol=3:1 molar ratio polyol Polycarbonate diol obtained by reacting the mixture with carbonate), 0.4 g of dibutyltin dilaurate/defoamer mixture, and 0.9 g of antioxidant ("IRGANOX 1726" manufactured by Toyotsu Chemiplas Co., Ltd.) were mixed to obtain a polywheel alkane mixture. 37.8 g (42% by mass) of DURANATE D201 and the prepared polyrotaxane liquid mixture were uniformly mixed with a rotary revolution mixer. The resulting mixture was poured into a polytetrafluoroethylene rubber mold and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a toluene swelling rate measurement test.

[Example 31]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 2.95g (3% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH2300P" manufactured by Advanced Softmaterials Co., Ltd.), 68.4g (61% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and the polycarbonate diol that dimethyl carbonate reaction obtains), the mixed solution of 0.50g dibutyltin dilaurate/defoamer , and 0.99 g of an antioxidant (“IRGANOX 1726” manufactured by Toyotsu Chemiplas Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. 39.9 g (36% by mass) of DURANATED 201 and the prepared polyrotaxane liquid mixture were uniformly mixed with a rotary revolution mixer. The resulting mixture was poured into a polytetrafluoroethylene rubber mold and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a toluene swelling rate measurement test.

[Example 32]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 4.45g (5% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH2300P" manufactured by Advanced Softmaterials Co., Ltd.), 49.9g (55% by mass) of ETERNACOLL (registered trademark) UM90 (3/1 ) (manufactured by Ube Industries; number average molecular weight 917; hydroxyl value 122 mgKOH/g; polyol composition is 1,4-cyclohexanedimethanol:1,6-hexanediol=3:1 molar ratio polyol Polycarbonate diol obtained by reacting the mixture with carbonate), 0.45 g of dibutyltin dilaurate/defoamer mixture, and 0.91 g of antioxidant ("IRGANOX 1726" manufactured by Toyotsu Chemiplas Co., Ltd.) were mixed to obtain a polywheel alkane mixture. 36.3 g (40% by mass) of DURANATE D201 and the prepared polyrotaxane liquid mixture were uniformly mixed with a rotary revolution mixer. The resulting mixture was poured into a polytetrafluoroethylene rubber mold and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a toluene swelling rate measurement test.

[Example 33]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 9.48g (10% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH2300P" manufactured by Advanced Softmaterials Co., Ltd.), 48.6g (50% by mass) of ETERNACOLL (registered trademark) UM90 (3/1 ) (manufactured by Ube Industries; number average molecular weight 917; hydroxyl value 122 mgKOH/g; polyol composition is 1,4-cyclohexanedimethanol:1,6-hexanediol=3:1 molar ratio polyol polycarbonate diol obtained by reacting the mixture with carbonate), 0.48 g of dibutyltin dilaurate/defoamer mixture, and 0.97 g of antioxidant ("IRGANOX 1726" manufactured by Toyotsu Chemiplas Co., Ltd.) were mixed to obtain a polywheel alkane mixture. 38.5 g (40% by mass) of DURANATE D201 and the prepared polyrotaxane liquid mixture were uniformly mixed with a rotary revolution mixer. The resulting mixture was poured into a polytetrafluoroethylene rubber mold and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a toluene swelling rate measurement test.

[Example 34]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 4.56g (5% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH2300P" manufactured by Advanced Softmaterials Co., Ltd.), 54.0g (59% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and the polycarbonate diol that dimethyl carbonate reaction obtains), the mixed solution of 0.46g dibutyltin dilaurate/defoamer , and 0.92 g of an antioxidant (“IRGANOX 1726” manufactured by Toyotsu Chemiplas Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. 32.9 g (36% by mass) of DURANATED 201 and the prepared polyrotaxane liquid mixture were uniformly mixed with a rotary revolution mixer. The resulting mixture was poured into a polytetrafluoroethylene rubber mold and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a toluene swelling rate measurement test.

[Comparative Example 9]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 1.28g (3% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH2300P" manufactured by Advanced Softmaterials Co., Ltd.), 30.0g (63% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and the polycarbonate diol that dimethyl carbonate reaction obtains), the mixed solution of 0.22g dibutyltin dilaurate/defoamer , 0.42 g of an antioxidant (“IRGANOX 1726” manufactured by Toyotsu Chemiplas Co., Ltd.), and 4.34 g of dimethylacetamide were mixed to obtain a polyrotaxane liquid mixture. 11.8 g (25% by mass) of DURANATE D201 and 36.2 g of the prepared polyrotaxane liquid mixture were uniformly mixed with a rotary revolution mixer. The resulting mixture was poured into a polytetrafluoroethylene rubber mold and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a toluene swelling rate measurement test.

[Comparative Example 10]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 1.04g (3% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super PolymerSH2300P" manufactured by Advanced Softmaterials Co., Ltd.), 33.6g (97% by mass) of ETERNACOLL (registered trademark) UH100 (Ube Industries, Ltd. Number average molecular weight 1010; Hydroxyl value 111mgKOH/g; 1,6-hexanediol and the polycarbonate diol that dimethyl carbonate reaction obtains), the mixed solution of 0.17g dibutyltin dilaurate/defoamer , and 0.38 g of an antioxidant (“IRGANOX 1726” manufactured by Toyotsu Chemiplas Co., Ltd.) were mixed to obtain a polyrotaxane liquid mixture. The polyrotaxane mixture was poured into a polytetrafluoroethylene rubber mold and cured by heating at 120° C. for 7 hours to obtain an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a gel fraction measurement test.

[Comparative Example 11]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 2.28 g (3% by mass) of caprolactone-modified polyrotaxane (HAPR-g-PCL; "Super Polymer SH2300P" manufactured by Advanced Softmaterials), 52.2 g (68% by mass) of polytetramethylene glycol (manufactured by Aldrich; Average molecular weight 966; hydroxyl value 116 mgKOH/g), 0.39 g of dibutyltin dilaurate/defoamer mixed solution, and 0.76 g of antioxidant ("IRGANOX 1726" manufactured by Toyotsu Chemiplas Co., Ltd.) were mixed to obtain a polyrotaxane mixed solution. 22.3 g (29% by mass) of DURANATE TPA-100 and the prepared polyrotaxane liquid mixture were uniformly mixed with a rotary revolution mixer. The resulting mixture was poured into a polytetrafluoroethylene rubber mold and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a toluene swelling rate measurement test.

[Comparative Example 12]

0.031 g of dibutyltin dilaurate (DBTDL) and 15.3 g of defoamers ("FLOWLEN AC2300-C" by Kyoeisha Chemical Co., Ltd.) were mixed, and the liquid mixture of dibutyltin dilaurate/defoamers was obtained. 101 g (61% by mass) of ETERNACOLL (registered trademark) UM90 (3/1) (manufactured by Ube Industries; number average molecular weight 917; hydroxyl value 122 mgKOH/g; polyol component: 1,4-cyclohexanedimethanol: 1 , the polycarbonate diol that the polyalcohol mixture of the molar ratio of 6-hexanediol=3:1 and carbonate reacts obtains), the mixed solution of 1.65g dibutyltin dilaurate/defoamer, and 1.65g An antioxidant ("IRGANOX 1726" manufactured by Toyotsu Chemiplas Co., Ltd.) was mixed to obtain a polyrotaxane liquid mixture. 64.0 g (39% by mass) of DURANATE D201 was uniformly mixed with the prepared polyrotaxane liquid mixture with a rotary revolution mixer. The resulting mixture was poured into a polytetrafluoroethylene rubber mold and heated at 120° C. for 7 hours to cure, thereby obtaining an injection-molded thermosetting polyurethane elastomer having a thickness of about 2 mm. The obtained sample was subjected to a toluene swelling rate measurement test.

(Evaluation of dilutable ratio)

1 ml of an organic solvent ("Pegasol 3040" manufactured by Mobil Oil Co., Ltd.) was gradually added to 10 ml of polyisocyanate heated to 40° C., and the point at which the mixed solution became cloudy was defined as an end point by visual observation.

The dilutable ratio was obtained by the following formula.

Dilutable ratio = A2/A1

In the above formula, A1 represents the volume (ml) of the polyisocyanate, and A2 represents the dropwise amount (ml) of the organic solvent at the point where the mixed liquid becomes cloudy.

The dilutable ratio of the polyisocyanate used for each experiment example is shown below.

・DURANATE D101 (manufactured by Asahi Kasei Co., Ltd., difunctional aliphatic polyisocyanate): 0.1

・DURANATE D201 (manufactured by Asahi Kasei Co., Ltd., difunctional aliphatic polyisocyanate): 0.1

・DURANATE TPA-100 (manufactured by Asahi Kasei Co., Ltd., isocyanurate type trifunctional aliphatic polyisocyanate): 0.1

・DURANATE TLA-100 (manufactured by Asahi Kasei Co., Ltd., isocyanurate type trifunctional polyisocyanate): 0.1

Desmodur XP2580 (manufactured by Bayer AG, hexamethylene diisocyanate-based aliphatic polyisocyanate): 0.4

Sumidur N3300 (Sumitomo Chemical Co., Ltd., hexamethylene diisocyanate-based isocyanurate-type polyisocyanate): 0.1

・Coronate HX (manufactured by Nippon Polyurethane Co., Ltd., polyisocyanate): 0.1

・Mitsui Chemicals Co., Ltd. hydrogenated xylylene diisocyanate (H6XDI): 0.4 or more

In addition, as a reference, the dilutable ratio of other polyisocyanates is shown below.

Desmodur N3600 (manufactured by Bayer AG, hexamethylene diisocyanate-based aliphatic polyisocyanate): 0.1

Desmodur N3800 (manufactured by Bayer AG, hexamethylene diisocyanate-based aliphatic polyisocyanate): 0.1

Desmodur N3900 (manufactured by Bayer AG, hexamethylene diisocyanate-based aliphatic polyisocyanate): 0.1

Desmodur XP2840 (manufactured by Bayer AG, hexamethylene diisocyanate-based aliphatic polyisocyanate): 0.1

・Coronate HXR (manufactured by Nippon Polyurethane Co., Ltd., polyisocyanate): 0.1

・Coronate HXLV (manufactured by Nippon Polyurethane Co., Ltd., polyisocyanate): 0.1

・DURANATE TKA-100 (manufactured by Asahi Kasei Co., Ltd., isocyanurate type trifunctional polyisocyanate): 0.1

(Evaluation of toluene swelling rate)

The toluene swelling rate was obtained from the mass before and after immersion in toluene (100° C., 22 hours) by the following formula.

W1: Mass before dipping (g)

W3: Mass after dipping (g)

Swelling rate=W3/W1×100(%)

(Evaluation of compression permanent strain)

A cylindrical molded body with a thickness of 12.5 mm and a diameter of 30.0 mm was produced, and the compression permanent strain was measured under the conditions of a compression ratio of 25% and 70° C.×22 hours in accordance with JIS K-7312.

(Evaluation of Taber wear test)

Taber wear test, for a test piece with a diameter of 100mm and a thickness of 2mm, using a Taber wear tester, under the conditions of H-22 wear wheel, load 1kg, and rotation speed 60rpm, the amount of wear (mg) at 1000 rotations was measured .

The evaluation of fluidity and the presence or absence of bubbles was as described above.

[Table 7]

From Comparative Examples 18 to 20, it can be seen that as the amount of polyrotaxane added increases, the swelling ratio of p-toluene decreases. In addition, since the value of NCO/OH is made constant, the addition amount of polyrotaxane increases and the addition amount of polycarbonate polyol decreases.

In addition, comparing Examples 29, 32, and 33 with Comparative Example 12, it can be seen that the amount of wear in the Taber abrasion test of Comparative Example 12 without using polyrotaxane is large, and the swelling rate to toluene is also large, but adding 3 mass Example 32 containing % polyrotaxane, Example 33 containing 5% by mass, and Example 29 containing 10% by mass showed a small amount of wear in the Taber abrasion test and a small swelling rate with respect to toluene. In addition, the same test was carried out with the sample shown in Example 2 of Table 1, and the result was that the permanent compression set was 94%, the result of the Taber abrasion test was 25 mg, and the swelling ratio was 526%. Compared with the examples in Tables 5 and 6, by using the polyisocyanate (B) with a dilutable ratio of 0.4 or less, the fluidity, the presence or absence of bubbles, and the viscosity were not changed, and the toluene swelling rate was further reduced.

Industrial availability

The injection molding thermosetting polyurethane elastomer of the present invention can be widely used as papermaking rolls, iron plate calendering rolls, printing rolls, office equipment rolls, main rolls for wire saws, embossed flat plates, skateboard wheels, solid tires, casters, storage batteries Forklifts, work trucks, industrial rollers, guide wheels for conveyor belts, guide rollers for cables or belts, Prairie springs (プレリースプリング), strip buffers (べルト Punch), oil seals, electronic equipment parts, cleaning blades, scrapers, gears, connecting rings, liners, pump liners, turbo cycloid cones, cyclone liners, grinding pads, precision Rollers for parts, conveyor rollers, game wheels, AJV wheels, urethane rubber for snowplows, shock-proof, shock-absorbing, shock-resistant urethane rubber, iron plate linings, metal parts linings, automotive linear brackets and brakes 1) Polyurethane rubber sheet materials, forklift wheels, heavy equipment conveying rollers, pinch rollers, guide rollers, buffer rollers, glass conveying string rollers, special processing rollers for pharmaceutical machinery, slitting machine blade bearing rollers, conductive polyurethane rubber Rolls, silicon wafer wire cutting rolls (main rolls), packaging and sheets, roller coaster tires, gaskets, seals, steel rolls, paper rolls, and their materials.

Claims (14)

1. An injection molding thermosetting polyurethane elastomer, which is obtained by at least reacting polycarbonate polyol (A), polyisocyanate (B) and polyrotaxane (C), and optionally as required Injection molding thermosetting polyurethane elastomer containing inorganic material (D), wherein, The polyrotaxane (C) has a cyclic molecule (Ca), a linear molecule (Cb) that penetrates the opening of the cyclic molecule (Ca) in a string, and is arranged on the linear molecule (Cb). A capping group (Cc) that prevents separation of the cyclic molecule (Ca) from the linear molecule (Cb), and a modifying group (Cd) that modifies the cyclic molecule (Ca), The mass addition rate of the polyrotaxane (C) is 1 to 10% by mass relative to the mass sum of the polycarbonate polyol (A), polyisocyanate (B), polyrotaxane (C) and inorganic material (D) The mass addition rate of the inorganic material (D) is 0 to 30% by mass relative to the mass sum of the polycarbonate polyol (A), polyisocyanate (B), polyrotaxane (C) and the inorganic material (D). 2. injection molding thermosetting polyurethane elastomer according to claim 1, wherein, the mass addition rate of inorganic material (D) is relative to polycarbonate polyol (A), polyisocyanate (B), polyrotaxane (C ) and the mass total of the inorganic material (D) contained if necessary is 0 to 9 mass%. 3. The injection molding thermosetting polyurethane elastomer according to claim 1 or 2, wherein the mass addition rate of polyrotaxane (C) is relative to polycarbonate polyol (A), polyisocyanate (B), polyrotaxane The mass sum of the alkane (C) and the inorganic material (D) contained as needed is 3-10 mass %. 4. The injection molding thermosetting polyurethane elastomer according to any one of claims 1 to 3, wherein the polycarbonate polyol (A) and polyrotaxane (C) have hydroxyl groups and polyisocyanate (B) The molar ratio of the isocyano group to have is NCO/OH=1/1 to 10/1. 5. The injection molding thermosetting polyurethane elastomer according to any one of claims 1 to 4, wherein the polycarbonate polyol (A) has a number average molecular weight of 500 to 1500. 6. The injection molding thermosetting polyurethane elastomer according to any one of claims 1 to 5, wherein the polycarbonate polyol (A) has an alicyclic ring content of 10% or less. 7. An injection molding thermosetting polyurethane elastomer, which is an injection molding thermosetting polyurethane elastomer obtained by reacting at least polycarbonate polyol (A), polyisocyanate (B) and polyrotaxane (C) without solvent body, of which, The polyrotaxane (C) has a cyclic molecule (Ca), a linear molecule (Cb) that penetrates the opening of the cyclic molecule (Ca) in a string, and is arranged on the linear molecule (Cb). A capping group (Cc) that prevents separation of the cyclic molecule (Ca) from the linear molecule (Cb), and a modifying group (Cd) that modifies the cyclic molecule (Ca), The polyrotaxane (C) has a viscosity of 5000 cP or less at 120°C. 8. injection molding thermosetting polyurethane elastomer according to claim 7, wherein, the mass addition rate of polyrotaxane (C) is relative to polycarbonate polyol (A), polyisocyanate (B), polyrotaxane ( The sum of the mass of C) is 3-10 mass %. 9. The injection molding thermosetting polyurethane elastomer according to claim 7 or 8, wherein the hydroxyl groups of the polycarbonate polyol (A) and the polyrotaxane (C) have the same isocyanate as that of the polyisocyanate (B). The molar ratio of cyanoyl groups is NCO/OH=1/1 to 10/1. 10. The injection molding thermosetting polyurethane elastomer according to any one of claims 7 to 9, wherein the mass ratio of the modifying group (Cd) is relative to the cyclic molecule (Ca), linear molecule (Cb), The mass sum of the capping group (Cc) and the modifying group (Cd) is 80% or less. 11. An injection molding thermosetting polyurethane elastomer, which is an injection molding thermosetting polyurethane elastomer obtained by reacting at least polycarbonate polyol (A), polyisocyanate (B) and polyrotaxane (C) without solvent body, of which The polyrotaxane (C) has a cyclic molecule (Ca), a linear molecule (Cb) that penetrates the opening of the cyclic molecule (Ca) in a string, and is arranged on the linear molecule (Cb). A capping group (Cc) that prevents separation of the cyclic molecule (Ca) from the linear molecule (Cb), and a modifying group (Cd) that modifies the cyclic molecule (Ca), The dilutable ratio of the polyisocyanate (B) is 0.4 or less. 12. injection molding thermosetting polyurethane elastomer according to claim 11, wherein, the mass addition rate of polyrotaxane (C) is relative to polycarbonate polyol (A), polyisocyanate (B), polyrotaxane ( The sum of the mass of C) is 2-10 mass %. 13. The injection molding thermosetting polyurethane elastomer according to claim 11 or 12, wherein the average number of functional groups in one molecule of polyisocyanate (B) is 2.5 to 5.0. 14. The injection molding thermosetting polyurethane elastomer according to any one of claims 11 to 13, wherein the polyisocyanate (B) has a dilutable ratio of 0.2 or less.