JP2017075301A - Cast thermosetting type polyurethane elastomer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cast thermosetting type polyurethane elastomer that has a long pot life, has no bubbles in the cast molded cured product as well as has only a small compression set.SOLUTION: A cast thermosetting type polyurethane elastomer comprises, as a component, a polyol compound (A) containing at least a polycarbonate polyol, a polyisocyanate (B), and a polyrotaxane (C), in which the mass addition rate of the polyrotaxane (C) is more than 10 mass% with respect to the total mass of the polycarbonate polyol-containing polyol compound (A), the polyisocyanate (B), and the polyrotaxane (C).SELECTED DRAWING: None

Description

  The present invention relates to a thermosetting polyurethane elastomer obtained by cast molding.

  A cyclic molecule, a linear molecule penetrating through the cyclic molecule, and a blocking group disposed at both ends of the linear molecule to prevent separation of the cyclic molecule and the linear molecule Polyrotaxane has been developed. This polyrotaxane is used as a raw material for a paint that gives a cured product having excellent scratch resistance, and as a raw material for an elastomer having characteristics such as low compression set (see Patent Document 1).

  Among them, it is known that a urethane material using polycarbonate polyol and polyrotaxane has characteristics such as desired flexibility and extensibility without containing a solvent and a softening agent (see Patent Document 2). Moreover, the urethane material which has a softness | flexibility and heat conductivity using the polycarbonate polyol, the polyrotaxane, and the heat conductive filler is proposed (refer patent document 3).

  In addition, it is known that an electrophotographic photoreceptor containing a polyrotaxane in the outermost surface layer has a characteristic that it is excellent in mechanical and electrical durability against repeated use for a long time (see Patent Document 4). ). In addition, a transparent plastic for automobiles containing polyrotaxane has been developed, and the plastic is known to have excellent scratch resistance and chipping resistance (see Patent Document 5).

JP 2011-046917 A International Publication No. 2011/108515 International Publication No. 2012/165401 JP 2012-181244 A JP 2007-106861 A Japanese Patent Application No. 2014-171408 Japanese Patent Application No. 2014-171432 Japanese Patent Application No. 2014-171440

  However, all of the urethane materials described in Patent Documents 2 and 3 cannot be cast-molded because the pot life (the pot life after mixing) is not sufficient and the fluidity of the liquid mixture is lost in a short time. There was a problem. In addition, since the material described in Patent Document 4 contains a solvent, it cannot be molded by any method other than the solution casting method (film formation method) or coating method. There was a problem of forming. The urethane material described in Patent Document 5 does not form a cross-linked structure, and has a problem that mechanical properties as an elastomer are poor because the compression set is large.

  Furthermore, Patent Document 6 describes a polyurethane elastomer material having a high gel fraction and low surface tack at 60 ° C. Patent Document 7 describes a polyurethane elastomer material having a high gel fraction. Furthermore, Patent Document 8 describes a polyurethane elastomer material having a low toluene swelling rate. On the other hand, Patent Documents 6 to 8 do not discuss polyurethane elastomer materials that satisfy both effects of pot life and compression set.

  An object of the present invention is to provide a cast thermosetting polyurethane elastomer having a long pot life, no bubbles in a cast-molded cured product, and a small compression set.

The present invention has been made in order to solve the above-described problems, and specifically has the following configuration.
[1] A cast thermosetting polyurethane elastomer comprising at least a polyol compound (A) containing a polycarbonate polyol, a polyisocyanate (B), and a polyrotaxane (C), wherein the polyrotaxane (C) is A cyclic molecule (Ca), a linear molecule (Cb) penetrating through the opening of the cyclic molecule (Ca), and a linear molecule (Cb) disposed at both ends of the cyclic molecule (Cb). Mass addition of the polyrotaxane (C) having a blocking group (Cc) that prevents separation of Ca and the linear molecule (Cb) and a modifying group (Cd) that modifies the cyclic molecule (Ca) Casting rate is greater than 10% by mass with respect to the total mass of polyol compound (A), polyisocyanate (B), and polyrotaxane (C) including polycarbonate polyol A curable polyurethane elastomers.
[2] The mass addition rate of the polyrotaxane (C) is greater than 10% by mass and less than 35% by mass with respect to the total mass of the polycarbonate polyol (A), polyisocyanate (B), and polyrotaxane (C). [1] The cast thermosetting polyurethane elastomer according to [1].
[3] The above [1] or [3], wherein the mass addition rate of the polyrotaxane (C) is 11 to 30% by mass with respect to the total mass of the polycarbonate polyol (A), polyisocyanate (B), and polyrotaxane (C). 2] is a cast thermosetting polyurethane elastomer.
[4] The mass addition rate of the polyrotaxane (C) is 15 to 25% by mass with respect to the total mass of the polycarbonate polyol (A), polyisocyanate (B), and polyrotaxane (C). 3]. The cast thermosetting polyurethane elastomer according to any one of 3).
[5] The cast thermosetting polyurethane elastomer according to any one of [1] to [4], wherein the polyol compound (A) further contains a polyether polyol.
[6] The molar ratio of the hydroxyl group of the polycarbonate polyol (A) and the polyrotaxane (C) to the isocyanate group of the polyisocyanate (B) is NCO / OH = 1/5 to 5/1. ] The cast thermosetting polyurethane elastomer according to any one of [5] to [5].
[7] The cast thermosetting polyurethane elastomer according to any one of [1] to [6], wherein the number average molecular weight of the polycarbonate polyol (A) is 300 to 3000.
[8] The method according to any one of [1] to [7], including a step of reacting a polyol compound (A) containing a polycarbonate polyol, a polyisocyanate (B), and a polyrotaxane (C) in the absence of a solvent. This is a method for producing a cast thermosetting polyurethane elastomer.

  The present invention can provide a cast thermosetting polyurethane elastomer having a long pot life, no bubbles in a cast-molded cured product, and a small compression set.

<Polyol compound (A)>
The polyol compound (A) of the present invention is a polyol compound containing a polycarbonate polyol.

<Polycarbonate polyol (Aa)>
The polycarbonate polyol (Aa) is obtained by reacting one or more polyol monomers with carbonate ester or phosgene. Polycarbonate polyols obtained by reacting one or more polyol monomers with a carbonate ester are preferred because they are easy to produce and have no side chlorination products.
The polyol monomer is not particularly limited, and examples thereof include an aliphatic polyol monomer, a polyol monomer having an alicyclic structure, and an aromatic polyol monomer.

  From the point that the viscosity of the mixture containing the polyol compound (A) containing the polycarbonate polyol, the polyisocyanate (B) and the polyrotaxane (C) is lowered, the polycarbonate polyol (Aa) is an aliphatic starting from an aliphatic polyol monomer. A polycarbonate polyol is preferred, and an aliphatic polycarbonate diol is more preferred.

The polycarbonate polyol (Aa) may be modified using a polyester polyol, a polyether polyol, a cyclic ester, or the like.
The modified polycarbonate polyol can be obtained by a transesterification reaction between a polycarbonate polyol, a polyester polyol, a polyether polyol, a cyclic ester, or the like, or a carbonate ester or phosgene, a polyol monomer, a polyester polyol or a polyether. It can also be obtained by reacting a polyol, a cyclic ester or the like.

  The aliphatic polyol monomer is not particularly limited, and examples thereof include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1 , 8-octanediol, 1,9-nonanediol, and the like; 2-methyl-1,3-propanediol, 1,5-hexanediol, 2-methyl-1,5-pentanediol, Examples include branched aliphatic diols such as 3-methyl-1,5-pentanediol and 2-methyl-1,9-nonanediol; polyfunctional alcohols having three or more functional groups such as trimethylolpropane and pentaerythritol.

  The polyol 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, Examples thereof include diols having an alicyclic structure in the main chain such as 4-cycloheptanediol, 2,7-norbornanediol, and 1,4-bis (hydroxyethoxy) cyclohexane.

  The aromatic polyol monomer is not particularly limited. For example, 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, 4,4′-naphthalenediethanol, 3,4 '-Naphthalene diethanol and the like.

  The polyester polyol for modifying the polycarbonate polyol (Aa) is not particularly limited. For example, polyester polyol of hydroxycarboxylic acid and diol such as polyester polyol of 6-hydroxycaproic acid and hexanediol, adipic acid and Examples include polyester polyols of dicarboxylic acids such as polyester polyols with hexanediol and diols.

The polyether polyol for modifying the polycarbonate polyol (Aa) is not particularly limited, and examples thereof include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
Although it does not restrict | limit especially as cyclic ester, Lactones, such as valerolactone, caprolactone, and laurolactone, etc. are mentioned.

  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. In addition, phosgene or the like capable of producing a polycarbonate polyol can be used. Among these, aliphatic carbonates are preferable and dimethyl carbonate is particularly preferable because of easy manufacture of polycarbonate polyols.

  The number average molecular weight of the polycarbonate polyol (Aa) is preferably 300 to 3000, and more preferably 300 to 2000. When the number average molecular weight is 300 or more, the pot life tends to be longer. When the number average molecular weight is 3000 or less, the compression set tends to be smaller.

  The number average molecular weight is the number average molecular weight calculated based on the hydroxyl value measured according to JIS K1557. Specifically, the hydroxyl value is measured, and is calculated as (56.1 × 1000 × valence) / hydroxyl value [mgKOH / g] by a terminal group quantification method. In the above formula, the valence is the number of hydroxyl groups in one molecule.

  The hydroxyl value of the above mixture is measured by the method described in JIS K0070.

  The polycarbonate polyol (Aa) may be used alone or in combination of two or more.

  As for the average functional group number of polycarbonate polyol (Aa), 2-5 are preferable. When the average number of functional groups is within this range, a polyurethane elastomer having a smaller compression set can be obtained, and the pot life tends to be longer.

  When the polycarbonate polyol (Aa) has an alicyclic structure, the alicyclic content is preferably 10% by mass or less. When the alicyclic content is 10% by mass or less, the strength of the cured product tends to be sufficiently high, and the compression set of the cured product tends to decrease.

Here, the alicyclic content in the polyol is a portion obtained by removing two hydrogen atoms from the alicyclic hydrocarbon (alicyclic hydrocarbon residue), such as cyclohexane when the alicyclic structure is a cyclohexane ring. It shows how much the part (cyclohexane residue) obtained by removing two hydrogen atoms from is present in mass percentage by weight in the polyol. The alicyclic content in the polyurethane resin indicates how much alicyclic hydrocarbon residues are present in mass percentage in the polyurethane resin.
Specifically, the alicyclic content can be derived from the following formula.
[Alicyclic content] = [molecular weight of alicyclic structure in polycarbonate polyol] / [molecular weight of polycarbonate polyol]

  The mass addition rate of the polycarbonate polyol (Aa) is preferably 5 to 80% by mass, more preferably 5%, based on the total mass of the polyol compound (A), polyisocyanate (B) and polyrotaxane (C) containing the polycarbonate polyol. -70 mass%. Moreover, Preferably, it is 5-60 mass%. When the raw material ratio is such, a polyurethane elastomer having a smaller compression set can be obtained.

<Other polyol compound (Ab)>
In addition to the said polycarbonate polyol (Aa), another polyol compound (Ab) can be used for the polyol compound (A) of this invention as needed.
Although it does not restrict | limit especially as another polyol compound (Ab), For example, polyether polyol, polyester polyol, a polyol monomer, etc. are mentioned.

  From the viewpoint that the viscosity of the mixture containing the polyol compound (A) containing the polycarbonate polyol, the polyisocyanate (B), and the polyrotaxane (C) is low, and from the viewpoint that the strength of the cured product is high, the polyol compound (A). It is preferable that a polyether polyol is further contained as the other polyol compound (Ab).

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

  The number average molecular weight of the polyether polyol is preferably 300 to 3000, and more preferably 300 to 2000. When the number average molecular weight is 300 or more, the pot life tends to be longer. When the number average molecular weight is 3000 or less, the compression set tends to be smaller.

  A polyether polyol may be used individually by 1 type, and may use multiple types together.

  As for the average functional group number of polyether polyol, 2-5 are preferable. When the average number of functional groups is within this range, a polyurethane elastomer having a smaller compression set can be obtained, and the pot life tends to be longer.

  Although it does not restrict | limit especially as polyester polyol, For example, dicarboxylic acids, such as polyester polyol of hydroxycarboxylic acid and diol, such as polyester polyol of 6-hydroxycaproic acid and hexanediol, and polyester polyol of adipic acid and hexanediol, and Examples thereof include polyester polyols with diols.

  The number average molecular weight of the polyester polyol is preferably 300 to 3000, more preferably 300 to 2000. When the number average molecular weight is 300 or more, the pot life tends to be longer. When the number average molecular weight is 3000 or less, the compression set tends to be smaller.

  A polyester polyol may be used independently and may use multiple types together.

  The average number of functional groups of the polyester polyol is preferably 2-5. When the average number of functional groups is within this range, a polyurethane elastomer having a smaller compression set can be obtained, and the pot life tends to be longer.

  The number average molecular weight and hydroxyl value of the polyether polyol and polyester polyol can be determined by the same method as described in the section of the polycarbonate polyol (Aa).

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

  The aliphatic polyol monomer is not particularly limited, and examples thereof include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1 Linear aliphatic diols such as 1,8-octanediol and 1,9-nonanediol; 2-methyl-1,3-propanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5 -Branched aliphatic diols such as pentanediol and 2-methyl-1,9-nonanediol; and trifunctional or higher functional polyhydric alcohols such as trimethylolpropane and pentaerythritol.

  The polyol 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, Examples thereof include diols having an alicyclic structure in the main chain such as 4-cycloheptanediol, 2,7-norbornanediol, and 1,4-bis (hydroxyethoxy) cyclohexane.

  The aromatic polyol monomer is not particularly limited. For example, 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, 4,4′-naphthalenediethanol, 3,4 '-Naphthalene diethanol and the like.

  A polyol monomer may be used independently and may use multiple types together.

  As for the average functional group number of a polyol monomer, 2-5 are preferable. When the average number of functional groups is within this range, a polyurethane elastomer having a smaller compression set can be obtained, and the pot life tends to be longer.

  The mass addition rate of the other polyol compound (Ab) is preferably 0 to 70% by mass, more preferably based on the total mass of the polyol compound (A), polyisocyanate (B), and polyrotaxane (C) containing polycarbonate polyol. Is 0-60 mass%. Moreover, Preferably it is 0-50 mass%, More preferably, it is 10-50 mass%, Especially preferably, it is 20-50 mass%, Most preferably, it is 30-50 mass%. When the raw material ratio is such, a polyurethane elastomer having a smaller compression set can be obtained.

<Polyisocyanate (B)>
Although it does not restrict | limit especially as polyisocyanate (B), For example, aromatic isocyanate, aliphatic isocyanate, alicyclic isocyanate, etc. are mentioned.

  The aromatic isocyanate is not particularly limited. For example, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene 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-naphthylene diisocyanate, 4,4 ', 4' '-triphenylmethane triisocyanate, m-isocyanatophenylsulfonyl isocyanate, p-isocyanatophenylsulfonyl isocyanate and the like. .

  Examples of the aliphatic isocyanate include, but are not limited to, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene. Diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexa Noate etc. are mentioned.

  The alicyclic isocyanate is not particularly limited. For example, isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis ( 2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate, hydrogenated xylylene diisocyanate (H6XDI) and the like.

  As 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. Moreover, it is preferable to use aromatic isocyanate from a reactive viewpoint. From the viewpoint of workability and availability, isophorone diisocyanate (IPDI) is preferably used for alicyclic isocyanate, and 2,4-tolylene diisocyanate (TDI) is preferably used for aromatic isocyanate. Moreover, polyisocyanate (B) may be used individually by 1 type, and may use multiple types together. A mixture of IPDI and TDI is particularly preferable because the pot life can be adjusted to a desired range by the blending ratio thereof while keeping the compression set at a small value.

  The average functional group number (average NCO group number) of the polyisocyanate (B) is preferably 2 to 5. It is more preferably 2.0 to 5.0, further preferably 2.0 to 4.0, and particularly preferably 2.0 to 3.0. By using such a polyisocyanate having an average number of functional groups, the pot life can be lengthened, or a polyurethane elastomer having a smaller compression set can be obtained.

  The mass addition rate of the polyisocyanate (B) is preferably 5 to 50% by mass, more preferably 10%, based on the total mass of the polyol compound (A), polyisocyanate (B) and polyrotaxane (C) including polycarbonate polyol. -40 mass%. When the mass addition rate of the polyisocyanate (B) is within such a range, the pot life can be lengthened, or a polyurethane elastomer having a smaller compression set can be obtained. By adjusting the mass addition ratio of the polyisocyanate (B), the pot life can be adjusted to a desired range while keeping the compression set at a small value.

<Polyrotaxane (C)>
The polyrotaxane (C) used in the present invention comprises a cyclic molecule (Ca), a linear molecule (Cb) penetrating through the opening of the cyclic molecule (Ca), and the linear molecule (Cb). ), A blocking group (Cc) that prevents separation of the cyclic molecule (Ca) and the linear molecule (Cb), and a modifying group (Cd) that modifies the cyclic molecule (Ca). Is an inclusion compound having a structure in which is arranged. As the polyrotaxane, CAS No. The polyrotaxane specified by 928045-45-8 is preferable.

<Cyclic molecule (Ca)>
The cyclic molecule (Ca) is not particularly limited as long as the opening has a size that allows the linear molecule (Cb) to penetrate like a skewer. In the production of the polyrotaxane (C), this cyclic molecule (Ca) may be used alone or in combination.

  The cyclic molecule (Ca) usually has a hydroxyl group, and at least a part of the hydroxyl group is an isocyanate group of a prepolymer comprising a polyol compound (A) containing a polycarbonate polyol and a polyisocyanate (B), or a polyisocyanate. It is modified with a modifying group (Cd) that causes a crosslinking reaction with the isocyanate group of (B).

  Since the modifying group (Cd) can be introduced, the cyclic molecule (Ca) is preferably a cyclodextrin such as α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin.

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

  In particular, the modifying group (Cd) preferably has a hydrophobic group that makes the polyrotaxane hydrophobic. This 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 carbon atoms, an arylene group which may have a substituent having 6 to 50 carbon atoms, and a substituent having 4 to 50 carbon atoms. A divalent polyether group derived from a heteroarylene group which may have a group, a diol having 3 to 12 carbon atoms or an oxyalkylene, a divalent group derived from a hydroxycarboxylic acid having 3 to 12 carbon atoms or a cyclic ester And a divalent polyamide group derived from a lactam having 3 to 8 carbon atoms.

Examples of the substituent include a halogen atom (for example, fluorine atom, chlorine atom, bromine atom), an alkyl group having 1 to 20 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group, dodecyloctyl group), aryl group (for example, phenyl group, naphthyl group), aralkyl group (for example, benzyl group) Group, phenethyl group), alkoxy group (for example, methoxy group, ethoxy group) and the like.
In addition, carbon in these substituents is not counted in the carbon number in the said alkylene group, arylene group, and heteroarylene group.

  Examples of the heteroarylene group include a furylene group, a thienylene group, a pyridinylene group, a pyridazinylene group, a pyrimidinylene group, a pyrazinylene group, a triazinylene group, an imidazolinylene group, a pyrazolinylene group, a thiazolinylene group, a quinazolinylene group, and a phthalazinylene group.

  Further, the reactive group bonded to the other end of the hydrophobic group modifying the cyclic molecule (Ca) reacts with the group capable of reacting with each other or the isocyanate group of the polyisocyanate (B). It is a group having properties. Examples of such groups include hydroxyl groups, amino groups, thiol groups, carboxy groups, (meth) acryloyl groups, photoreactive groups such as vinyl groups and allyl groups, isocyanato groups, block isocyanato groups, ketone groups, aldehydes. Groups, epoxy groups, oxetane groups and carbodiimide groups.

  In view 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 polycaprolactone or polycaprolactam, the portion other than the portion corresponding to the group exemplified as the reactive group constitutes a part of the hydrophobic group.

  Moreover, as a method for introducing the modifying group (Cd) described above into the cyclic molecule (Ca), for example, the following method can be employed. Using cyclodextrin as the cyclic molecule (Ca), hydroxypropylating the hydroxyl group of the cyclodextrin with propylene oxide (the hydroxyl group of the cyclodextrin is modified with a hydrophobic group), and then adding ε-caprolactone as a catalyst Add tin 2-ethylhexanoate. Thereby, the modifying group (Cd) having a carboxy group as a reactive group is introduced into the cyclic molecule (Ca).

  The modification degree can be arbitrarily controlled by changing the ratio of propylene oxide and ε-caprolactone added to cyclodextrin at this time. Here, when the maximum number of hydroxyl groups of the cyclodextrin that can be modified is 1, it is preferably modified with a modification degree of 0.02 or more. In addition, this modification degree was modified with respect to all hydroxyl groups (including those modified with a hydrophobic group) in a plurality of cyclodextrin molecules contained in the polyrotaxane when viewed with a single molecule of polyrotaxane (C). This is the ratio of hydroxyl groups.

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

  As described above, when a crosslinking point is introduced at a position slightly away from the main body of the polyrotaxane (C) molecule by the modifying group (Cd), the crosslinking reaction with the polyisocyanate (B) is caused by the reason that steric hindrance is reduced. Easy to progress.

<(Cb) linear molecule>
The linear molecule (Cb) used for the polyrotaxane (C) is not particularly limited as long as it can penetrate through the opening of the cyclic molecule (Ca) in a skewered manner and be included in the cyclic molecule (Ca). . In addition, the functional group used as the reaction point at the time of introduce | transducing the blocking group (Cc) mentioned later exists in the both ends of a linear molecule (Cb). Examples of the functional group include a hydroxyl group, a carboxy group, an amino group, a mercapto group, and a sulfonyl group.

  In the production of the polyrotaxane (C), only one type of 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 resins (carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, etc.), polyacrylamide, polyethylene oxide. , Polyethylene glycol, polypropylene glycol, polyvinyl acetal resin, polyvinyl methyl ether, polyamine, polyethyleneimine, casein, gelatin, starch, polyester resin, poly (meth) acrylic acid, polycarbonate resin, polyurethane resin, polytetrahydrofuran, polyaniline, polyamide Resins, polyimide resins, polyisoprenes, polybutadienes such as polybutadiene, polydimethylsiloxane Examples include polysiloxanes, polysulfones, polyimines, polyacetic anhydrides, polyureas, polysulfides, polyphosphazenes, polyketones, polyphenylenes, polyhaloolefins, and derivatives and copolymers thereof. .

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

  Among these, polycaprolactone, polyethylene glycol, polypropylene glycol, polytetrahydrofuran and polydimethylsiloxane are more preferable, polycaprolactone and polyethylene glycol are more preferable, and polyethylene glycol is particularly preferable because it is water-soluble.

  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 reducing the compression set in the cast thermosetting polyurethane elastomer of the present invention. 000 or less, preferably 80,000 or less. More preferably, it is 40,000 or less.

  The weight average molecular weight is a value in terms of polystyrene measured by gel filtration chromatography (GPC).

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

  The maximum inclusion amount 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). it can. 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. Sought experimentally.

<(Cc) blocking group>
The blocking group (Cc) of the polyrotaxane (C) used in the present invention is arranged at both ends of the linear molecule (Cb) so that the cyclic molecule (Ca) and the linear molecule (Cb) are not separated. If it is a group which acts, it will not specifically limit. As such a blocking group (Cc), only one type may be used or a plurality of types may be used.

  Examples of the blocking group (Cc) include a dinitrophenyl group, a group derived from cyclodextrin, an adamantyl group, a trityl group, a fluorenyl group, a pyrenyl group, a substituted phenyl group (the substituent of the phenyl group includes an alkyl group, Examples thereof include, but are not limited to, an alkyloxy group, a hydroxyl group, a halogen, a cyano group, a sulfonyl group, a carboxy group, an amino group, and a phenyl group, and one or more substituents may be present. The polycyclic aromatic group that may be present (the substituents of the polycyclic aromatic group include, but are not limited to, the same as those described above. One or more substituents may be present. ) And steroids.

  Among these, from the viewpoint of easy introduction of the blocking group (Cc), a dinitrophenyl group, a group derived from cyclodextrin, an adamantyl group, a trityl group, a fluoresenyl group, and a pyrenyl group are preferable, and an adamantyl group and more preferably Trityl group.

  The blocking group (Cc) has a group that reacts with the functional groups present at both ends of the linear molecule (Cb), and a compound having a site that becomes the blocking group (Cc) separately from the group, It can introduce | transduce into the both ends of a linear molecule (Cb) by making it react with a linear molecule (Cb).

  In the present invention, the mass addition rate of the polyrotaxane (C) is greater than 10 mass% with respect to the total mass of the polyol compound (A), polyisocyanate (B), and polyrotaxane (C) including the polycarbonate polyol. Preferably it is larger than 10 mass% and less than 35 mass%, More preferably, it is 11-30 mass%, More preferably, it is 15-25 mass%. When the mass addition rate of the polyrotaxane (C) is within such a range, a polyurethane elastomer having a smaller compression set can be obtained, or the pot life can be lengthened.

<Polyurethane resin composition>
The composition for polyurethane resin (hereinafter sometimes simply referred to as “composition”) is a mixed liquid containing a polyol compound (A) containing a polycarbonate polyol, a polyisocyanate (B), and a polyrotaxane (C), The polyrotaxane (C) is a mixed liquid in which the mass addition ratio of the polyrotaxane (C) is greater than 10 mass% with respect to the total mass of the polyol compound (A), the polyisocyanate (B), and the polyrotaxane (C) including polycarbonate polyol.

  An inorganic material may be added to the polyurethane resin composition as necessary. Although it does not restrict | limit especially as an inorganic material, For example, a metal, a metal oxide, a metal nitride, a metal carbide, an alloy etc. are mentioned.

  Although it does not restrict | limit especially as a metal, For example, aluminum, copper, nickel, etc. are mentioned.

  Although it does not restrict | limit especially as a metal oxide, For example, an alumina, magnesium oxide, beryllium oxide, chromium oxide, a titanium oxide etc. are mentioned.

  The metal nitride is not particularly limited, and examples thereof include boron nitride and aluminum nitride.

  Although it does not restrict | limit especially as a metal carbide, For example, boron carbide, titanium carbide, silicon carbide etc. are mentioned.

  Although it does not restrict | limit especially as an alloy, For example, Fe-Si alloy, Fe-Al alloy, Fe-Si-Al alloy, Fe-Si-Cr alloy, Fe-Ni alloy, Fe-Ni-Co alloy, Fe-Ni -Mo alloy, Fe-Co alloy, Fe-Si-Al-Cr alloy, Fe-Si-B alloy, Fe-Si-Co-B alloy, etc. are mentioned.

  The mass addition rate of the inorganic material is 0 to 30% by mass with respect to the total mass of the polyol compound (A), polyisocyanate (B), polyrotaxane (C) and inorganic material including polycarbonate polyol, but preferably 0. -9 mass%. When the addition amount of the inorganic material is 30% by mass or less, the compression set tends to be smaller.

  Polyurethane resin compositions include catalysts, antioxidants, defoamers, UV absorbers, reaction modifiers, plasticizers, mold release agents, reinforcing agents, fillers (inorganic fillers / organic fillers), Various materials used in conventionally known compositions for forming polyurethane resin compositions such as stabilizers, colorants (pigments / dyes), flame retardants, light stabilizers, etc. as optional components Can be contained.

  The catalyst is not particularly limited, and examples thereof include salts of metals such as tin (tin) catalysts (trimethyltin laurate, dibutyltin dilaurate, etc.) and lead catalysts (lead octylate, etc.), organic and inorganic acids, and organic metals. Derivatives, amine catalysts (triethylamine, N-ethylmorpholine, triethylenediamine, etc.), diazabicycloundecene catalysts, and the like can be given. Of these, dibutyltin dilaurate and dioctyltin dilaurate are preferable from the viewpoint of reactivity. The amount of the catalyst to be 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. For example, IRGANOX 1726 (BASF Japan), IRGANOX 1010 (BASF Japan), IRGANOX 1076 (BASF Japan), IRGANOX245 (BASF Japan) and Banox 830 (phenolic compound, alkylated diphenylamine and And trialkyl phosphite blends) (RT Banderbilt).

  The mass addition ratio of the antioxidant is preferably 0.01 to 10% by mass, more preferably based on the total mass of the polyol compound (A), polyisocyanate (B), and polyrotaxane (C) containing polycarbonate polyol. Is 0.1-5 mass%. When the addition rate of the antioxidant is within such a range, yellowing can be suppressed without greatly affecting the physical properties of the polyurethane elastomer.

  Defoamer, UV absorber, reaction modifier, plasticizer, mold release agent, reinforcing agent, filler (inorganic filler / organic filler), stabilizer, colorant (pigment / dye), flame retardant As for other components such as a light stabilizer, the kind and amount thereof are not particularly limited, and appropriate amounts known to those skilled in the art can be used.

  In the present invention, the molar ratio of the hydroxyl group (OH) of the polyol compound (A) containing the polycarbonate polyol and the polyrotaxane (C) to the isocyanate group (NCO) of the polyisocyanate (B) in the polyurethane resin composition. NCO / OH is preferably 1/10 to 10/1. Further, NCO / OH is more preferably 1/5 to 5/1, more preferably 1/3 to 3/1, and still more preferably 1/2 to 2/1. By setting the value of NCO / OH within such a range, the pot life can be adjusted to an appropriate length.

<Manufacturing method of cast thermosetting polyurethane elastomer>
Next, a method for producing the cast thermosetting polyurethane elastomer of the present invention will be described.
For example, the cast thermosetting polyurethane elastomer of the present invention is produced in the following first to third steps.
First step: A step of mixing a polyol compound (A) containing a polycarbonate polyol, a polyisocyanate (B), a polyrotaxane (C), and an inorganic material that can be used as necessary.
2nd process: The process of applying a liquid mixture in a type | mold.
3rd process: The process of making a liquid mixture react in a type | mold, and thermosetting.

<< First step: Step of mixing a polyol compound (A) containing a polycarbonate polyol, a polyisocyanate (B), a polyrotaxane (C), and an inorganic material that can be used if necessary >>
As a mixing method of each component for producing the cast thermosetting polyurethane elastomer of the present invention, the mixing method and the operation sequence are not particularly limited. For example, a polyol compound (A) containing a polycarbonate polyol, a polyisocyanate ( B), a polyrotaxane (C) and a so-called one-shot method in which an inorganic material that can be used if necessary is mixed, or a polyol compound (A) containing a polycarbonate polyol and a polyisocyanate (B) are reacted in advance and synthesized. Examples include a so-called prepolymer method in which a prepolymer having an isocyanato group at the molecular end, a polyrotaxane (C) and an inorganic material that can be used as necessary are mixed.

  A polyisocyanate (B) or polyurethane prepolymer having an isocyanato group, a polyol compound (A) containing a polycarbonate polyol having a substituent reactive with the isocyanato group, and a polyrotaxane (C) are put into a tank, and the temperature is kept and desorbed. Perform foaming, dehydration, etc. Although the operation order is not particularly limited, for example, it may be put into separate tanks for heat retention, defoaming, dehydration, etc., and when mixing two kinds of components in advance, heat retention, defoaming, Mixing may be performed after dehydration or the like, or premixed materials may be put into the same tank for heat retention, defoaming, dehydration and the like. In the case of using the other polyol compound (Ab) in the polyol compound (A) containing the polycarbonate polyol, the other polyol compound (Ab) is obtained in advance from the polycarbonate polyol (Aa) and / or the polyrotaxane (C). Heating, defoaming, dehydration, etc. may be carried out by mixing and feeding into a tank, or heat insulation, defoaming, dehydration, etc. may be carried out separately by feeding into a tank. When using an inorganic material as needed, it is preferable to mix with the same tank as the polyol compound (A) containing a polycarbonate polyol. The catalyst, additive, chain extender and the like are preferably mixed in the same tank as the polyol compound (A) containing polycarbonate polyol.

<<<< One-shot method >>>>>
In the case of a so-called one-shot method in which a polyol compound (A) containing a polycarbonate polyol, a polyisocyanate (B), a polyrotaxane (C) and an inorganic material that can be used as needed are mixed, the mixing method and operation sequence are not particularly limited. However, for example, there are a method of mixing all the components at once, a method of mixing the remaining components in a mixture of two types of components in advance, and the like. 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 >>>>
A prepolymer having an isocyanate group at the molecular end synthesized by reacting a polyol compound (A) containing a polycarbonate polyol and a polyisocyanate (B) in advance, a polyrotaxane (C), and an inorganic material that can be used as needed. In the case of the so-called prepolymer method, the mixing method and the operation sequence are not particularly limited. For example, the molecular terminal synthesized by reacting a polyol compound (A) containing polycarbonate polyol and polyisocyanate (B) in advance is used. A method of mixing a polyrotaxane (C) and an inorganic material that can be used if necessary with a prepolymer having an isocyanato group, or a polyol compound containing a polycarbonate polyol in a mixture of a polyrotaxane (C) and an inorganic material that can be used if necessary (A) and polyisocyanate Preparative (B) and a method for mixing a prepolymer having an isocyanato group at the molecular end was synthesized by reacting in advance, and the like.

  A part of the polyol compound (A) containing the polycarbonate polyol is reacted in advance with the polyisocyanate (B) to synthesize a prepolymer having an isocyanate group at the molecular end, and the remainder of the polyol compound (A) containing the polycarbonate polyol Polyrotaxane (C) and a mixture of inorganic materials that can be used as necessary may be mixed. The order of mixing the prepolymer and other components is not particularly limited, but examples include a method of mixing all components at once, a method of mixing the two components in advance, and a method of mixing the remaining components. It is done. 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.

  The step of mixing the polyol compound (A) containing the polycarbonate polyol, the polyisocyanate (B), the polyrotaxane (C) and the inorganic material that can be used as necessary can be performed at 0 to 150 ° C., preferably 20 to 120. It can be carried out at ° C. By mixing within such a temperature range, more efficient mixing and casting can be performed.

  The mixing time in the step of mixing the polyol compound (A) containing the polycarbonate polyol, the polyisocyanate (B), the polyrotaxane (C) and the inorganic material that can be used as necessary can be 5 seconds to 5 hours. Preferably, it is 10 seconds to 1 hour. By setting it as such mixing time, a polyurethane elastomer can be manufactured more efficiently.

  In the process of mixing the polyol compound (A) containing the polycarbonate polyol, the polyisocyanate (B), the polyrotaxane (C) and an inorganic material that can be used as necessary, known stirring such as a revolving stirrer, a mixer, an agitator mixer, etc. An apparatus can be used.

<< Second Step: Step of Applying Mixed Liquid in Mold >>
A mixed liquid which is a composition of a polyol compound (A) containing a polycarbonate polyol, a polyisocyanate (B), a polyrotaxane (C) and an inorganic material that can be used as needed is poured into a mold.
From the casting machine, each liquid, which is a raw material, is discharged at a predetermined ratio into a heat-insulated mold for casting.

  Examples of the material of the mold include metals, plastics, inorganic materials, and wood. As the shape of the mold, a shape known to those skilled in the art can be used. If necessary, a mold release agent can be applied in the mold before casting the composition.

In addition, when the curing rate of the composition is relatively slow, the composition can be applied and then depressurized for further defoaming. At this time, when an open mold is used as the mold, it can be defoamed in a vacuum oven.
The temperature during the defoaming is preferably 20 to 100 ° C, more preferably 50 to 80 ° C. By performing defoaming at such a temperature, defoaming can be performed more efficiently. Depending on the temperature at which the defoaming is performed, the defoaming can be performed simultaneously with the thermosetting step described later.

  The defoaming time is preferably 1 to 60 minutes, more preferably 2 to 30 minutes. By performing defoaming in such a time, the polyurethane elastomer can be produced more efficiently.

«Third step: a step of reacting the mixed solution in the mold and thermosetting»
A mixed liquid of a polyol compound (A) containing a polycarbonate polyol, a polyisocyanate (B), a polyrotaxane (C) and an inorganic material that can be used as needed has a polyol compound (A) containing a polycarbonate polyol and a polyrotaxane (C). The hydroxyl group and the isocyanate group of the polyisocyanate (B) can be reacted and cured. Thereby, the cast thermosetting polyurethane elastomer which is a hardened | cured material of a composition is obtained.

Examples of the heating method include a heating method using its own reaction heat, a heating method using both the reaction heat and positive heating of the mold.
Examples of the positive heating of the mold include a method of heating the mold in a hot air oven, an electric furnace, or an infrared induction heating furnace.

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

  The heating time is preferably 0.5 to 30 hours, more preferably 1 to 25 hours. By setting it as such a heating time, a polyurethane elastomer with higher hardness can be obtained.

  Alternatively, the cured product may be peeled from the base material to obtain a cast thermosetting polyurethane elastomer.

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

<Synthesis of prepolymer>
In a reactor equipped with a stirrer and a heater, ETERNACOLL (registered trademark) PH50 (manufactured by Ube Industries; number average molecular weight 499; hydroxyl value 255 mgKOH / g; polyol component is 1,5-pentanediol: 1,6-hexanediol = 204 g of a polycarbonate diol obtained by reacting a polyol mixture having a molar ratio of 1: 1 and a carbonic ester, 106 g of tolylene diisocyanate (TDI), and 136 g of isophorone diisocyanate (IPDI) were mixed under a nitrogen atmosphere. Heating at 80-90 ° C. for 3 hours gave Prepolymer “P-1”.

  In a reactor equipped with a stirrer and a heater, ETERNACOLL (registered trademark) PH50 (manufactured by Ube Industries; number average molecular weight 499; hydroxyl value 255 mgKOH / g; polyol component is 1,5-pentanediol: 1,6-hexanediol = 227 g of a polycarbonate diol obtained by reacting a polyol mixture of a 1: 1 molar ratio and a carbonate ester, 178 g of tolylene diisocyanate (TDI), and 75.8 g of isophorone diisocyanate (IPDI) were mixed in a nitrogen atmosphere. And heated at 80-90 ° C. for 3 hours to obtain a prepolymer “P-2”.

  In a reaction apparatus equipped with a stirrer and a heater, 69.8 g of MPOPCD (polycarbonate diol (molecular weight: 496) obtained by reacting 2-methyl-1,3-propanediol and dimethyl carbonate) and tolylene diisocyanate ( (TDI) 37.2 g and isophorone diisocyanate (IPDI) 47.5 g were mixed under a nitrogen atmosphere and heated at 80 to 90 ° C. for 3 hours to obtain a prepolymer “P-3”.

  PDLPCD 0% (polycarbonate diol obtained by reacting 1,5-pentanediol and dimethyl carbonate (molecular weight: 513) in a reaction apparatus equipped with a stirrer and a heater. Here, “0%” 76.1 g) (representing that the amount of 1,5-hexanediol is 0 mol% based on the total of 5-hexanediol and 1,5-pentanediol), 39.0 g of tolylene diisocyanate (TDI), and isophorone Diisocyanate (IPDI) 50.1 g was mixed under a nitrogen atmosphere and heated at 80 to 90 ° C. for 3 hours to obtain a prepolymer “P-4”.

  PDLPCD 10% (polycarbonate diol (molecular weight: 494) obtained by reacting 1,5-hexanediol, 1,5-pentanediol and dimethyl carbonate) in a reaction apparatus equipped with a stirrer and a heater, where “10 % ”Represents 78.2 g of 1,5-hexanediol based on the total of 1,5-hexanediol and 1,5-pentanediol), and tolylene diisocyanate (TDI). 41.4 g and 52.8 g of isophorone diisocyanate (IPDI) were mixed in a nitrogen atmosphere and heated at 80 to 90 ° C. for 3 hours to obtain a prepolymer “P-5”.

  In a reactor equipped with a stirrer and a heater, PDLPCD 20% (polycarbonate diol (molecular weight: 496) obtained by reacting 1,5-hexanediol, 1,5-pentanediol and dimethyl carbonate, where “20 % ”Represents 69.8 g of 1,5-hexanediol and 20 mol% of 1,5-hexanediol and 1,5-pentanediol, and tolylene diisocyanate (TDI). 37.4 g and 47.9 g of isophorone diisocyanate (IPDI) were mixed under a nitrogen atmosphere and heated at 80 to 90 ° C. for 3 hours to obtain a prepolymer “P-6”.

<Preparation of additive mixture>
Dibutyltin dilaurate (DBTDL) 0.20 g, antioxidant IRGANOX 1726 (manufactured by BASF Japan) 39.8 g, and defoamer BYK-A535 (manufactured by BYK) 19.9 g are mixed in a glass bottle, and 100 ° C. For 1 hour. Then, it mixed for 5 minutes with the self-revolution stirrer, and additive liquid mixture "A-1" was obtained.

  0.027 g of dibutyltin dilaurate (DBTDL), 2.71 g of an antioxidant IRGANOX 1726 (manufactured by BASF Japan) and 2.70 g of a defoaming agent BYK-A535 (manufactured by BYK) are mixed in a glass bottle and mixed at 100 ° C. For 1 hour. Then, it mixed for 5 minutes with the self-revolution stirrer, and obtained additive liquid mixture "A-2".

[Example 1]
1.74 g of additive mixture “A-1”, 33.5 g of polypropylene glycol (“Uniol D-700” manufactured by NOF Corporation), and caprolactone-modified polyrotaxane (HAPR-g-PCL; manufactured by Advanced Soft Materials) “Superpolymer SH2400P”) 7.00 g was mixed to obtain a polyrotaxane mixed solution. 22.3 g of the prepolymer “P-1” and the prepared polyrotaxane mixed solution were mixed, and uniformly stirred and degassed by a self-revolving stirrer. The obtained mixture was poured into a Teflon (registered trademark) rubber mold and cured by heating at 120 ° C. for 15 hours to obtain a cast thermosetting polyurethane elastomer having a thickness of about 12.5 mm.

[Example 2]
1.68 g of additive mixture “A-1”, 26.9 g of Uniol D-700 (polypropylene glycol; manufactured by NOF Corporation), caprolactone-modified polyrotaxane (HAPR-g-PCL; manufactured by Advanced Soft Materials) Superpolymer SH2400P ") 8.41 g was mixed to obtain a polyrotaxane mixed solution. 21.2 g of the prepolymer “P-1” and the prepared polyrotaxane mixed solution were mixed, and uniformly stirred and degassed by a self-revolving stirrer. The obtained mixture was poured into a Teflon (registered trademark) rubber mold and cured by heating at 120 ° C. for 15 hours to obtain a cast thermosetting polyurethane elastomer having a thickness of about 12.5 mm.

[Example 3]
1.44 g of additive mixture “A-1”, 21.1 g of Uniol D-700 (polypropylene glycol; manufactured by NOF Corporation), caprolactone-modified polyrotaxane (HAPR-g-PCL; manufactured by Advanced Soft Materials, Inc.) Superpolymer SH2400P ") 9.63 g was mixed to obtain a polyrotaxane mixed solution. 18.0 g of the prepolymer “P-1” and the prepared polyrotaxane mixed solution were mixed, and uniformly stirred and degassed by a self-revolving stirrer. The obtained mixture was poured into a Teflon (registered trademark) rubber mold and cured by heating at 120 ° C. for 15 hours to obtain a cast thermosetting polyurethane elastomer having a thickness of about 12.5 mm.

[Example 4]
1.48 g of additive mixture “A-1”, 19.5 g of Uniol D-700 (polypropylene glycol; manufactured by NOF Corporation), caprolactone-modified polyrotaxane (HAPR-g-PCL; manufactured by Advanced Soft Materials) 12.4 g of superpolymer SH2400P ") was mixed to obtain a polyrotaxane mixed solution. 18.0 g of the prepolymer “P-1” and the prepared polyrotaxane mixed solution were mixed, and uniformly stirred and degassed by a self-revolving stirrer. The obtained mixture was poured into a Teflon (registered trademark) rubber mold and cured by heating at 120 ° C. for 15 hours to obtain a cast thermosetting polyurethane elastomer having a thickness of about 12.5 mm.

[Example 5]
Additive mixture “A-1” 1.57 g, Uniol D-700 (polypropylene glycol; manufactured by NOF Corporation) 19.3 g, caprolactone-modified polyrotaxane (HAPR-g-PCL; manufactured by Advanced Soft Materials) 14.7 g of superpolymer SH2400P ") was mixed to obtain a polyrotaxane mixed solution. 18.8 g of the prepolymer “P-1” and the prepared polyrotaxane mixed solution were mixed, and uniformly stirred and degassed by a self-revolving stirrer. The obtained mixture was poured into a Teflon (registered trademark) rubber mold and cured by heating at 120 ° C. for 15 hours to obtain a cast thermosetting polyurethane elastomer having a thickness of about 12.5 mm.

[Example 6]
1.58 g of additive mixture “A-1”, 17.2 g of Uniol D-700 (polypropylene glycol; manufactured by NOF Corporation), caprolactone-modified polyrotaxane (HAPR-g-PCL; manufactured by Advanced Soft Materials) 17.4 g of superpolymer SH2400P ") was mixed to obtain a polyrotaxane mixed solution. 18.7 g of the prepolymer “P-1” and the prepared polyrotaxane mixed solution were mixed, and uniformly stirred and degassed by a self-revolving stirrer. The obtained mixture was poured into a Teflon (registered trademark) rubber mold and cured by heating at 120 ° C. for 15 hours to obtain a cast thermosetting polyurethane elastomer having a thickness of about 12.5 mm.

[Example 7]
4.60 g of additive mixture “A-1”, 65.6 g of Uniol D-700 (polypropylene glycol; manufactured by NOF Corporation), and caprolactone-modified polyrotaxane (HAPR-g-PCL; manufactured by Advanced Soft Materials) Superpolymer SH2400P ") 30.1 g was mixed to obtain a polyrotaxane mixed solution. 55.7 g of the prepolymer “P-1” and the prepared polyrotaxane mixed solution were mixed, and uniformly stirred and degassed by a self-revolving stirrer. The obtained mixture was poured into a Teflon (registered trademark) rubber mold and cured by heating at 120 ° C. for 25 hours to obtain a cast thermosetting polyurethane elastomer having a thickness of about 12.5 mm.

[Example 8]
4.60 g of additive mixture “A-1”, 65.6 g of Uniol D-700 (polypropylene glycol; manufactured by NOF Corporation), and caprolactone-modified polyrotaxane (HAPR-g-PCL; manufactured by Advanced Soft Materials) Superpolymer SH2400P ") 30.1 g was mixed to obtain a polyrotaxane mixed solution. 55.7 g of the prepolymer “P-1” and the prepared polyrotaxane mixed solution were mixed, and uniformly stirred and degassed by a self-revolving stirrer. The obtained mixture was poured into a Teflon (registered trademark) rubber mold and cured by heating at 130 ° C. for 10 hours to obtain a cast thermosetting polyurethane elastomer having a thickness of about 12.5 mm.

[Example 9]
4.60 g of additive mixture “A-1”, 65.6 g of Uniol D-700 (polypropylene glycol; manufactured by NOF Corporation), and caprolactone-modified polyrotaxane (HAPR-g-PCL; manufactured by Advanced Soft Materials) Superpolymer SH2400P ") 30.1 g was mixed to obtain a polyrotaxane mixed solution. 55.7 g of the prepolymer “P-1” and the prepared polyrotaxane mixed solution were mixed, and uniformly stirred and degassed by a self-revolving stirrer. The obtained mixture was poured into a Teflon (registered trademark) rubber mold and cured by heating at 130 ° C. for 25 hours to obtain a cast thermosetting polyurethane elastomer having a thickness of about 12.5 mm.

[Example 10]
1.74 g of additive mixture “A-1” and ETERNACOLL (registered trademark) PH80 (manufactured by Ube Industries; number average molecular weight 813; hydroxyl value 138 mg KOH / g; polyol component is 1,5-pentanediol: 1,6- 19.1 g of a polycarbonate diol obtained by reacting a polyol mixture of a hexanediol = 1: 1 molar ratio and a carbonic acid ester, and caprolactone-modified polyrotaxane (HAPR-g-PCL; “Super Polymer” manufactured by Advanced Soft Materials, Inc. SH2400P ") 18.0 g was mixed to obtain a polyrotaxane mixed solution. 18.2 g of the prepolymer “P-1” and the prepared polyrotaxane mixed solution were mixed, and uniformly stirred and defoamed by a self-revolving stirrer. The obtained mixture was poured into a Teflon (registered trademark) rubber mold and cured by heating at 120 ° C. for 15 hours to obtain a cast thermosetting polyurethane elastomer having a thickness of about 12.5 mm.

[Example 11]
Additive mixture “A-1” 1.51 g, Uniol D-700 (polypropylene glycol; manufactured by NOF Corporation) 22.8 g, caprolactone-modified polyrotaxane (HAPR-g-PCL; manufactured by Advanced Soft Materials, Inc.) Superpolymer SH2400P ") 10.1 g was mixed to obtain a polyrotaxane mixed solution. 19.5 g of the prepolymer “P-2” and the prepared polyrotaxane mixed solution were mixed, and the mixture was uniformly stirred and defoamed by a self-revolving stirrer. The obtained mixture was poured into a Teflon (registered trademark) rubber mold and cured by heating at 130 ° C. for 7 hours to obtain a cast thermosetting polyurethane elastomer having a thickness of about 12.5 mm.

[Example 12]
Additive mixture “A-2” 0.14 g, Uniol D-700 (polypropylene glycol; manufactured by NOF Corporation) 34.2 g, caprolactone-modified polyrotaxane (HAPR-g-PCL; manufactured by Advanced Soft Materials) Superpolymer SH2400P ") 10.5 g was mixed to obtain a polyrotaxane mixed solution. 25.4 g of the prepolymer “P-3” and the prepared polyrotaxane mixed solution were mixed, and the mixture was uniformly stirred and degassed by a self-revolving stirrer. The obtained mixture was poured into a Teflon (registered trademark) rubber mold and cured by heating at 120 ° C. for 15 hours to obtain a cast thermosetting polyurethane elastomer having a thickness of about 4 mm.

[Example 13]
Additive mixture “A-2” 0.14 g, Uniol D-700 (polypropylene glycol; manufactured by NOF Corporation) 32.6 g, caprolactone-modified polyrotaxane (HAPR-g-PCL; manufactured by Advanced Soft Materials) Superpolymer SH2400P ") 10.5 g was mixed to obtain a polyrotaxane mixed solution. 27.0 g of the prepolymer “P-4” and the prepared polyrotaxane mixed solution were mixed, and the mixture was uniformly stirred and defoamed with a self-revolving stirrer. The obtained mixture was poured into a Teflon (registered trademark) rubber mold and cured by heating at 120 ° C. for 15 hours to obtain a cast thermosetting polyurethane elastomer having a thickness of about 4 mm.

[Example 14]
Additive mixture “A-2” 0.14 g, Uniol D-700 (polypropylene glycol; manufactured by NOF Corporation) 33.2 g, caprolactone-modified polyrotaxane (HAPR-g-PCL; manufactured by Advanced Soft Materials) Superpolymer SH2400P ") 10.5 g was mixed to obtain a polyrotaxane mixed solution. 26.5 g of the prepolymer “P-5” and the prepared polyrotaxane mixed solution were mixed, and uniformly stirred and degassed by a self-revolving stirrer. The obtained mixture was poured into a Teflon (registered trademark) rubber mold and cured by heating at 120 ° C. for 15 hours to obtain a cast thermosetting polyurethane elastomer having a thickness of about 4 mm.

[Example 15]
Additive mixture “A-2” 0.14 g, Uniol D-700 (polypropylene glycol; manufactured by NOF Corporation) 33.2 g, caprolactone-modified polyrotaxane (HAPR-g-PCL; manufactured by Advanced Soft Materials) Superpolymer SH2400P ") 10.5 g was mixed to obtain a polyrotaxane mixed solution. 26.5 g of the prepolymer “P-6” and the prepared polyrotaxane mixed solution were mixed, and uniformly stirred and degassed by a self-revolving stirrer. The obtained mixture was poured into a Teflon (registered trademark) rubber mold and cured by heating at 120 ° C. for 15 hours to obtain a cast thermosetting polyurethane elastomer having a thickness of about 4 mm.

[Comparative Example 1]
1.64 g of additive mixture “A-1”, 31.4 g of Uniol D-700 (polypropylene glycol; manufactured by NOF Corporation), caprolactone-modified polyrotaxane (HAPR-g-PCL; manufactured by Advanced Soft Materials, Inc.) Superpolymer SH2400P ”) 4.37 g was mixed to obtain a polyrotaxane mixed solution. 19.5 g of the prepolymer “P-1” and the prepared polyrotaxane mixed solution were mixed, and uniformly stirred and defoamed with a self-revolving stirrer. The obtained mixture was poured into a Teflon (registered trademark) rubber mold and cured by heating at 120 ° C. for 15 hours to obtain a cast thermosetting polyurethane elastomer having a thickness of about 12.5 mm.

[Comparative Example 2]
1.64 g of additive mixture “A-1” and ETERNACOLL (registered trademark) PH80 (manufactured by Ube Industries; number average molecular weight 813; hydroxyl value 138 mg KOH / g; polyol component is 1,5-pentanediol: 1,6- 31.4 g of a polycarbonate diol obtained by reacting a polyol mixture of a hexanediol = 1: 1 molar ratio and a carbonic ester, and caprolactone-modified polyrotaxane (HAPR-g-PCL; “Superpolymer” manufactured by Advanced Soft Materials, Inc. SH2400P ") 4.37 g was mixed to obtain a polyrotaxane mixed solution. 19.5 g of the prepolymer “P-1” and the prepared polyrotaxane mixed solution were mixed, and uniformly stirred and defoamed with a self-revolving stirrer. The obtained mixture was poured into a Teflon (registered trademark) rubber mold and cured by heating at 120 ° C. for 15 hours to obtain a cast thermosetting polyurethane elastomer having a thickness of about 12.5 mm.

(Evaluation of polyurethane elastomer)
About the polyurethane elastomer obtained by the Example and the comparative example, evaluation of various physical properties was performed by the method shown below. The results are shown in Table 1.

(Evaluation of pot life)
In accordance with JIS K 7301, the pot life was measured by the following method. The polyrotaxane mixed solution and the prepolymer were mixed and stirred for 1 minute with a self-revolving stirrer, and then the viscosity was measured at 80 ° C. using an E-type viscometer. The time (minutes) at which the viscosity reached 50,000 cP from the start of measurement was defined as the pot life.

(Evaluation of compression set)
A cylindrical molded body having a thickness of 12.5 mm and a diameter of 30.0 mm was prepared using the samples of each Example and Comparative Example, and the compression rate was 25% and 70 ° C. × 22 hours in accordance with JIS K-7312 Compression set was measured under the conditions.

(Evaluation of toluene swelling rate)
The sample was immersed in toluene (100 ° C., 22 hours), and the swelling ratio into toluene was determined from the mass before and after the immersion using the following formula.
Swelling ratio = W2 / W1 × 100 (%)
In the above formula, W1 represents mass (g) before immersion, and W2 represents mass (g) after immersion.

(Evaluation of gel fraction)
After immersing the sample in toluene (100 ° C., 22 hours), the sample was dried in a vacuum oven (180 ° C., 3 hours), and the gel fraction was determined by the following formula from the mass after drying.
Gel fraction = W3 / W1 × 100 (%)
In the above formula, W1 represents mass (g) before immersion, and W3 represents mass (g) after drying.

(hardness)
A cylindrical molded body having a thickness of 12.5 mm and a diameter of 30.0 mm was prepared using the samples of each example and comparative example, and the durometer E hardness was measured according to JIS K 6253.

(Evaluation of tackiness)
A columnar molded body having a thickness of 12.5 mm and a diameter of 30.0 mm was prepared using the samples of each Example and Comparative Example, and tackiness was measured with a tackiness checker (HTC-1 manufactured by Toyo Seiki Seisakusho). Five measurements were taken and the median was used.

(Evaluation of presence of bubbles)
The surface and the inside of the cured product after heating were visually observed and evaluated according to the following criteria.
○: Air bubbles are hardly contained on the surface or inside of the cured product.
X: The surface of the cured product contains a lot of bubbles inside

  In any of Examples 1 to 15, a polyurethane elastomer could be obtained by cast molding using a polyol compound containing various polycarbonate polyols as a raw material without producing bubbles in the cured product. Furthermore, it is clear from Table 1 that when the proportion of polyrotaxane is larger than 10% by mass, the obtained polyurethane elastomer has a low compression set while maintaining a pot life with a length that is not problematic in terms of workability. It became. On the other hand, when the ratio of the polyrotaxane is less than 10%, although the pot life becomes long, the compression set becomes very large, so that it was revealed that sufficient mechanical properties as a polyurethane elastomer cannot be obtained.

  The cast thermosetting polyurethane elastomer of the present invention includes a papermaking roller, an iron plate rolling roller, a printing roller, a roller for office equipment, a main roller for wire saw, a platen, a skate roller, a solid tire, a caster, a battery forklift, a work transport vehicle, Industrial track wheels, conveyor belt idlers, cable and belt guide rolls, prairies springs, belt cushions, oil seals, electronics components, cleaning blades, squeegees, gears, connection ring liners, pump linings, impeller cyclocones , Cyclone liners, polishing pads, precision parts rollers, transport rollers, play wheels, AJV wheels, urethane rubber for snow plows, anti-vibration, vibration-damping and earthquake-resistant urethane rubber, iron plate Lining, metal fitting lining, automobile line holders / stoppers, urethane rubber plate material, wheels for forklifts, rollers for transporting heavy machinery, pinch rolls, guide rolls, snubber rolls, glass feed skewer rolls, special processing rollers for chemical machines, slitter blade support rollers , Conductive urethane rubber roller, silicon wafer wire cut roller (main roller), packing sheet material, roller coaster tire, gasket, seal, steel roll, paper roll and these materials can be widely used.

Claims (8)

  A cast thermosetting polyurethane elastomer comprising at least a polyol compound (A) containing a polycarbonate polyol, a polyisocyanate (B), and a polyrotaxane (C), wherein the polyrotaxane (C) is a cyclic molecule ( Ca), a linear molecule (Cb) penetrating through the opening of the cyclic molecule (Ca), and arranged at both ends of the linear molecule (Cb), the cyclic molecule (Ca) It has a blocking group (Cc) that prevents separation from the linear molecule (Cb) and a modifying group (Cd) that modifies the cyclic molecule (Ca), and the mass addition rate of the polyrotaxane (C) is: Cast thermosetting greater than 10% by mass with respect to the total mass of polyol compound (A), polyisocyanate (B), and polyrotaxane (C) including polycarbonate polyol Polyurethane elastomer.   The mass addition rate of the polyrotaxane (C) is greater than 10 mass% and less than 35 mass% with respect to the total mass of the polycarbonate polyol (A), polyisocyanate (B), and polyrotaxane (C). The cast thermosetting polyurethane elastomer described.   The mass addition rate of a polyrotaxane (C) is 11-30 mass% with respect to the sum total of the mass of a polycarbonate polyol (A), a polyisocyanate (B), and a polyrotaxane (C), The note of Claim 1 or 2 Type thermosetting polyurethane elastomer.   The mass addition rate of the polyrotaxane (C) is 15 to 25% by mass with respect to the total mass of the polycarbonate polyol (A), polyisocyanate (B), and polyrotaxane (C). The cast thermosetting polyurethane elastomer according to Item.   The cast thermosetting polyurethane elastomer according to any one of claims 1 to 4, wherein the polyol compound (A) further comprises a polyether polyol.   The molar ratio of the hydroxyl group of the polycarbonate polyol (A) and the polyrotaxane (C) and the isocyanate group of the polyisocyanate (B) is NCO / OH = 1/5 to 5/1. The cast thermosetting polyurethane elastomer according to any one of the above.   The cast thermosetting polyurethane elastomer according to any one of claims 1 to 6, wherein the polycarbonate polyol (A) has a number average molecular weight of 300 to 3,000.   The cast thermosetting according to any one of claims 1 to 7, comprising a step of reacting a polyol compound (A) containing a polycarbonate polyol, a polyisocyanate (B), and a polyrotaxane (C) in the absence of a solvent. For producing a molded polyurethane elastomer.