JPH09227648A - Two-component polyurethane elastomer composition for casting and method for producing polyurethane elastomer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a urethane elastomer composition for two-pack casting with excellent workability, improved physical strength and improved weather resistance, and a method for producing a polyurethane elastomer using the composition. SOLUTION: An NCO group-terminated prepolymer using an MDI-based polyisocyanate and an HDI-based polyisocyanate as specific isocyanates and a lactone-based and carbonate-based polyol as a polyol, and / or a curing agent as a curing agent A composition comprising a mixture of a polycaprolactone polyol, a carbonate polyol, a carbonate-lactone-based polyol, a short-chain glycol and a short-chain triol is used.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a two-component polyurethane elastomer composition for casting. More specifically, N
The present invention relates to a method for producing a polyurethane elastomer composition comprising a CO group-terminated prepolymer and a long-chain polyol, a short-chain glycol, a short-chain triol, etc. for two-component casting, which has excellent workability and physical strength. .

[0002]

2. Description of the Related Art Conventionally, molding techniques of cast urethane elastomers are generally classified into two types, one-shot method and prepolymer method. The one-shot method is a method in which all the raw materials are mixed and stirred in a reactor at a time, then cast, the reaction is almost completed by primary cure, the mold is released, and then the secondary cure is performed. So is the most economical way. However, since a polymerization reaction such as urethanization proceeds at a time, a large amount of heat is generated, and it is difficult to obtain stable physical characteristics. On the other hand, the prepolymer method employs a two-step method including a step of preliminarily reacting a polyol and an excess of isocyanate to synthesize a prepolymer, and a step of reacting the prepolymer with other insufficient raw materials to finally produce an elastomer. In the case of the prepolymer method, most cast urethane elastomers are produced by this method because the heat associated with the urethanization reaction has already been released during the prepolymerization and has the advantages described below. (A) Since the reaction proceeds uniformly, an elastomer having high physical properties can be obtained. (B) The total heat generation is small, and large-sized molding is possible. (C) A segmented polyurethane in which a curing agent such as glycol or amine is freely selected can be produced. However, drawbacks of this prepolymer method include high viscosity and offset of the mixture ratio. If the viscosity is high, poor defoaming, poor mixing with the curing agent, and the like may occur, while if the mixture ratio is uneven, there is a concern that a change in physical properties due to a shift in stoichiometry.

In Japanese Patent Publication No. 3-41833, diphenylmethane diisocyanate, tolylene diisocyanate or the like is used as an organic polyisocyanate, which is reacted with polycaprolactone ester to obtain a prepolymer, and as a curing agent, 1,4-butanediol or Urethane rubber is obtained using diamine. This urethane rubber aims at stability against temperature change, durability against heat, and stability for a long period of time. JP-A-5-24049 discloses a polyurethane molded product obtained by reacting diphenylmethane diisocyanate with polyethylene adipate polyol as a polyisocyanate to obtain a prepolymer, and using polyethylene adipate polyol and 1,4-butanediol as a curing agent. It has gained. The purpose of this elastomer is to reduce distortion without reducing low-temperature properties. JP-A-5-278045 discloses that a polyurethane molded product is obtained by reacting diphenylmethane diisocyanate with polycaprolactone ester diol as a polyisocyanate to obtain a prepolymer, and using a high molecular polyol and a low molecular polyol as a curing agent. ing. The purpose of this elastomer is to obtain abrasion resistance and durability. Tokuhei 7-7222
In JP-A No. 2, a prepolymer is obtained by using diphenylmethane diisocyanate or tolylene diisocyanate as a polyisocyanate and reacting polyoxytetramethylene glycol in the presence of a plasticizer. A polyurethane molded product is obtained by reacting with an amine as a curing agent in the presence of a plasticizer. The purpose of this elastomer is to have good moldability, low hardness, and rubber elasticity.

[0004]

SUMMARY OF THE INVENTION The present inventors have solved the drawbacks of the conventional casting technique, especially the prepolymer method, and have conducted intensive studies and studies on improvement of workability and various physical properties. By using an NCO-terminated prepolymer and a polyol composed of a polyester polyol, etc., the change in physical properties due to the stoichiometric deviation is remarkably improved, and the defoaming property and the demolding time are shortened by lowering the viscosity. As a result, the castability was improved, and the obtained elastomer was found to have excellent physical strength, and reached the present invention.

[0005]

That is, the present invention provides (A)
A polyurethane elastomer composition comprising a mixture of an NCO group terminated prepolymer as a component and a long chain polyol, a short chain diol and a short chain triol as the component (B), wherein diphenylmethane diisocyanate (hereinafter, MD) is used as the polyisocyanate of the NCO group terminated prepolymer.
I)) polyisocyanate and hexamethylene diisocyanate (hereinafter abbreviated as HDI) polyisocyanate are used in combination, and the polyol for prepolymer and (B)
A two-component casting polyurethane elastomer composition, characterized in that a polycarbonate polyol and a polycaprolactone polyol are used in combination as a long-chain polyol as a component, and / or a poly (carbonate / caprolactone) polyol is used.

The present invention is based on M as a polyisocyanate used in the NCO group-terminated prepolymer as the component (A).
DI-based polyisocyanate is MDI containing MDI and / or MDI dimer compound and / or MDI containing carbodide-modified MDI, and HDI-based polyisocyanate is HDI isocyanurate ring-containing modified product,
Alternatively, it is a polyurethane elastomer composition for two-component casting, which is a modified product of uretdione ring and isocyanurate ring of HDI.

In the present invention, the component (A) and the component (B) are mixed with each other by using a two-component casting polyurethane elastomer composition.
A method for producing a polyurethane elastomer, comprising mixing and casting at 5 to 95 ° C.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION NCO which is the component (A) of the present invention
Examples of the MDI-based polyisocyanate constituting the group-terminated prepolymer include MDI, MDI dimer, carbodide-modified MDI, polyphenyl polymethylene polyisocyanate (hereinafter abbreviated as polymeric MDI), MD
Various isomers of I, 4,4'-MDI, 2,4'-M
DI, 2,2'-MDI, etc. and mixtures of these isomers,
There are derivatives of such polyisocyanates, which can be used alone or as a mixture of two or more kinds.

[0009] The MDI dimer used in the present invention is MD
It can be obtained by adding a catalyst that promotes dimerization to a polyol adduct of I or MDI, carrying out a reaction at 50 to 90 ° C. for 4 to 9 hours, and adding a catalyst deactivator. As a catalyst for promoting dimerization, tri-n-butylphosphine, tri-n-octylphosphine, tris-
There are (dimethylamino) phosphine and the like, and examples of the catalyst deactivator include methyl p-toluenesulfonate and di- (2-ethylhexyl) -ester phosphate.

The carbodiimidated modified M used in the present invention
DI is MDI or a polyol adduct of MDI as a carbodiimidization catalyst, for example, 3-methyl-1-phenyl-3-phosphorene-1-oxide, 3-methyl-1-ethyl-3-phosphorene- which is a phospholene catalyst.
1-oxide, 3-methyl-1-phenyl-2-phospholen-1-oxide, 1-methyl-3-phospholen-1-oxide, 1-phenyl-2-phosphorene-
1-oxide, 1-methoxy-3-phosphorene-1-
Toxide, 3-methyl-1-phenyl-3-phospholen-1-sulfide and the like are used at 50 to 90 ° C. for 3 to
The reaction is carried out for 5 hours, and trichlorosilane, dichloroaphenylsilane, trichloromethylsilane, trichlorovinylsilane, dichlorodimethylsilane and the like are added as catalyst deactivators to terminate the reaction.

The MDI polyol adduct used in the present invention can be obtained by reacting MDI and a polyol at about 50 to 100 ° C. In this case, 20% by weight or less of the NCO group of MDI is reacted with a polyol,
It is a polyol adduct of MDI. The molecular weight of the polyol for obtaining the MDI polyol adduct is 62 to 3
000, having a functionality of 2-3, for example, 1,3-butanediol (hereinafter abbreviated as 1,3-BD), dipropylene glycol, 1,6-hexane glycol (hereinafter, 1,6-BD)
HG), 3-methyl-1,5-pentanediol, neopentyl glycol (hereinafter abbreviated as NPG),
2,2-diethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2-n-butyl-2
-Ethyl-1,3-propanediol (hereinafter referred to as BEPG
Abbreviated), glycerin, trimethylolpropane, etc., polyester polyols obtained by ester reaction of these diols and triols with dibasic acids, polyether polyols obtained by addition reaction of these diols and triols with alkylene oxides. Etc. These can be used alone or as a mixture of two or more.

[0012] The present invention relates to a polyisocyanate, MD
Since an I-based polyisocyanate is used, it has good physical properties such as tensile strength, tear strength and abrasion resistance, and has excellent durability. Further, the calpositimide-modified MDI obtained from the polyol adduct of MDI, or the MDI dimer and the calpositimide-modified MDI has very excellent compatibility with the HDI-based polyisocyanate.

The HDI-based polyisocyanate constituting the NCO group-terminated prepolymer which is the component (A) of the present invention is an isocyanurate ring-containing modified product of HDI or a polyol adduct of HDI (hereinafter abbreviated as nurate modified product). Alternatively, a uretdione nurate modified product of HDI or a polyol adduct of HDI is most suitable. Besides, there are derivatives of HDI, hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate and the like, which can be used alone or in combination as a mixture of two or more kinds.

[0014] As a catalyst for obtaining a modified HDR of HDI, propionic acid, butyric acid, valeric acid, caproic acid,
Heptanoic acid, caprylic acid, pelargonic acid, capric acid,
Undecylic acid and the potassium or sodium salts of these branched fatty acids. As a co-catalyst that can be used in combination with the catalyst, a phenolic hydroxy compound (phenol, cresol, etc.), an alcoholic hydroxy compound (ethanol, cyclohexanol, etc.), or a tertiary amine (triethylamine, methylpiperidine, etc.) is used. be able to. The reaction proceeds easily with this co-catalyst. The amount of the catalyst used is 0.001 to 0.25% by weight based on the polyisocyanate, and the cocatalyst is 0.01 to 0.2% by weight.
0.2% by weight. In addition, a reaction terminator can be used. As the terminating agent, for example, phosphoric acid, sulfuric acid, methyl p-toluenesulfonate and the like can be used, and the used amount can be 0.5 to 5.0 times the catalyst equivalent.

Examples of effective catalysts for obtaining modified uretdione / nurate derivatives of HDI include phosphines such as triethylphosphine, dibutylethylphosphine, tri-n-propylphosphine, trioctylphosphine and triamylphosphine.

The reaction for obtaining such a modified form of HDR or a modified uretdione / nurate can be obtained by reacting at 50 to 100 ° C. for 3 to 7 hours. The reaction mixture thus obtained can remove unreacted HDI, for example, by thin-film distillation.
The uretdione / nurate modified form of HDI has a ratio of the isocyanurate cyclic trimer content of 11 to 40% by weight to the uretdione dimer content of 20 to 60% by weight.
The NCO group content is 17 to 25% by weight.

The polyol adduct of HDI used in the present invention is one in which a part (20% by weight or less) of all NCO groups is a polyol adduct. As the polyol that can be used here, the polyol used when obtaining the MDI polyol adduct can be used. The uretdione dimer content and isocyanurate cyclic trimer content were determined from a calibration curve based on the area percentage of each peak obtained by gel permeation chromatography using differential refractometer detection.

As the polyol constituting the NCO group-terminated prepolymer which is the component (A) of the present invention, a polycarbonate polyol and a polycaprolactone polyol are used in combination, and / or poly (carbonate / caprolactone).
There are polyols. Polycarbonate polyols having a molecular weight of 500 to 4000, for example, a dealcoholization condensation reaction of glycols and dialkyl carbonates such as dimethyl and diethyl, or a phenol condensation reaction of glycols and diphenyl carbonate, or glycols and ethylene carbonate, diethyl carbonate and the like And those obtained by the ethylene glycol condensation reaction. As the glycols, for example,
1,6-HG, diethylene glycol, propylene glycol, 1,4-butanediol, 3-methyl-1,5
-Aliphatic diols such as pentanediol and NPG; and alicyclic diols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol. For example, there is poly (hexamethylene carbonate) polyol obtained by a condensation reaction between 1,6-HG and diethyl carbonate.

The polycaprolactone polyol used in the present invention has a molecular weight of 500 to 4000, for example, α
Lactones such as caprolactone, β-caprolactone, γ-caprolactone, δ-caprolactone, α-methyl-ε-caprolactone, β-methyl-ε-caprolactone and ethylene glycol, propylene glycol, 1,4-butanediol, 5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-
It can be obtained by reaction with HG, NPG, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, decamethylene glycol, polyethylene glycol, polytetramethylene glycol and the like. Preferred molecular weights are between 1000 and 3000. For example, specifically, Praxel P-210 (molecular weight: 1000) and Praxel P-22 manufactured by Daicel Chemical Industries, Ltd.
0 (molecular weight 2000), TONE POLYO made by UNION CARBIDE
L 0210 (molecular weight 530, hydroxyl value 212), TONE POLYO
L 0210 (molecular weight: 830, hydroxyl value: 135). Further, as a triol, TONE POLYOL 0305 (molecular weight 54
0, hydroxyl value 310), TONE POLYOL 0301 (molecular weight 30)
0, hydroxyl value 560), TONE POLYOL 0310 (molecular weight 90
0, hydroxyl value 187) and the like.

Further, a lactone type polyester polyether polyol can also be used. This can be obtained by conducting a ring-opening addition polymerization reaction of a lactone with a polyol having two or more active hydrogen groups in the presence of a catalyst, followed by adding an alkylene oxide in the presence of a catalyst to carry out the reaction. As the polyol or lactone, the compound used for obtaining polycaprolactone polyol can be used. Examples of the catalyst include alkali metals such as lithium, sodium, and potassium, and hydroxides and alcoholates thereof, and these can be used alone or as a mixture of two or more.

The poly (carbonate caprolactone) polyol used in the present invention has a molecular weight of 500 to 4
000, a method of transesterifying a polycarbonate polyol with a polycaprolactone polyol, or a method of reacting a polycarbonate polyol with a lactone, the polycarbonate polyol and the polycaprolactone) polyol and the lactone and / or the carbonate. It can be obtained by a method or the like by reacting in the presence of a compound. The usage ratio of the polycarbonate polyol and the polycaprolactone polyol used in the present invention is 25 to 75% by weight of the polycarbonate polyol and 75 to 25% by weight of the polycaprolactone polyol. By the use of such various polyols,
Elastomers have hydrolysis resistance, tensile strength, tear strength,
It has excellent durability such as abrasion resistance.

The NCO group-terminated prepolymer, which is the component (A) of the present invention, is prepared at a molar ratio of NCO group / active hydrogen group of 3.0 to 30, preferably 4.0 to 20. Be seen. The reaction between the polyisocyanate and the polyol may be carried out according to a conventional method. The reaction is usually carried out at a temperature of 50 to 100 ° C. to obtain an NCO-terminated prepolymer.

As the component (B) of the present invention, long-chain polyols, short-chain diols, short-chain triols and the like are used.
As the long-chain polyol, the polyol used to obtain the NCO group-terminated prepolymer is used. Molecular weight is 5
00 to 4000.

The short-chain diol used in the component (B) of the present invention has a molecular weight of 62 to less than 500, for example, ethylene glycol, propanediol, butanediol, pentanediol, 1,6-HG, methylpentanediol, NPG, Cyclohexanedimethanol, 1,4-bis (2-hydroxyethoxy) benzene (hereinafter, BHE
B), diethylene glycol, dipropylene glycol and the like. Preferred molecular weights are from 62 to 25.
0.

The short-chain triol used in the component (B) of the present invention has a molecular weight of 92 to less than 500, preferably 92 to 350. For example, glycerin, trimethylolpropane (TMP), 1,2,6-hexanetriol, 1,2,4-butanetriol, diglycerin, pentaerythritol, trimethylolethane, triisopropanolamine, triethanolamine, diisopropanolamine and the like Can be used alone or in combination of two or more.

Polyol in component (B) of the present invention /
The weight mixing ratio of short chain diol / short chain triol is used in the range of 75 to 95/5 to 25/0 to 10, respectively.
A preferred range is from 80 to 90/6 to 20/0 to 5. Outside this range, the time required for demolding during molding is insufficiently reduced, and the physical properties are also poor.

The components (A) and (B) of the present invention are NC
It is used so that the equivalent ratio of O group / active hydrogen group becomes 0.8 to 1.20. In this case, the weight mixing ratio A / B is 100
/ 40 to 100/222. If necessary, a catalyst, an additive or the like can be used. As the catalyst, a metal system such as dibutyltin dilaurate and an amine system such as diethanolamine are used. Casting is (A) /
(B) The mixture is poured into a pre-heated mold,
Primary crosslinking at a temperature of ° C. After this primary crosslinking, 10
After secondary crosslinking at 0 to 170 ° C and aging, a urethane elastomer is obtained. The elastomer obtained by using the composition of the present invention is useful in various fields such as rolls, tires and pipes. Also, it can be suitably used for OA equipment.

[0028]

The cast polyurethane elastomer using the composition according to the present invention can be used without impairing general physical properties such as hardness, tensile strength, elongation and compression set.
It also has good casting workability and shows excellent properties such as heat resistance and weather resistance. In particular, by using the isocyanurate ring of HDI together, more excellent heat resistance, weather resistance and the like can be obtained.

[0029]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. “Parts” and “%” in the examples indicate “parts by weight” and “% by weight”, respectively.

Synthesis Example 1 Preparation of NDI modified product (A-1) of HDI 300 parts of HDI was put into a 500 ml separable flask equipped with a thermometer, a stirrer and a nitrogen seal tube, and then 0.05 parts of potassium caprate as a catalyst. Then, 0.3 part of phenol as a cocatalyst was added, and an isocyanurate-forming reaction was carried out at 60 ° C. for 4.5 hours. To this reaction solution, 0.042 part of phosphoric acid was added as a terminator, and after stirring at 60 ° C. for 1 hour, free HDI was removed by a molecular distillation apparatus. The obtained liquid was a pale yellow transparent liquid with an NCO content of 22.0% and a viscosity of 2100 m.
Pa · S / 25 ° C, free HDI content was 0.4%. This H
The nurate modified form of DI is designated as A-1.

Synthesis Example 2 Production of Nurate Modified Product (A-2) of HDI 300 parts of HDI, 1,3-using the same apparatus as in A-1
BD 10.2 parts, potassium propionate 0.1 as a catalyst.
The reaction was carried out in the same manner as in A-2 using 06 parts, 0.3 parts of phenol and 0.072 parts of phosphoric acid. After reacting the polyol with HDI, the NCO content was 45.3%. After distillation,
The NCO content was 19.2%, the viscosity was 2800 mPa · s / 25 ° C., and the free HDI content was 0.3%. This HDR nurate modified product is designated as A-2.

Synthetic Example 3 Production of Nurate Modified Product (A-3) of HDI 300 parts of HDI, 1,6-
The reaction was carried out in the same manner as in A-2 using 3.3 parts of HD, 0.03 parts of sodium undecylate and 0.198 parts of phosphoric acid. After reacting the polyol with HDI, the NCO content is 48.6.
%Met. After distillation, NCO content 20.5%, viscosity 3
The free HDI content was 0.4% at 000 mPa · s / 25 ° C. This HDR-modified nurate is referred to as A-3.

Synthesis Example 4 Preparation of uretdione nurate modified product (A-4) of HDI
HDI300 parts using the same apparatus as forming A-2, NPG
6.4 parts, 0.4 part of tributylphosphine, phosphoric acid 0.1 part.
The reaction was carried out in the same manner as in A-2 using 6 parts. After the reaction
The CO content was 37.1%. After distillation, the NCO content is 2
The content was 1.2%, the viscosity was 215 mPa · s / 25 ° C, and the free HDI content was 0.2%. This HDI dimer is 32%, H
The DI trimer was 28%. This uretdione-nurate modified form of HDI is designated as A-4.

Synthesis Example 5 Preparation of uretdione nurate modified product (A-5) of HDI
HDI300 parts using the same apparatus as forming A-4, BEPD
The reaction was carried out in the same manner as in A-5, using 6.0 parts, 0.3 parts of tributylphosphine and 0.33 parts of methyl paratoluenesulfonate. After the reaction, the NCO content was 39.0%. After distillation, NCO content 21.9%, viscosity 170mPa
-S / 25 ° C, free HDI content was 0.2%. The dimer of HDI was 43%, and the trimer of HDI was 31%. This H
The uretdione nurate modified form of DI is designated as A-5.

Examples 1 to 4 of polyurethane elastomer composition and elastomer
Production (A) MDI-based polyisocyanate and HDI-based polyisocyanate are used as the polyisocyanate for the NCO group-terminated prepolymer, and the HDI-based polyisocyanate uses A-1 of Synthesis Example 1, and poly (hexamethylene carbonate) is used as the polyol. ) Using diol and polycaprolactone polyol, a polyurethane elastomer composition comprising (B) poly (hexamethylene carbonate) diol), polycaprolactone polyol, BHEB and TMP was obtained. [Production of Elastomer] In a separable flask equipped with a thermometer, a stirrer, and a nitrogen sealed tube, the HDR-nullated modified product (A-1) of Synthesis Example 1 and MDI-based polyisocyanate were used to prepare poly (hexamethylene carbonate) diol. Using polycaprolactone diol in the proportions shown in Table 1,
The reaction was carried out at 70 ° C. for 3 hours while stirring under a nitrogen stream.
A viscous prepolymer (A) was obtained. Table 1 shows the NCO group content and the like. Poly (hexamethylene carbonate) diol, polycaprolactone polyol, BHEB, and TMP were added to the thus obtained prepolymer (A) at the ratio shown in Table 1 as the component (B), and the mixture was thoroughly stirred until the mixture became completely uniform. After that, defoaming was performed at a reduced pressure of 10 Torr or less until the foaming stopped. This mixture was poured into a centrifugal molding machine preheated to 130 ° C., primary curing was performed at 130 ° C. for 1 hour, and the obtained plate-like polyurethane was secondarily crosslinked at 120 ° C. for 2 hours, and then further cured at room temperature for 1 hour.
After aging for a week, an elastomer was obtained. The prescription is shown in Table 1 and the results are shown in Table 2.

[0036]

[Table 1]

Description of Table 1 MT (1): 4,4'-MDI (Nippon Polyurethane Industry Co., Millionate MT) MT (2): 4,4'-MDI dimer modified product (containing 15% dimer compound) NCO Content 31.1% MTL (1): Carbodiimide modified MDI (manufactured by Nippon Polyurethane Industry, Millionate MTL, NCO content 2
9.5%) Polyol (A): Poly (hexamethylene carbonate) polyol (molecular weight 1000, OH value 112) Polyol (B): Poly (hexamethylene carbonate) polyol (molecular weight 1500, OH value 74.8) Polyol (C): Poly (hexamethylene carbonate) polyol (molecular weight 2000, OH value 56.1) Polyol (D): polycaprolactone polyol,
(Molecular weight 1000, OH value 112) Polyol (E): polycaprolactone polyol,
(Molecular weight 1500, OH value 74.8) Polyol (F): polycaprolactone polyol,
(Molecular weight 2000, OH value 56.1) Short-chain diol: BHEB Short-chain triol: TMP

[0038]

[Table 2]

Explanation of Table 2 Hardness (JIS A) was measured 1 day and 1 week after the completion of secondary crosslinking. The demolding time was such that the molded product had no tackiness and could be easily removed from the mold at a primary curing temperature of 130 ° C. Physical property values conformed to JIS K6301.

Examples 5-8 Polyurethane Elastomer Compositions and Elastomers
Production (A) MDI-based polyisocyanate and HDI-based polyisocyanate are used as the polyisocyanate for the NCO group-terminated prepolymer, and HDI-based polyisocyanate is A-2 of Synthesis Example 2, and poly (hexamethylene carbonate) is used as the polyol. ) Using a diol and a polycaprolactone polyol, a polyurethane elastomer composition comprising (B) a poly (hexamethylene carbonate) diol, a polycaprolactone polyol, BHEB and TMP was obtained. [Production of Elastomer] Using polyisocyanate and polyol under the conditions shown in Table 3, the reaction was carried out in the same manner as in Example 1 to obtain viscous prepolymer A. Table 3 shows the NCO group content and the like. Prepolymer A thus obtained
A polyurethane elastomer was obtained in the same manner as in Example 1, except that the component (B) was used under the conditions shown in Table 3. The results are shown in Table 4.

[0041]

[Table 3]

[0042]

[Table 4]

Examples 9-12 Polyurethane Elastomer Compositions and Elastomers
Production (A) MDI-based polyisocyanate and HDI-based polyisocyanate are used as the polyisocyanate for the NCO-terminated prepolymer, and HDI-based polyisocyanate is A-3 of Synthesis Example 3, and poly (hexamethylene carbonate) is used as the polyol ) Using diol and polycaprolactone polyol, a polyurethane elastomer composition comprising (B) poly (hexamethylene carbonate) diol), polycaprolactone polyol, BHEB and TMP was obtained. [Production of Elastomer] Using polyisocyanate and polyol under the conditions shown in Table 5, the reaction was carried out in the same manner as in Example 1 to obtain viscous prepolymer A. Table 5 shows the NCO group content and the like. Prepolymer A thus obtained
A polyurethane elastomer was obtained in the same manner as in Example 1, except that the component (B) was used under the conditions shown in Table 5. Table 6 shows the results.

[0044]

[Table 5]

[0045]

[Table 6]

Examples 13-16 Polyurethane Elastomer Compositions and Elastomers
Production (A) MDI-based polyisocyanate and HDI-based polyisocyanate are used as the polyisocyanate for the NCO group-terminated prepolymer, and the HDI-based polyisocyanate uses A-4 of Synthesis Example 4, and poly (hexamethylene carbonate) is used as the polyol. ) Using diol and polycaprolactone polyol, a polyurethane elastomer composition comprising (B) poly (hexamethylene carbonate) diol), polycaprolactone polyol, BHEB and TMP was obtained. [Production of Elastomer] Using polyisocyanate and polyol under the conditions shown in Table 7, the reaction was carried out in the same manner as in Example 1 to obtain viscous prepolymer A. Table 7 shows the NCO group content and the like. Prepolymer A thus obtained
A polyurethane elastomer was obtained in the same manner as in Example 1, except that the component (B) was used as the component under the conditions shown in Table 7. Table 8 shows the results.

[0047]

[Table 7]

[0048]

[Table 8]

Examples 17-20 Polyurethane Elastomer Compositions and Elastomers
Production (A) MDI-based polyisocyanate and HDI-based polyisocyanate were used as the polyisocyanate for the NCO-terminated prepolymer, A-5 of Synthesis Example 5 was used as the HDI-based polyisocyanate, and poly (hexamethylene carbonate) was used as the polyol. ) A diol and polycaprolactone polyol were used to obtain a polyurethane elastomer composition comprising (B) poly (hexamethylene carbonate) diol), polycaprolactone polyol, BHEB and TMP. [Production of Elastomer] Using polyisocyanate and polyol under the conditions shown in Table 9, the reaction was carried out in the same manner as in Example 1 to obtain viscous prepolymer A. Table 9 shows the NCO group content and the like. Prepolymer A thus obtained
A polyurethane elastomer was obtained in the same manner as in Example 1, except that the component (B) was used as the component under the conditions shown in Table 9. Table 10 shows the results.

[0050]

[Table 9]

[0051]

[Table 10]

Comparative Examples 1 to 4 Polyisocyanates and polyols were used under the conditions of Table 11, and the reaction was carried out at a temperature of 60 to 70 ° C. for 3 hours while stirring under a nitrogen stream to give a viscous prepolymer A component. Got Table 11 shows the NCO group content and the like. The component (B) was used for the prepolymer A component thus obtained under the conditions shown in Table 11, and the mixture was thoroughly stirred until the A / B mixture became completely transparent. Was performed for 60 minutes until foaming subsided. This A / B mixture was injected into a centrifugal molding machine preheated to 130 ° C, and primary curing was performed at 130 ° C for 1 hour. The obtained plate-like polyurethane was secondarily crosslinked at 120 ° C. for 2 hours, and then aged at room temperature for 1 week to obtain a polyurethane elastomer. Table 12 shows the results.

[0053]

[Table 11]

[0054]

[Table 12]

Claims (3)

[Claims] 1. A polyurethane elastomer composition comprising a mixture of an NCO group-terminated prepolymer as the component (A) and a long-chain polyol, a short-chain diol and a short-chain triol as the component (B). Diphenylmethane diisocyanate-based polyisocyanate and hexamethylene diisocyanate-based polyisocyanate are used in combination as the isocyanate, and polycarbonate polyol and polycaprolactone polyol are used in combination as the prepolymer polyol and the long-chain polyol of the component (B), and / or poly (carbonate. A two-component polyurethane elastomer composition for casting, which is a caprolactone) polyol. 2. A diphenylmethane diisocyanate-based polyisocyanate as a polyisocyanate used as a polyisocyanate used in an NCO group-terminated prepolymer as the component (A) is a diphenylmethane diisocyanate and / or diphenylmethane diisocyanate containing a dimer compound and / or a carbodide-modified diphenylmethane diisocyanate. The diphenylmethane diisocyanate contained, wherein the hexamethylene diisocyanate-based polyisocyanate is an isocyanurate ring-containing modified product of hexamethylene diisocyanate or a uretdione ring- and isocyanurate ring-containing modified product of hexamethylene diisocyanate. The two-component cast polyurethane elastomer composition described. 3. A two-component casting polyurethane elastomer composition according to claim 1 or 2 is used (A).
A method for producing a polyurethane elastomer, which comprises mixing and casting the component and the component (B) at 35 to 95 ° C.