Composition for compression molding, and compression molding method

Abstract

To provide a composition for compression molding, excellent in storage stability in a state before thermal hardening, and becoming a molded product having high versatility by expressing various characteristics in a good balance after thermal hardening, and to provide a compression molding method for obtaining a polyurethane molded product from the composition for compression molding.SOLUTION: A composition for compression molding is a mixture containing (A) a main agent, (B) a hardening agent, and a polyurea component, and is a clay-like compound. (A) is a mixture of (A-1) a specific polyol component and (A-2) a specific diamine component, and (B) is a mixture of (B-1) a specific alicyclic polyisocyanate compound and (B-2) a specific aliphatic polyisocyanate compound.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a compression molding composition and a compression molding method. [Background technology]

[0002] Compression molding is a classic molding method that has been used since plastics were first invented, and is widely known as a typical molding method for obtaining thermosetting plastics (see, for example, Patent Document 1). Specifically, in compression molding, for example, a compression molding composition (clay-like compound) is placed in a concave-convex mold heated to an appropriate temperature, compressed and hardened, and the mold is removed after the hardening reaction inside the mold is completed to obtain a thermosetting plastic.

[0003] Compression molding is also used to produce many rubber molded products, including tires. Specifically, the compression molding process for producing rubber molded products involves placing a compression molding composition (clay-like rubber compound) containing, as essential components, sulfur, which serves as a crosslinking agent for diene rubbers such as natural rubber, butadiene rubber, and styrene-butadiene rubber, and carbon black, which serves as a reinforcing filler, as well as other components such as reinforcing agents, fillers, plasticizers, and additives, into a concave-convex mold to compress and harden the composition. The curing reaction is completed within the mold, and the mold is then removed to produce a rubber molded product. The diene rubbers described above are used as materials for many rubber molded products because of their excellent tensile properties and abrasion resistance, good processability, and low cost.

[0004] Furthermore, compression molding is also applied to the production of large molded articles such as bathtubs. Specifically, the compression molding method for obtaining large molded articles is a molding method in which, for example, a compression molding composition (clay-like SMC compound) containing an unsaturated polyester, a radical initiator, and a filler is formed into sheets, and the sheets are stacked according to the wall thickness and then compression molded.

[0005] In addition to the compression molding method described above, a casting method has also been widely known as another molding method. The casting method is a molding method in which a mixed liquid containing, for example, a polyol component, an isocyanate component, and a filler such as calcium carbonate or silica powder is poured into an open mold and a curing reaction is completed within the mold to obtain a molded product. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 63-004918 Summary of the Invention [Problem to be solved by the invention]

[0007] The clay-like rubber compounds described above are black in color due to the carbon black, and have drawbacks such as poor heat resistance, weather resistance, and ozone resistance. Therefore, clay-like rubber compounds do not exhibit a balanced range of properties after heat curing, making it difficult to produce versatile molded products. Another drawback is that obtaining clay-like rubber compounds requires appropriate equipment and skilled mixing techniques.

[0008] Furthermore, since the above-mentioned SMC compound contains an unsaturated polyester and a radical initiator, it has a short stability period before heat curing and poor storage stability. Furthermore, SMC compounds are often used for large, highly rigid products. The large molded products obtained by heat curing SMC compounds are large, so their uses are limited and their versatility is poor.

[0009] Furthermore, in the above-mentioned casting molding method, one side of the molded product obtained after heat curing often becomes flat. This limits the uses of the molded product, making it less versatile. Furthermore, in the above-mentioned mixed liquid, moisture adhering to the surface of the filler may react with the isocyanate component, causing foaming. Therefore, when the mixed liquid is made into a clay-like compound, the generated foam may reduce the storage stability of the compound at room temperature.

[0010] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a compression molding composition that has excellent storage stability before heat curing and that, after heat curing, exhibits a variety of well-balanced properties to form a highly versatile molded product, and a compression molding method for obtaining a polyurethane molded product from the compression molding composition. [Means for solving the problem]

[0011] The above problems can be solved by the following means. [1] A compression molding composition which is a mixture containing (A) a base agent, (B) a curing agent, and a polyurea component, and is a clay-like compound, The (A) main component is a mixture of an (A-1) polyol component and an (A-2) diamine component, the amount of the (A-1) polyol component added is 75 to 95 parts by mass relative to 100 parts by mass of the total amount of the (A-1) polyol component and the (A-2) diamine component added, The (A-1) polyol component is a liquid diol compound having two hydroxyl groups, a number average molecular weight (Mn) of 500 to 2000, and a primary hydroxyl group at the end of the main chain, the amount of the (A-2) diamine component added is 3 to 15 parts by mass relative to 100 parts by mass of the total amount of the (A-1) polyol component and the (A-2) diamine component added, The (A-2) diamine component is a liquid aromatic diamine compound having two amino groups and an amine value of 350 to 700 mgKOH / g, the (B) curing agent is a mixture of (B-1) an alicyclic polyisocyanate compound and (B-2) an aliphatic polyisocyanate compound, the amount of the (B-1) alicyclic polyisocyanate compound added is 5 to 15 parts by mass relative to 100 parts by mass of the total amount of the (B-1) alicyclic polyisocyanate compound and the (B-2) aliphatic polyisocyanate compound added, The (B-1) alicyclic polyisocyanate compound has an isocyanate group at a terminal thereof, and the number of functional groups of the isocyanate group is 3, the amount of the aliphatic polyisocyanate compound (B-2) added is 85 to 95 parts by mass relative to 100 parts by mass of the total amount of the alicyclic polyisocyanate compound (B-1) and the aliphatic polyisocyanate compound (B-2), The (B-2) aliphatic polyisocyanate compound has an isocyanate group with a functionality of 2. Compression molding composition. [2] The compression molding composition according to [1], wherein the liquid diol compound is a reaction product of 3-methyl-1,5-pentanediol and adipic acid. [3] The compression molding composition according to [2], wherein the liquid aromatic diamine compound is dimethylthiotoluenediamine. [4] The (B-1) alicyclic polyisocyanate compound is a trimer of hexamethylene diisocyanate, The compression molding composition according to [3], wherein the (B-2) aliphatic polyisocyanate compound is an allophanate-modified product of hexamethylene diisocyanate. [5] A compression molding method in which the compression molding composition according to any one of [1] to [4] is compression molded at 100 to 200°C to obtain a polyurethane molded product.

[0012] In the present invention and this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. For example, when it is written as "A to B," the numerical range is "not less than A and not more than B."

[0013] The "composition for compression molding" described in the following embodiments of this specification refers to a clay-like compound before thermal curing (before the cross-linked structure of urethane bonds is sufficiently formed). Also, the "room temperature" described in the following embodiments refers to, for example, 5 to 35°C.

[0014] The method for measuring the "number average molecular weight (Mn)" herein is not particularly limited. For example, it can be determined as a polystyrene-equivalent molecular weight by gel permeation chromatography (GPC). In this case, for example, a GPC apparatus "HLC-8220" (trade name, manufactured by Tosoh Corporation) and columns G3000HXL+G2000HXL (both trade names, manufactured by Tosoh Corporation) may be used, and detection may be performed using a differential refractometer (RI detector) at a measurement temperature of 23°C and a flow rate of 1 mL / min. The eluent may be selected from, for example, THF (tetrahydrofuran), chloroform, NMP (N-methyl-2-pyrrolidone), and a m-cresol / chloroform mixture (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). When the measurement sample is soluble, for example, THF may be used.

[0015] The method for calculating the "amine value mg KOH / g" herein is not particularly limited, but for example, the (A-2) diamine component may be dissolved in a mixed solution of 1-butanol and toluene, and an automatic titrator (product name: AT-510) manufactured by Kyoto Electronics Manufacturing Co., Ltd., connected to a burette manufactured by the same company under the product name "APB-510-01B," may be used. Potentiometric titration may be performed using, for example, a 0.1 mol / L 2-propanolic hydrochloric acid solution as the titration reagent, and the number of mg of hydrochloric acid and the equivalent amount of KOH (potassium hydroxide) per 1 g of the (A-2) diamine component may be calculated as the amine value of the (A-2) diamine component.

[0016] Alternatively, the "amine value mgKOH / g" in this specification may be measured, for example, according to the method for measuring the total amine value described in JIS K 1557-7:2011 "Plastics - Test methods for polyurethane raw polyols - Part 7: Determination of basicity (indication of nitrogen content and total amine value)." [Effects of the Invention]

[0017] The compression molding composition of the present invention has excellent storage stability before heat curing, and after heat curing, various properties are exhibited in a well-balanced manner, resulting in a highly versatile molded product. Furthermore, the compression molding method of the present invention allows the production of a highly versatile polyurethane molded product by heat curing the compression molding composition. [Brief explanation of the drawings]

[0018] [Figure 1] 1 is a table summarizing the amounts of each compounded component added and the results of characteristic tests according to Examples and Comparative Examples. [Figure 2] FIG. 10 is an enlarged cross-sectional view schematically showing an example of the configuration of a concave mold according to a modified example. DETAILED DESCRIPTION OF THE INVENTION

[0019] Preferred embodiments of the compression molding composition of the present invention will be described below, but the present invention is not limited to the following embodiments except as defined by the present invention.

[0020] [Compression molding composition] The compression molding composition according to the present invention is a mixture containing (A) a main agent, (B) a curing agent, and a polyurea component, and is a clay-like compound, wherein the main agent (A) is a mixture of (A-1) a polyol component and (A-2) a diamine component, and the amount of the (A-1) polyol component added is 75 to 95 parts by mass per 100 parts by mass of the total amount of the (A-1) polyol component and the (A-2) diamine component added, The (A-1) polyol component is a liquid diol compound having two hydroxyl groups, a number average molecular weight (Mn) of 500 to 2000, and a primary hydroxyl group at the end of the main chain, the amount of the (A-2) diamine component added is 3 to 15 parts by mass relative to 100 parts by mass of the total amount of the (A-1) polyol component and the (A-2) diamine component added, and the (A-2) diamine component has two amino groups and an amine value of 350 to 700 mgKOH / g. The curing agent is a liquid aromatic diamine compound, and the (B) curing agent is a mixture of an alicyclic polyisocyanate compound (B-1) and an aliphatic polyisocyanate compound (B-2). The amount of the alicyclic polyisocyanate compound (B-1) added is 5 to 15 parts by mass per 100 parts by mass of the total amount of the alicyclic polyisocyanate compound (B-1) and the aliphatic polyisocyanate compound (B-2). The alicyclic polyisocyanate compound (B-1) has an isocyanate group at its terminal, and the functionality of the isocyanate group is 3. The amount of the aliphatic polyisocyanate compound (B-2) added is 85 to 95 parts by mass per 100 parts by mass of the total amount of the alicyclic polyisocyanate compound (B-1) and the aliphatic polyisocyanate compound (B-2). The functionality of the isocyanate group of the aliphatic polyisocyanate compound (B-2) is 2.

[0021] Due to the above-described embodiment, the compression molding composition of the present invention has excellent storage stability before heat curing. This allows for the production and storage of a desired amount of the compression molding composition in small quantities. Furthermore, by varying the types and amounts of the blended components, a wide variety of compression molding compositions with different properties after heat curing can be produced. In other words, a wide variety of compression molding compositions can be produced in small quantities. Furthermore, due to the above-described embodiment, the compression molding composition of the present invention exhibits a well-balanced range of properties (appearance and mechanical strength) after heat curing, resulting in a highly versatile polyurethane molded product. Specifically, as described in the Examples section below, the well-balanced range of properties in the polyurethane molded product obtained after heat curing allows the polyurethane molded product to be widely used, for example, as a cushioning material, vibration-proofing material, shock-absorbing material, or packing, making it highly versatile and extremely convenient. Below, each component contained in the compression molding composition of the present invention will be described in order.

[0022] <(A) Main ingredient> The compression molding composition according to the present invention contains a main component, namely, (A) a base component, which is a mixture of (A-1) a polyol component and (A-2) a diamine component.

[0023] ((A-1) Polyol Component) The polyol component (A-1) according to the present invention is a diol compound that is liquid at room temperature, has two hydroxyl groups, a number average molecular weight (Mn) of 500 to 2000, and has a primary hydroxyl group at the end of its main chain. If the polyol component (A-1) were solid at room temperature, this would be undesirable because it would hinder homogeneous mixing with the diamine component (A-2), which will be described later.

[0024] The polyol component (A-1) is a diol compound having a primary hydroxyl group. Here, diol compounds having a secondary or tertiary hydroxyl group are significantly less reactive than diol compounds having a primary hydroxyl group. Therefore, when a compression molding composition containing a diol compound having a secondary or tertiary hydroxyl group is loaded between a mold and then compression molded at, for example, 100 to 200°C, the curing time required is longer than that required for a compression molding composition containing a diol compound having a primary hydroxyl group, resulting in poor work efficiency and poor mechanical strength of the polyurethane molded product obtained after heat curing. Therefore, in the present invention, the polyol component (A-1) is a diol compound having a primary hydroxyl group.

[0025] The polyol component (A-1) has two hydroxyl groups. If the number of hydroxyl groups is less than two, the compression molding composition is likely to become an uncured composition. On the other hand, if the number of hydroxyl groups is more than two, a network-like crosslinked structure is formed in the compression molding composition, which may make it difficult to maintain an appropriate clay state. Furthermore, the mechanical strength of the polyurethane molded product obtained after heat curing may also be reduced. Therefore, in the present invention, the number of hydroxyl groups in the polyol component (A-1) is set to two.

[0026] The (A-1) polyol component has a number average molecular weight (Mn) of 500 to 2000. The number average molecular weight (Mn) of the (A-1) polyol component may be, for example, 550 to 1900, 600 to 1800, 650 to 1700, or 700 to 1600.

[0027] If the number-average molecular weight (Mn) of the (A-1) polyol component is less than 500, the storage stability of the compression molding composition at room temperature may decrease. On the other hand, if the number-average molecular weight (Mn) is greater than 2000, the mechanical strength of the polyurethane molded article obtained after heat curing may decrease. Therefore, in the present invention, the number-average molecular weight (Mn) of the (A-1) polyol component is set to 500 to 2000.

[0028] The amount of the (A-1) polyol component added is 75 to 95 parts by mass, preferably 85 to 95 parts by mass, and also preferably 90 to 93 parts by mass, per 100 parts by mass of the total amount of the (A-1) polyol component and the (A-2) diamine component added.

[0029] The (A-1) polyol component may be, for example, a liquid carbonate diol compound, a liquid ε-caprolactone diol compound, liquid polytetramethylene ether glycol (PTMG), a liquid diol compound that is a reaction product of 3-methyl-1,5-pentanediol and adipic acid (hereinafter referred to as a liquid polyester diol compound), or poly(oxyethylene) glycol (PEG), etc. Among these, the (A-1) polyol component is preferably a liquid polyester diol compound from the viewpoints of ease of compounding and maintaining an appropriate viscosity state of the compression molding composition.

[0030] Specific examples of the carbonate diol compound include those available under the trade names "DURANOL T-5650E (number of hydroxyl groups: 2, number average molecular weight (Mn): 500)," "DURANOL T-5650J (number of hydroxyl groups: 2, number average molecular weight (Mn): 785)," and "DURANOL T-5651 (number of hydroxyl groups: 2, number average molecular weight (Mn): 2000)," all manufactured by Asahi Kasei Corporation.

[0031] Specific examples of the ε-caprolactone diol compound include those available under the trade names "PLACCEL 212AL (number of hydroxyl groups: 2, number average molecular weight (Mn): 1250)" and "PLACCEL 220AL (number of hydroxyl groups: 2, number average molecular weight (Mn): 2000)" manufactured by Daicel Chemical Industries, Ltd.

[0032] Liquid polyester diol compounds have a chemical structure having a repeating ester group structure, and the repeating ester group structure may act secondarily with other components through, for example, intermolecular hydrogen bonding, etc. This makes mixtures containing the diol compounds more likely to be compounded.

[0033] Furthermore, the liquid polyester diol compound has, in addition to the repeating ester group structure, multiple methyl groups intermittently formed along the extension direction of the main chain. Therefore, when the compression molding composition contains a liquid polyester diol compound as the (A-1) polyol component, the action of these multiple methyl groups maintains non-crystallization and low viscosity, resulting in excellent workability and handling efficiency. Therefore, the (A-1) polyol component of the present invention is preferably a liquid polyester diol compound among the diol compounds listed above.

[0034] The liquid polyester-based diol compound is, for example, a polymer compound obtained by a dehydration condensation reaction between 3-methyl-1,5-pentanediol (MPD) and adipic acid. Specifically, examples of liquid polyester-based diol compounds that can be used include products manufactured by Kuraray Co., Ltd., such as "Kuraray Polyol P510 (number of hydroxyl groups: 2, number average molecular weight (Mn): 500)," "Kuraray Polyol P1010 (number of hydroxyl groups: 2, number average molecular weight (Mn): 1000)," and "Kuraray Polyol P2010 (number of hydroxyl groups: 2, number average molecular weight (Mn): 2000)."

[0035] Alternatively, the (A-1) polyol component may be a mixture of any one of "Kuraray Polyol P510," "Kuraray Polyol P1010," and "Kuraray Polyol P2010" and at least one of the carbonate diol compound, ε-caprolactone diol compound, and polytetramethylene ether glycol listed above.

[0036] ((A-2) Diamine component) The diamine component (A-2) according to the present invention is a liquid aromatic diamine compound having two amino groups and an amine value of 350 to 700 mgKOH / g.

[0037] The (A-2) diamine component has a higher reactivity with the (B) curing agent (described later) than the (A-1) polyol component, and reacts preferentially with the (B) curing agent. As a result, the compression molding composition contains a polyurea component formed by the reaction of the (A-2) diamine component with the (B) curing agent. The action of this polyurea component maintains a clay-like state for a predetermined period of time, improving workability (handling). Meanwhile, after the polyurea component is formed, the unreacted (A-1) polyol component contained in the compression molding composition reacts very slowly with the unreacted (B) curing agent that has not reacted with the (A-2) diamine component at room temperature. The compression molding composition maintains a stable state for approximately two weeks at room temperature and for approximately three months under refrigeration. The term "stable state" refers to a state in which the compression molding composition maintains a clay-like state, allowing subsequent compression molding. This also applies to the following explanations.

[0038] The diamine component (A-2) has two amino groups. If the number of amino groups is less than two, the shape and clay state of the compression molding composition will be unstable. On the other hand, if the number of amino groups is more than two, a network-like crosslinked structure will be formed in the compression molding composition, which may cause shape deterioration such as settling in the polyurethane molded product obtained after heat curing. Therefore, in the present invention, the number of amino groups in the diamine component (A-2) is set to two.

[0039] The diamine component (A-2) has an amine value of 350 to 700 mgKOH / g. The amine value of the diamine component (A-2) may be, for example, 400 to 650 mgKOH / g, 450 to 600 mgKOH / g, or 500 to 550 mgKOH / g.

[0040] If the amine value of the diamine component (A-2) is less than 350 mg KOH / g, the mixture containing the base resin (A) and the curing agent (B) may become liquid and not be compounded. In this case, the mixture cannot be compression molded. On the other hand, if the amine value is greater than 700 mg KOH / g, the mixture containing the base resin (A) and the curing agent (B) may generate heat during compounding, and the mixture may not be homogeneously compounded. Therefore, in the present invention, the amine value of the diamine component (A-2) is set to 350 to 700 mg KOH / g. The "amine value" refers to the amount of potassium hydroxide (KOH) (equivalent to the amount of hydrochloric acid) required to neutralize the amines present in 1 g of the diamine component (A-2).

[0041] The amount of the (A-2) diamine component added is 3 to 15 parts by mass, preferably 5 to 10 parts by mass, per 100 parts by mass of the total amount of the (A-1) polyol component and the (A-2) diamine component. If the amount is less than 3 parts by mass, the compression molding composition may become excessively soft and liquefy during compression molding at 100 to 200°C. On the other hand, if the amount is more than 15 parts by mass, the fluidity of the compression molding composition may decrease during compression molding, and the mechanical strength (hardness and strength) of the polyurethane molded product obtained after heat curing may increase excessively. Therefore, in the present invention, the amount of the (A-2) diamine component added is 3 to 15 parts by mass per 100 parts by mass of the total amount of the (A-1) polyol component and the (A-2) diamine component.

[0042] Specific examples of the (A-2) diamine component include 2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene, dimethylthiotoluenediamine (3,5-dimethylthio-2,4-toluenediamine, or 3,5-dimethylthio-2,6-toluenediamine), or diaminodiphenylmethane compounds (e.g., 4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, or 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane). Alternatively, the (A-2) diamine component may be a mixture of two or more selected from these.

[0043] More specifically, the (A-2) diamine component may be, for example, "Heartcure 10 (amine value: 630.0 mg KOH / g)," a product name manufactured by Kumiai Chemical Industry Co., Ltd., "Heartcure 30 (amine value: 531.0 mg KOH / g)," a product name manufactured by Kumiai Chemical Industry Co., Ltd., or "WANAMINE MDA-100 (amine value: 568.0 mg KOH / g)," a product name manufactured by Mitsui Chemicals Fine Chemicals, Inc. Among these, "Heartcure 30" is preferred because it allows the mixture containing the (A) base agent and the (B) curing agent to be converted slowly into a compression molding composition, improving storage stability.

[0044] <(B) Hardener> The compression molding composition according to the present invention contains, in addition to the base resin (A), a curing agent (B) as a main component. The curing agent (B) is a mixture of an alicyclic polyisocyanate compound (B-1) and an aliphatic polyisocyanate compound (B-2).

[0045] ((B-1) Alicyclic polyisocyanate compound) The (B-1) alicyclic polyisocyanate compound is an alicyclic compound having an isocyanate group at its terminal, and the number of functional groups of the isocyanate group is three.

[0046] The amount of the (B-1) alicyclic polyisocyanate compound added is 5 to 15 parts by mass, preferably 5 to 10 parts by mass, per 100 parts by mass of the total amount of the (B-1) alicyclic polyisocyanate compound and the (B-2) aliphatic polyisocyanate compound. If the amount is less than 5 parts by mass, the compression molding composition may liquefy during compression molding at 100 to 200°C. On the other hand, if the amount is more than 15 parts by mass, the hardness of the polyurethane molded product obtained after heat curing is improved, but the tensile elongation may decrease, resulting in poor strength. Therefore, in the present invention, the amount of the (B-1) alicyclic polyisocyanate compound added is 5 to 15 parts by mass per 100 parts by mass of the total amount of the (B-1) alicyclic polyisocyanate compound and the (B-2) aliphatic polyisocyanate compound.

[0047] The (B-1) alicyclic polyisocyanate compound may be, for example, a trimer of an aliphatic diisocyanate compound. Specifically, the (B-1) alicyclic polyisocyanate compound may be, for example, a trimer of hexamethylene diisocyanate (number of functional groups in the isocyanate group: 3) or a trimer of isophorone diisocyanate (number of functional groups in the isocyanate group: 3).

[0048] More specifically, the (B-1) alicyclic polyisocyanate compound may be, for example, a product name of "Duranate THA-100," "Duranate TLA-100 (number of functional groups of isocyanate groups: 3)," or "Duranate TUL-100 (number of functional groups of isocyanate groups: 3)," manufactured by Asahi Kasei Corporation.

[0049] ((B-2) Aliphatic polyisocyanate compound) The (B-2) aliphatic polyisocyanate compound is an aliphatic compound in which the functionality of the isocyanate group is two.

[0050] The amount of the aliphatic polyisocyanate compound (B-2) added is 85 to 95 parts by mass, and preferably 90 to 95 parts by mass, per 100 parts by mass of the total amount of the alicyclic polyisocyanate compound (B-1) and the aliphatic polyisocyanate compound (B-2). An amount greater than 95 parts by mass is not preferred because the fluidity of the compound may decrease during compression molding.

[0051] The (B-2) aliphatic polyisocyanate compound may be, for example, an allophanate-modified product of hexamethylene diisocyanate. An example of such a modified product is "Duranate A-201H" (number of functional groups in isocyanate groups: 2) manufactured by Asahi Kasei Corporation. Alternatively, the (B-2) aliphatic polyisocyanate compound may be, for example, a reaction product having an isocyanate group at a terminal, obtained by reacting hexamethylene diisocyanate with a fixed amount or less of a diol. Specifically, examples of such a reaction product include "Duranate D-201" (number of functional groups in isocyanate groups: 2) and "Duranate D-101" (number of functional groups in isocyanate groups: 2) manufactured by Asahi Kasei Corporation.

[0052] While the reaction ratio between the (A) polyol component and the (B) curing agent is not particularly limited, the equivalent ratio of the isocyanate groups (NCO) of the (B) curing agent to the hydroxyl groups (OH) of the (A) polyol component, i.e., the NCO / OH equivalent ratio, is preferably 0.95 to 1.3. An NCO / OH equivalent ratio greater than 1.3 is undesirable because foaming may occur during the curing process of the compression molding composition. On the other hand, an NCO / OH equivalent ratio less than 0.95 is undesirable because the compression molding composition may dissolve due to heat during compression molding, causing shape deterioration such as distortion in the polyurethane molded product obtained after heat curing.

[0053] <Other ingredients> In addition to the (A) polyol component and the (B) curing agent, the above-mentioned compression molding composition may contain additives such as a urethane catalyst, a colorant, a plasticizer, a stabilizer, a flame retardant, an antifoaming agent, a dispersant, a surface modifier, and a moisture adsorbent, as appropriate, within the range that does not impair the effects of the present invention.

[0054] (Urethanization catalyst) The urethanization catalyst may be a common catalyst such as a tertiary amine compound or an organometallic compound, etc. Specifically, the urethanization catalyst may be, for example, triethylenediamine, N,N-dimethylhexamethylenediamine, N,N-dimethyl-1,4-butanediamine, diazabicycloundecene (DBU®) and salts of DBU®, bismuth tris(2-ethylhexanoate), diisopropoxybis(ethylacetoacetate)titanium, lead octoate, and dibutyltin dilaurate.

[0055] (coloring agent) The colorant may be added to the (A) polyol component in advance. The amount of the colorant added is preferably less than 5 parts by mass, more preferably less than 1 part by mass, per 100 parts by mass of the total amount of the (A) base agent and the (B) curing agent.

[0056] The colorant is not particularly limited as long as it is a colorant for urethane resin, but may be, for example, a low-viscosity two-component paste colorant for urethane resin (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd., product name: FTR) that uses a special polyol as a vehicle.

[0057] (plasticizer) By controlling the amount of plasticizer added, it is possible to control to some extent the hardness of the polyurethane molded product obtained after heat curing. The amount of plasticizer added is preferably less than 15 parts by mass per 100 parts by mass of the total amount of (A) base resin and (B) curing agent added. If the amount is 15 parts by mass or more, the mechanical properties of the polyurethane molded product obtained after heat curing will deteriorate and bleeding due to the plasticizer may occur in the polyurethane molded product, which is not preferable.

[0058] The plasticizer may be, for example, a plasticizer for a typical polyurethane resin, such as diethylhexyl phthalate (DEHP), diisononyl phthalate (DINP), dibutyl phthalate, tris(2-chloroethyl)phosphate, tris(chloropropyl)phosphate (TCPP), or a product name "Hxamoll (registered trademark) DINCH (registered trademark)" manufactured by BASF.

[0059] (stabilizer) The stabilizer may be, for example, one or more selected from a heat stabilizer, an antioxidant, an ultraviolet absorber, an ultraviolet stabilizer, and a filler.

[0060] [Method for compression molding of a compression molding composition] Next, a method for preparing the compression molding composition and a compression molding method for compression molding the compression molding composition will be described.

[0061] (Method for preparing a compression molding composition) The (A-1) polyol component and the (A-2) diamine component are placed in a plastic beaker (Desco cup), dispersed, and mixed. The (B) curing agent is then added, and if necessary, a urethane catalyst is added. The mixture is dispersed and mixed at room temperature or under elevated temperatures, and then allowed to stand for a predetermined period of time to obtain a compression molding composition. During this process, the (A-2) diamine component reacts preferentially with the (B) curing agent over the (A-1) polyol component, resulting in the production of a polyurea component. The resulting compression molding composition therefore contains the (A-1) polyol component, unreacted (B) curing agent that did not react with the (A-2) diamine component, and the polyurea component. The polyurea component allows the compression molding composition to become a clay-like compound, which remains stable at room temperature for approximately 10 days and remains stable under refrigeration for approximately 3 months. The hardness of the compound produced varies depending on the type and amount of compounded ingredients, and can be designed to be appropriate, for example, from a clay-like hardness to a rubber hardness of about A50°.

[0062] The (B) curing agent is typically a mixture of an alicyclic polyisocyanate compound (B-1) and an aliphatic polyisocyanate compound (B-2). However, if necessary, it may be either an alicyclic polyisocyanate compound (B-1) or an aliphatic polyisocyanate compound (B-2). When adding the additives listed above, the additives may be added to the polyol component (A-1) in advance. Alternatively, the additives may be added to a plastic beaker when the polyol component (A-1) and the diamine component (A-2) are added.

[0063] (Compression molding method) The compression molding composition prepared by the above-mentioned preparation method is loaded between two upper and lower concave and convex molds, and then compression molded at 100 to 200°C for 5 to 60 minutes to obtain a polyurethane molded product with a rubber hardness A of approximately 20 to 90°. The compression molding time is inversely proportional to the molding temperature; for example, when the molding temperature is 100°C, 150°C, or 180°C, the compression molding time is approximately 60 minutes, approximately 10 minutes, or approximately 5 minutes, respectively. The obtained polyurethane molded product can be used immediately after preparation, but it is preferably conditioned (aged) for 2 weeks at room temperature or 2 hours at 100°C. [Example]

[0064] Next, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

[0065] [Preparation of Compression Molding Composition] Example 1 95 g of (A-1) polyol component (trade name: Kuraray Polyol P-1010 (number of hydroxyl groups: 2, number average molecular weight (Mn): 1000, manufacturer: Kuraray Co., Ltd.)) and 5 g of (A-2) diamine component (trade name: Heartcure 30 (amine value: 531.0 mg KOH / g), manufacturer: Kumiai Chemical Industry Co., Ltd.) were added to a plastic beaker (500 cc Desco cup), and the mixture was dispersed and mixed at room temperature. Next, 0.75 mg of a urethane catalyst (dibutyltin dilaurate) was added, and then a mixture of 3.2 g (5 parts by mass) of (B-1) alicyclic polyisocyanate compound (trade name: Duranate TLA-100 (number of isocyanate groups: 3, free NCO %: 23.4%), manufacturer: Asahi Kasei Corporation) and 61.1 g (95 parts by mass) of (B-2) aliphatic polyisocyanate compound (trade name: Duranate A-201H (number of isocyanate groups: 2, free NCO %: 17.2%), manufacturer: Asahi Kasei Corporation) was poured into a plastic beaker, and the mixture (NCO / OH equivalent ratio: 1.15) containing the (A-1) polyol component, (B-1) alicyclic polyisocyanate compound, and (B-2) aliphatic polyisocyanate compound was dispersed and mixed at room temperature. Thereafter, the mixture was left at room temperature for a predetermined time, to obtain a compression molding composition according to Example 1 (rubber hardness A: about 30°, shape: substantially block-like). In Example 1, the time required from pouring the mixed liquid of (B-1) the alicyclic polyisocyanate compound and (B-2) the aliphatic polyisocyanate compound into a plastic beaker to obtaining a compression molding composition (hereinafter referred to as compounding time) was 48 hours.

[0066] The free NCO% of the (B-1) alicyclic polyisocyanate compound is a value calculated, for example, by the following formula (1), and the free NCO% of the (B-2) aliphatic polyisocyanate compound is a value calculated, for example, by the following formula (2).

[0067] Free NCO% of (B-1) alicyclic polyisocyanate compound = [{(B-1) alicyclic polyisocyanate compound) isocyanate group functionality × 42 (NCO molecular weight)} / (B-1) alicyclic polyisocyanate compound molecular weight] × 100 (1)

[0068] (B-2) Free NCO% of aliphatic polyisocyanate compound = [{(B-2) Free NCO% of aliphatic polyisocyanate compound (B-2) (number of functional groups of isocyanate group of compound × 42 (molecular weight of NCO)) / (molecular weight of aliphatic polyisocyanate compound) × 100 (2)

[0069] <Example 2> A compression molding composition according to Example 2 was obtained in the same manner as in Example 1, except that the amount of the (B-2) aliphatic polyisocyanate compound added was 60.0 g (95 parts by mass). The time required for compounding according to Example 2 was 36 hours.

[0070] Example 3 A compression molding composition according to Example 3 was obtained in the same manner as in Example 1, except that the amount of the alicyclic polyisocyanate compound (B-1) added was 3.1 g (5 parts by mass) and the amount of the aliphatic polyisocyanate compound (B-2) added was 59.1 g (95 parts by mass). The time required for compounding according to Example 3 was 30 hours.

[0071] Example 4 A compression molding composition according to Example 4 was obtained in the same manner as in Example 1, except that the amounts of the (A-1) polyol component and the (A-2) diamine component were 90 g and 10 g, respectively, and the amounts of the (B-1) alicyclic polyisocyanate compound and the (B-2) aliphatic polyisocyanate compound were 8.0 g (10 parts by mass) and 72.2 g (90 parts by mass), respectively. The compounding time according to Example 4 was 24 hours.

[0072] <Example 5> A compression molding composition according to Example 5 was obtained in the same manner as in Example 4, except that the amount of the alicyclic polyisocyanate compound (B-1) added was 7.9 g (10 parts by mass) and the amount of the aliphatic polyisocyanate compound (B-2) added was 70.9 g (90 parts by mass). The time required for compounding according to Example 5 was 12 hours.

[0073] Example 6 A compression molding composition according to Example 6 was obtained in the same manner as in Example 4, except that the amount of the alicyclic polyisocyanate compound (B-1) added was 7.8 g (10 parts by mass) and the amount of the aliphatic polyisocyanate compound (B-2) added was 69.7 g (90 parts by mass). The time required for compounding according to Example 6 was 12 hours.

[0074] Example 7 A compression molding composition according to Example 7 was obtained in the same manner as in Example 1, except that the amounts of the (A-1) polyol component and the (A-2) diamine component were 85 g and 15 g, respectively, and the amounts of the (B-1) alicyclic polyisocyanate compound and the (B-2) aliphatic polyisocyanate compound were 14.4 g (15 parts by mass) and 81.7 g (85 parts by mass), respectively. The compounding time according to Example 7 was 12 hours.

[0075] Example 8 A compression molding composition according to Example 8 was obtained in the same manner as in Example 7, except that the amount of the alicyclic polyisocyanate compound (B-1) added was 14.2 g (15 parts by mass) and the amount of the aliphatic polyisocyanate compound (B-2) added was 80.2 g (85 parts by mass). The time required for compounding according to Example 8 was 4 hours.

[0076] Example 9 A compression molding composition according to Example 9 was obtained in the same manner as in Example 7, except that the amount of the alicyclic polyisocyanate compound (B-1) added was 13.9 g (15 parts by mass) and the amount of the aliphatic polyisocyanate compound (B-2) added was 79.0 g (85 parts by mass). The time required for compounding according to Example 9 was 4 hours.

[0077] Example 10 A compression molding composition according to Example 10 was obtained in the same manner as in Example 4, except that the (A-2) diamine component was changed to "Trade name: Heartcure 10 (amine value: 630.0 mg KOH / g)" manufactured by Kumiai Chemical Industry Co., Ltd., and the amounts of the (B-1) alicyclic polyisocyanate compound and the (B-2) aliphatic polyisocyanate compound added were 11.0 g (15 parts by mass) and 62.7 g (85 parts by mass), respectively. The compounding time according to Example 10 was 0.016 hours (60 seconds).

[0078] Example 11 A compression molding composition according to Example 11 was obtained in the same manner as in Example 4, except that the (A-2) diamine component was changed to "Trade name: WANAMINE MDA-100 (amine value: 568.0 mg KOH / g)" manufactured by Mitsui Chemicals Fine Chemicals, Inc., and the amounts of the (B-1) alicyclic polyisocyanate compound and the (B-2) aliphatic polyisocyanate compound added were 11.0 g (15 parts by mass) and 60.0 g (85 parts by mass), respectively. The compounding time according to Example 11 was 0.066 hours (4 minutes).

[0079] Example 12 A compression molding composition according to Example 12 was obtained in the same manner as in Example 4, except that the (A-1) polyol component was changed to "Trade name: Kuraray Polyol P-2010 (number of hydroxyl groups: 2, number average molecular weight (Mn): 2000)" manufactured by Kuraray Co., Ltd., and the amounts of the (B-1) alicyclic polyisocyanate compound and the (B-2) aliphatic polyisocyanate compound added were 5.4 g (10 parts by mass) and 48.2 g (90 parts by mass), respectively. The time required for compounding according to Example 12 was 24 hours.

[0080] Example 13 A compression molding composition according to Example 13 was obtained in the same manner as in Example 4, except that the (A-1) polyol component was changed to "Trade name: Kuraray Polyol P-510 (number of hydroxyl groups: 2, number average molecular weight (Mn): 500)" manufactured by Kuraray Co., Ltd., and the amounts of the (B-1) alicyclic polyisocyanate compound and the (B-2) aliphatic polyisocyanate compound added were 12.3 g (10 parts by mass) and 116.0 g (90 parts by mass), respectively. The time required for compounding according to Example 13 was 24 hours.

[0081] <Comparative Example 1> The amounts of the (A-1) polyol component and the (A-2) diamine component added were 100 g and 0 g (not added), respectively, and the amounts of the (B-1) alicyclic polyisocyanate compound added, the (B-2) aliphatic polyisocyanate compound added, and the urethane catalyst added were 4.8 g (10 parts by mass), 43.1 g (90 parts by mass), and 75.00 mg, respectively. An attempt was made to prepare a compression molding composition according to Comparative Example 1 in the same manner as in Example 1. However, the mixture containing each component did not form a clay-like compound because the polyurea component was not produced due to the absence of the (A-2) diamine component, and instead became a viscous liquid, and it was not possible to prepare a compression molding composition.

[0082] <Comparative Example 2> An attempt was made to prepare a compression molding composition according to Comparative Example 2 in the same manner as in Example 1, except that the amounts of the (A-1) polyol component and the (A-2) diamine component added were 98 g and 2 g, the amounts of the (B-1) alicyclic polyisocyanate compound and the (B-2) aliphatic polyisocyanate compound added were 2.6 g (5 parts by mass) and 49.6 g (95 parts by mass), and the amount of the urethane catalyst added was 1.25 mg. However, because the amount of the (A-2) diamine component added was too small, the mixture containing the components became hard and syrup-like, and it was not possible to prepare a compression molding composition.

[0083] <Comparative Example 3> A compression molding composition according to Comparative Example 3 was obtained in the same manner as in Comparative Example 2, except that the (A-2) diamine component was changed to "Trade name: Heartcure 10 (amine value: 630.0 mgKOH / g)" manufactured by Kumiai Chemical Industry Co., Ltd., and the amounts of the (B-1) alicyclic polyisocyanate compound and the (B-2) aliphatic polyisocyanate compound added were 2.4 g (5 parts by mass) and 45.6 g (95 parts by mass), respectively. The compounding time according to Comparative Example 3 was 0.0028 hours (10 seconds).

[0084] <Comparative Example 4> An attempt was made to prepare a compression molding composition according to Comparative Example 4 in the same manner as in Example 11, except that the (A-2) diamine component was changed to "Product name: Elasmer (registered trademark) 1000P (amine value: 90.6 mg KOH / g)" manufactured by Kumiai Chemical Industry Co., Ltd., and the amounts of the (B-1) alicyclic polyisocyanate compound and the (B-2) aliphatic polyisocyanate compound added were changed to 7.4 g (15 parts by mass) and 41.8 g (85 parts by mass), respectively. However, due to the low amine value of the (A-2) diamine component, the mixture containing the components turned into a starch syrup-like liquid, and it was not possible to prepare a compression molding composition.

[0085] <Comparative Example 5> An attempt was made to prepare a compression molding composition according to Comparative Example 5 in the same manner as in Comparative Example 4, except that the (A-2) diamine component was changed to "Product name: Elasmer (registered trademark) 650P (amine value: 126.0 mg KOH / g)" manufactured by Kumiai Chemical Industry Co., Ltd., and the amounts of the (B-1) alicyclic polyisocyanate compound and the (B-2) aliphatic polyisocyanate compound added were changed to 11.2 g (15 parts by mass) and 63.4 g (85 parts by mass), respectively. However, due to the low amine value of the (A-2) diamine component, the mixture containing the components turned into a starch syrup-like liquid, and it was not possible to prepare a compression molding composition.

[0086] [Measurement of compound stability period] The compression molding compositions according to Examples 1 to 13 and Comparative Example 3 were wrapped in Saran Wrap, and the compression molding compositions wrapped in Saran Wrap were left at room temperature until they became unable to be compression molded (compound stability period) was measured. The results are shown in the table in Figure 1. Note that "Ex. 1" to "Ex. 13" in the table in Figure 1 refer to Examples 1 to 13, respectively, and "Comp. 1" to "Comp. 5" refer to Comparative Examples 1 to 5, respectively.

[0087] 1, it was found that the compression molding compositions according to Examples 1 to 13 and Comparative Example 3 maintained a stable state for at least 9 days after preparation. Therefore, it was found that the compression molding compositions according to Examples 1 to 13 and Comparative Example 3 maintained a stable state for more than one week in the state before heat curing, and had excellent storage stability at room temperature. Note that, as mentioned above, in Comparative Examples 1, 2, 4, and 5, it was not possible to prepare a compression molding composition, and therefore it was not possible to measure the compound stability period.

[0088] [Preparation of polyurethane molded products and thin films] 2 is an enlarged cross-sectional view showing a schematic configuration example of concave molds M1 and M2 according to a modified example. The concave mold M1 is a metal plate-like structure having a cup-shaped depression d1 (diameter W1: 17 mm, maximum depth H1: 4 mm, volume: 0.85 cm 3 The concave mold M2 is a metal plate-like structure having a cup-shaped depression d2 (diameter W2: 17 mm, maximum depth H2: 4 mm, volume: 0.85 cm 3 ) and an annular deburring groove R (bottom dimension D1: 2 mm, top dimension D2: 1 mm, height h: 1 mm) surrounding the periphery of the recess d2.

[0089] Compression molding compositions according to Examples 1 to 13 and Comparative Example 3 were loaded between the recessed mold M1 and the recessed mold M2, and then compression molding was performed (molding temperature: 100 to 200°C, molding time: 5 to 60 minutes). Next, the recessed molds M1 and M2 were demolded, and flash of about 0.1 mm in thickness was removed from the obtained compression-molded product to produce the polyurethane molded products according to Examples 1 to 13, which were the portions of the compression-molded product formed by the cup-shaped depressions d1 and d2. Here, for Comparative Example 3, an attempt was made to produce a polyurethane molded product in the same manner as in Examples 1 to 13, but the compression molding composition containing each component became petrolatum-like (liquid) due to the heat of compression molding, and a polyurethane molded product could not be obtained.

[0090] For Comparative Examples 1, 2, 4, and 5, which failed to produce a compression molding composition, and Comparative Example 3, which failed to produce a cured product by compression molding, we attempted to produce thin films according to Comparative Examples 1 to 5 by open casting at 100°C for 2 hours. Specifically, the mixed solutions according to Comparative Examples 1 to 5 were mixed for 60 seconds using a homogenizer at 3000 rpm and then degassed in a vacuum. The degassed mixture was then poured into a silicone open mold (thickness: 2 mm, width: 200 mm, depth: 200 mm) and thermally cured at 100°C for 2 hours. After demolding, the mixture was aged at room temperature for 3 days to attempt to produce sheet-like thin films (thickness: 2 mm). However, for Comparative Examples 2 and 3, although thin films were prepared in the same manner as Comparative Examples 1, 4, and 5, the crosslinked structure of the urethane bonds was not sufficiently formed, resulting in thin films with insufficient hardness. Therefore, the thin films according to Comparative Examples 2 and 3 could not be subjected to subsequent property evaluation.

[0091] [Characteristics evaluation] <Appearance> The polyurethane molded articles according to Examples 1 to 13 were placed in a thermostatic bath and left at 100°C for 100 days. Thereafter, the polyurethane molded articles according to Examples 1 to 13 were visually inspected for changes in appearance before and after being placed in the thermostatic bath, and the results were evaluated as "good" or "bad." The results are shown in the table of FIG. 1. The evaluation criteria for "good" and "bad" were as follows:

[0092] (Judgment criteria) ◯: No settling or cracks in the polyurethane molded product after being placed in the thermostatic bath. ×: The polyurethane molded product shows settling or cracks after being placed in the thermostatic bath.

[0093] <Rubber hardness> The rubber hardness of the polyurethane molded products according to Examples 1 to 13 and the thin films according to Comparative Examples 1, 4, and 5 was measured using a durometer (type A) in accordance with JIS K 6253-3:2012. The results are shown in the table in Figure 1. The values ​​shown in the "Rubber hardness A" column in Figure 1 indicate the measurement results 10 seconds after the durometer (type A) pressed against the sample.

[0094] <Tensile test> In accordance with JIS K 6251:2017 (formerly JIS K 6301), dumbbell-shaped test pieces (No. 3) were prepared from the polyurethane molded products of Examples 1 to 13 and the thin films of Comparative Examples 1, 4, and 5. The 100% tensile stress, tensile strength, and tensile elongation of these test pieces were calculated to obtain the 100% tensile stress, tensile strength, and tensile elongation of the polyurethane molded products of Examples 1 to 13 and the thin films of Comparative Examples 1, 4, and 5. The results are shown in the table in FIG.

[0095] 1, Comparative Example 1, which did not contain the (A-2) diamine component, was inferior in 100% tensile stress and tensile strength, and the thin film did not exhibit the desired mechanical strength. Also, Comparative Examples 4 and 5, in which the (A-2) diamine component had an amine value of less than 350 mgKOH / g, were inferior in tensile strength, and like Comparative Example 1, the thin film did not exhibit the desired mechanical strength.

[0096] On the other hand, the polyurethane molded articles of Examples 1 to 13 had excellent appearance after heat curing, and none of rubber hardness A, 100% tensile stress, tensile strength, and tensile elongation were inferior or significantly superior, and they exhibited well-balanced and favorable properties. As a result, the polyurethane molded articles of Examples 1 to 13 are highly versatile and can be widely used in applications such as cushioning materials, vibration-proofing materials, shock-absorbing materials, and packing.

Claims

1. A compression molding composition which is a mixture containing (A) a base agent, (B) a curing agent, and a polyurea component, and is a clay-like compound, The (A) main component is a mixture of an (A-1) polyol component and an (A-2) diamine component, the amount of the polyol component (A-1) added is 75 to 95 parts by mass relative to 100 parts by mass of the total amount of the polyol component (A-1) and the diamine component (A-2), The polyol component (A-1) is a liquid diol compound having two hydroxyl groups, a number average molecular weight (Mn) of 500 to 2000, and a primary hydroxyl group at the end of the main chain, the amount of the diamine component (A-2) added is 3 to 15 parts by mass relative to 100 parts by mass of the total amount of the polyol component (A-1) and the diamine component (A-2), The diamine component (A-2) is a liquid aromatic diamine compound having two amino groups and an amine value of 350 to 700 mgKOH / g, the (B) curing agent is a mixture of (B-1) an alicyclic polyisocyanate compound and (B-2) an aliphatic polyisocyanate compound, the amount of the alicyclic polyisocyanate compound (B-1) added is 5 to 15 parts by mass relative to 100 parts by mass of the total amount of the alicyclic polyisocyanate compound (B-1) and the aliphatic polyisocyanate compound (B-2), The alicyclic polyisocyanate compound (B-1) has an isocyanate group at a terminal thereof, and the number of functional groups of the isocyanate group is 3, the amount of the aliphatic polyisocyanate compound (B-2) added is 85 to 95 parts by mass relative to 100 parts by mass of the total amount of the alicyclic polyisocyanate compound (B-1) and the aliphatic polyisocyanate compound (B-2), The (B-2) aliphatic polyisocyanate compound has an isocyanate group having a functionality of 2. Compression molding composition.

2. 2. The compression molding composition according to claim 1, wherein the liquid diol compound is a reaction product of 3-methyl-1,5-pentanediol and adipic acid.

3. The compression molding composition according to claim 2 , wherein the liquid aromatic diamine compound is dimethylthiotoluenediamine.

4. The alicyclic polyisocyanate compound (B-1) is a trimer of hexamethylene diisocyanate, The compression molding composition according to claim 3, wherein the (B-2) aliphatic polyisocyanate compound is an allophanate-modified product of hexamethylene diisocyanate.

5. A compression molding method, comprising compression molding the compression molding composition according to any one of claims 1 to 4 at 100 to 200°C to obtain a polyurethane molded product.

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