JP2020033494A - Polyurethane foam and molded article thereof, and method for producing molded article of polyurethane foam - Google Patents

Abstract

To provide a polyurethane foam which is heat compression moldable and has good strain characteristics, and to provide a molded article.MEANS FOR SOLVING THE PROBLEM: There is provided a polyurethane foam obtained by a mechanical froth method from a polyurethane reaction composition comprising a polyol component, a foam stabilizer, a catalyst, and an isocyanate component and an inert gas, wherein the polyol component comprises a polymer polyol and the polyurethane reaction composition comprises an acid-modified polyolefin powder. A sheet of the polyurethane foam is subjected to heat compression molding to obtain a molded article 10 having recessed parts 101, 103 and protruding parts 102, 104, 106 formed on the surface thereof.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a polyurethane foam suitable for thermocompression molding and a molded article thereof.

Thermoplastic resins can be shaped by heating, but have the problem of poor strain characteristics (large strain).
On the other hand, a thermosetting resin can be shaped by pre-processing using a mold and is difficult to post-process, but has an advantage of good distortion characteristics (less distortion).
Further, the conventional polyurethane foam can be subjected to thermocompression molding at a high temperature, but has a problem that it cannot be said that the strain characteristics are good.

JP 2009-013304 A

  The present invention has been made in view of the above points, and an object of the present invention is to provide a polyurethane foam that can be subjected to thermocompression molding and has good distortion characteristics and a molded article thereof.

  The invention according to claim 1 is a polyurethane foam obtained by a mechanical floss method from a polyurethane reaction composition containing a polyol component, a foam stabilizer, a catalyst, and an isocyanate component, and an inert gas, wherein the polyol component contains a polymer. A polyol is contained, and the polyurethane reaction composition contains an acid-modified polyolefin powder.

  According to a second aspect of the present invention, in the first aspect, the acid-modified polyolefin powder is a polyolefin powder modified with maleic anhydride.

  The invention according to claim 3 is characterized in that in claim 1 or 2, the total weight of the solid content of the polymer polyol and the acid-modified polyolefin powder is 5 to 40% by weight based on the weight of the polyurethane reaction composition. I do.

  According to a fourth aspect of the present invention, in any one of the first to third aspects, the polyurethane foam has a compression set (based on JIS 6401) of 10% or less.

  According to a fifth aspect of the present invention, there is provided a molded article having irregularities formed by thermocompression molding on the surface of a polyurethane foam sheet, wherein the polyurethane foam is the polyurethane foam according to any one of the first to fourth aspects. It is characterized by being a body.

  According to the polyurethane foam of the present invention, by including the polymer polyol and the acid-modified polyolefin powder in the polyurethane reaction composition, the polyurethane foam can be thermoplastically deformed at a decomposition temperature of the polyurethane bond or lower, and the strain characteristics are improved. However, it is possible to maintain the shape at the time of hot compression molding.

  According to the molded article of the polyurethane foam of the present invention, a sheet-shaped molded article having good distortion characteristics capable of maintaining the surface irregularities formed by the thermal compression molding can be obtained.

It is a top view which shows one Embodiment of the molded object of a polyurethane foam. It is sectional drawing which shows 2-2 cross section of FIG. It is a table | surface which shows the value and evaluation of the combination of Example and a comparative example, molding retention, 25% CLD, and compression set.

An embodiment of the polyurethane foam of the present invention will be described. The polyurethane foam of the present invention is obtained from the polyurethane reaction composition and an inert gas by a mechanical floss method.
In the mechanical floss method, a polyurethane foam is formed by supplying a mixed raw material obtained by compressing and mixing an inert gas into a polyurethane reaction composition to an Oak mixer or a nozzle having a narrowed tip and discharging the mixture from the Oak mixer or the nozzle. How to In the mechanical floss method, when the mixed raw material is discharged, the compressed inert gas expands to form air bubbles, and in this state, the polyol component and the isocyanate component react and cure to form a polyurethane foam. You. For this reason, the polyurethane foam is a polyurethane foam using an inert gas as a foaming function agent (foaming agent) of the polyurethane reaction composition, and the cell of the polyurethane foam contains an inert gas.

The polyurethane reaction composition contains a polyol component, a foam stabilizer, a catalyst, and an isocyanate component, further contains an acid-modified polyolefin powder in the present invention, and further contains an inert gas as a foaming function agent (foaming agent) as a mixed raw material. It is.
The polyol component includes a polyol other than the polymer polyol together with the polymer polyol.

  Examples of the polymer polyol include those obtained by graft-polymerizing acrylonitrile, styrene, and the like to polyether polyol. The polymer polyol preferably has a molecular weight of 2,000 to 5,000, a number of functional groups of 2 to 4, and a solid content of 10 to 50% by weight (wt%) such as acrylonitrile and styrene in the polymer polyol. Two or more polymer polyols may be used in combination. By including the polymer polyol in the polyol component, the strain characteristics can be improved.

The amount of the polymer polyol in the polyurethane reaction composition is preferably 5 to 40% by weight. If the amount of the polymer polyol is too small, an appropriate hardness cannot be obtained, and if the amount is too large, the viscosity of the polyurethane reaction composition becomes too high and foaming by mechanical floss becomes difficult. The solid content of the polymer polyol in the polyurethane reaction composition is preferably 2 to 13% by weight. When the solids content of the polymer polyol is low, heat shaping becomes difficult and the molding retention is deteriorated. Conversely, when the solids content is high, heat shaping is easy, but the viscosity of the polymer polyol is too high and it may be difficult to handle.

  As the polyol other than the polymer polyol, known polyols such as polyether polyol and polyester polyol can be used. As the polyether polyol, those having a molecular weight of 400 to 5000 and 2 to 4 functional groups are preferable, and as the polyester polyol, those having a molecular weight of 300 to 3000 and 2 to 4 functional groups are preferable. Two or more polyols other than the polymer polyol may be used in combination.

  As the foam stabilizer, those known for polyurethane foam can be used. For example, silicone-based foam stabilizers, fluorine-based foam stabilizers, and known surfactants can be used. The amount of the foam stabilizer is appropriately determined, and examples thereof include 1.0 to 6.0 parts by weight per 100 parts by weight of the polyol component.

  As the catalyst, an amine-based catalyst and an organometallic catalyst for a polyurethane foam are used alone or in combination. Examples of the amine catalyst include a monoamine compound, a diamine compound, a triamine compound, a polyamine compound, a cyclic amine compound, an alcoholamine compound, an etheramine compound, and the like. One of these may be used alone, or two or more thereof may be used in combination. Examples of the organometallic catalyst include an organic tin compound, an organic iron compound, an organic bismuth compound, an organic lead compound, an organic zinc compound, and the like, and one or more of these may be used. The amount of the catalyst is appropriately determined, and examples thereof include 0.03 to 3.0 parts by weight per 100 parts by weight of the polyol component.

  As the isocyanate component, any of aromatic, alicyclic and aliphatic isocyanates may be used, and bifunctional isocyanates having two isocyanate groups in one molecule, or It may be a trifunctional or more isocyanate having three or more isocyanate groups, and these may be used alone or in combination.

  For example, bifunctional isocyanates include 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate (TDI), m-phenylene diisocyanate, p-phenylene diisocyanate, and 4,4′-diphenylmethane diisocyanate (MDI), 2,4'-diphenylmethane diisocyanate (MDI), 2,2'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'- Aromatic compounds such as dimethoxy-4,4'-biphenylene diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, methylcyclohexane diisocyanate Those alicyclic such as isocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, there may be mentioned aliphatic, such as lysine isocyanate.

  Examples of the bifunctional or more isocyanate include polymethylene polyphenylisocyanate (polymeric MDI). Examples of trifunctional or higher functional isocyanates include 1-methylbenzol-2,4,6-triisocyanate, 1,3,5-trimethylbenzol-2,4,6-triisocyanate, and biphenyl-2,4,4′-triisocyanate. Isocyanate, diphenylmethane-2,4,4'-triisocyanate, methyldiphenylmethane-4,6,4'-triisocyanate, 4,4'-dimethyldiphenylmethane-2,2 ', 5,5'tetraisocyanate, triphenylmethane -4, 4 ', 4 "-triisocyanate, etc. The isocyanate is not limited to one kind, and may be one or more kinds. For example, one kind of aliphatic isocyanate and aromatic Two kinds of group-based isocyanates may be used in combination. Preferably, the isocyanate index is a value obtained by multiplying the number of moles of isocyanate groups per mole of active hydrogen groups contained in the urethane raw material by 100 by [(isocyanate equivalent in foaming raw material / active hydrogen in foaming raw material). ) × 100].

  Examples of the acid-modified polyolefin powder include polyethylene (PE), polypropylene (PP), polybutene (PB), polypentene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, styrene-ethylene-butene-styrene copolymer ( SEBS) and the like, which are modified with unsaturated carboxylic acids or anhydrides thereof.

Among the acid-modified polyolefins, an acid-modified polyolefin modified with maleic anhydride is preferable. Examples of the acid-modified polyolefin modified with maleic anhydride include maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, and maleic anhydride-modified ethylene-propylene copolymer. The maleic anhydride-modified polypropylene shall include a polypropylene that is a random copolymer with ethylene and modified with maleic anhydride.Ethylene and propylene are copolymerized in the maleic anhydride-modified ethylene-propylene copolymer. In addition, it is intended to include a polypropylene which is a so-called block copolymer modified with maleic anhydride. In particular, maleic anhydride-modified polyethylene and maleic anhydride-modified polypropylene are preferable because they have better mold retention than other acid-modified polyolefins. The acid-modified polyolefin powder is not limited to one type, and may include a plurality of types. The powder refers to a particle size of 5 to 250 μm. The melting point of the acid-modified polyolefin is from 80 to 165 ° C, preferably from 90 to 140 ° C.
By including the acid-modified polyolefin powder in the polyurethane reaction composition together with the polymer polyol, the polyurethane foam is preheated at a temperature higher than the melting point of the acid-modified polyolefin powder, and the polyurethane foam is thermoplastically heated below the decomposition temperature of the urethane bond. Deformation (thermal compression molding) can be performed, and distortion characteristics are improved.

  Further, the amount of the acid-modified polyolefin powder in the polyurethane reaction composition is preferably from 3 to 35% by weight. If the amount of the acid-modified polyolefin powder is too small, heat shaping cannot be carried out. Conversely, if the amount is too large, foaming by mechanical floss cannot be carried out due to an increase in viscosity.

  The total weight of the solid content of the polymer polyol and the acid-modified polyolefin powder is preferably 5 to 40% by weight based on the weight of the polyurethane reaction composition. If the total weight of the solid content of the polymer polyol and the acid-modified polyolefin powder is reduced, thermal shaping cannot be performed. Conversely, if the total weight is increased, the viscosity of the polyurethane reaction composition becomes too high and foaming by mechanical floss cannot be performed.

Other optional additives may be added to the polyurethane reaction composition. Optional additives include, for example, crosslinking agents, fillers, dyes, pigments, antioxidants, flame retardants, and the like.
Examples of the crosslinking agent include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1-4 butanediol, and 1,6-hexanediol.
Examples of the filler include alumina trihydrate, silica, talc, calcium carbonate, clay and the like.

  As the inert gas used as the foaming function agent (foaming agent), a gas that does not adversely affect the reaction between the polyol and the isocyanate, such as dry air or nitrogen, is suitable. The inert gas preferably has a mixing ratio of 31% by volume to 91% by volume in the polyurethane reaction composition. In addition, the mixing ratio of the inert gas refers to the volume% of the foaming gas with respect to 100 parts by volume of the polyurethane reaction composition excluding the inert gas.

The polyurethane foam of the present invention has a residual compression set (based on JIS K6401) of 10% or less and little plastic deformation due to long-term use.
Further, the polyurethane foam of the present invention has a 25% compression load (25% CLD, JIS K 6254: compressive stress when a sample of φ50 mm is compressed by 25% at a speed of 1 mm / min) from 0.01 to 0. 1 MPa is preferred.

  The polyurethane foam of the present invention is shaped by hot compression molding to obtain a molded body. The heat compression molding is performed by preheating the polyurethane foam at 190 ° C. to 210 ° C. for 3 to 10 minutes, and performing a compression press using a mold at normal temperature (20 ° C. to 30 ° C.). Irregularities are provided on the mold surface of the mold, and irregularities are formed on the surface of the molded body. The compression ratio at the time of hot pressing is preferably 25 to 75%. The compression ratio is calculated as follows: compression ratio = [(original thickness−thickness at compression) / original thickness × 100].

  The example of the molded object of a polyurethane foam is shown. The molded article 10 of the polyurethane foam shown in FIGS. 1 and 2 is obtained by preheating a sheet of the polyurethane foam of the present invention having a predetermined thickness at 200 ° C. for 5 minutes and compression-molding the sheet at room temperature (25 ° C.). It is shaped and used as an insole. In the molded body 10 of the polyurethane foam, concave portions 101 and 103 and convex portions 102, 104 and 106 are formed near the base of the toes, the arch portion, and the portion corresponding to the heel portion. Reference numeral 107 denotes a general portion 107 having no irregularities.

  Since the polyurethane foam of the present invention used has a good distortion characteristic, the unevenness is hardly plastically deformed even when pressed for a long period of time, and the molded article 10 of the polyurethane foam formed by thermocompression molding has good quality. Can be maintained.

Using the following raw materials, the mixture ratio of the inert gas (nitrogen) was adjusted to 85% by volume in the polyurethane reaction composition having the composition shown in FIG. 3, and the mixture was mixed and stirred by a mechanical floss foaming machine, and continuously mixed on release paper. Then, the mixture was heated to 120 to 200 ° C. to produce a sheet-like polyurethane foam having a thickness of 10 mm.
-Polyol 1: polyether polyol, product name: PP-3000, manufactured by Sanyo Chemical Industries, Ltd., molecular weight 3000, number of functional groups 3, propylene oxide content 100%
-Polyol 2: Polymer polyol, product name: EX-914, manufactured by Asahi Glass Co., Ltd., molecular weight 3000, number of functional groups 3, solid content 22.9% by weight
-Polyol 3: Polymer polyol, product name: EX-913, manufactured by Asahi Glass Co., Ltd., molecular weight 3000, number of functional groups 2, solid content 20% by weight
-Polyol 4: polymer polyol, product name: FS-7301, manufactured by Sanyo Chemical Industries, Ltd., molecular weight 3000, number of functional groups 3, solid content 43% by weight
・ Normal polyethylene (PE) powder: 1050, melting point = 105 ° C., manufactured by Tokyo Ink Co., Ltd. ・ Polyamide resin powder: SK-1, melting point = 115 ° C., manufactured by Tokyo Ink Co., Ltd. ・ Polyester resin powder: G-120, melting point = 125 ° C. , Manufactured by Tokyo Ink Co., Ltd.-Acid-modified polyethylene (PE) powder: maleic anhydride-modified polyethylene, product name: Admer AT1000, melting point = 123 ° C, manufactured by Mitsui Chemicals, Inc.
-Acid-modified polypropylene (PP) powder: maleic anhydride-modified polypropylene, product name: Umex 1010, melting point = 135 ° C, manufactured by Sanyo Chemical Co., Ltd.-Silicone foam stabilizer: product name: SZ-1952, manufactured by Dow Corning Toray Co., Ltd. Iron catalyst: Product name: Product name; FIN-P1, manufactured by Nippon Chemical Industry Co., Ltd. ・ Isocyanate: Product name: M5S, manufactured by BASF INOAC polyurethane, Polymeric MDI (crude MDI), NCO%; 34%
In general, polyethylene (PE) powder, polyamide resin powder, polyester resin powder, acid-modified polyethylene (PE) powder, and acid-modified polypropylene (PP) powder are all thermoplastic resin powders. In No. 3, it was shown as "thermoplastic powder".
"Wt%" in Fig. 3 is the weight% in the polyurethane reaction composition. The total resin amount (wt%) is the weight% of the total amount of the solid content of the thermoplastic resin powder and the polymer polyol in the polyurethane reaction composition with respect to the polyurethane reaction composition.

  About each Example and each Comparative Example, the foaming state was visually determined. The evaluation was evaluated as “◎” when there was no breakage or the like, and “x” when there was a defective portion such as breakage.

For each of Examples and Comparative Examples, thermocompression molding was performed, and the initial moldability, the mold retention after 24 hours at normal temperature (normal temperature × 24 h), and the mold retention after 1 week at ordinary temperature (normal temperature × 1 week).
In the thermal compression molding, a 10 mm thick (original thickness) polyurethane foam sheet is preheated at 200 ° C. for 5 minutes, and then compressed to a thickness of 5 mm (compression rate of 50%) by a normal-temperature press device, and the state is changed for 5 minutes. Maintained. At the time of pressing, the pressing amount was adjusted to 5 mm by arranging 5 mm thick spacers on both sides of the polyurethane foam sheet and pressing.
The initial formability (%) was calculated by [(former thickness-thickness immediately after forming) / (former thickness-thickness of spacer) × 100] the forming retention rate immediately after forming while maintaining the compressed state for 5 minutes.
The molding retention (room temperature × 24 h (%)) is defined as: [(original thickness−thickness after 24 hours) / (original thickness−thickness immediately after molding)] × 100].
The molding retention (room temperature × 1 week (%)) is defined as the molding retention after molding and standing at room temperature for 1 week, [(original thickness−thickness after 1 week) / (original thickness−thickness immediately after molding). ) × 100].
The initial moldability and the mold retention were evaluated as “x” when the mold retention was less than 50%, “△” when the mold retention was less than 50% to less than 70%, “〇” when the mold retention was less than 70% to less than 90%, 90% In the case of １００100%, it was evaluated as “◎”.

Moreover, about each Example and each comparative example, 25% CLD and compression residual strain were measured.
25% CLD (MPa) is a compressive stress when a sample of φ50 mm is compressed by 25% at a speed of 1 mm / min based on JIS K 6254.
The compression set (%) is obtained by compressing a 50 × 50 mm sample in the thickness direction by 50% in accordance with JIS K6401 and leaving it to stand at a predetermined temperature (70 ° C.) for 22 hours. Was released, and the thickness of the sample 30 minutes after the release (thickness after release) was measured, and the value was calculated by the following equation.
Residual compression set (%) = [(thickness before compression−thickness after release) / thickness before compression × 100]
The evaluation of the compression set was evaluated as “◎” when the value of the compression set was less than 5%, and “x” when the value was 5% or more.
A comprehensive evaluation was performed according to the results of each test item. In the comprehensive evaluation, the lowest evaluation among the evaluations of each test item was regarded as the comprehensive evaluation. For example, if there is at least one "x" in the evaluation of a test item, the overall evaluation is "x", and if all the evaluations of the test items are "△" or more and at least one is "△", the overall evaluation Is “△”, the evaluation of all test items is “〇” or more, and there is at least one “〇”, the overall evaluation is “〇”, and the evaluation of all test items is “◎”, The evaluation was “◎”.

  Comparative Example 1 is an example in which the polyol component contains a polymer polyol, and ordinary polyethylene powder is added as a thermoplastic resin powder. The results of Comparative Example 1 were not performed for the other tests because there was foam breakage in the foamed state. The overall evaluation is "x".

  Comparative Example 2 is an example in which the polymer polyol was not contained and the thermoplastic resin powder was not added. In Comparative Example 2, the foaming state was “◎”, the initial moldability was 10.6%, the evaluation was “×”, the molding retention (normal temperature × 24 h) was 90.5%, the evaluation was “◎”, the molding retention (normal temperature) × 1 week) was 66.7%, the evaluation was “Δ”, the 25% CLD was 0.015 MPa, the compression residual strain was 2.8%, the evaluation was “◎”, the initial moldability was poor, and the overall evaluation was “X”. It is.

  Comparative Example 3 is an example in which the polymer polyol was contained, the thermoplastic resin powder was not added, and the solid content of the polymer polyol in the polyurethane reaction composition was 5 wt% and the total resin amount was 5.0 wt%. In Comparative Example 3, the foaming state was “◎”, the initial moldability was 20.5%, the evaluation was “×”, the molding retention (normal temperature × 24 h) was 93.5%, the evaluation was “◎”, the molding retention (normal temperature) × 1 week) was 41.9%, evaluation was “×”, 25% CLD was 0.050 MPa, compression residual strain was 2.7%, evaluation was “◎”, initial moldability and mold retention (normal temperature × 1) Week) is poor, and the overall evaluation is “×”.

  Comparative Example 4 is an example in which the polymer polyol was contained, the thermoplastic resin powder was not added, and the solid content of the polymer polyol in the polyurethane reaction composition was 7.5 wt%, and the total resin amount was 7.5 wt%. In Comparative Example 4, the foaming state was “◎”, the initial moldability was 35.1%, the evaluation was “×”, the molding retention (normal temperature × 24 h) was 91.7%, the evaluation was “◎”, the molding retention (normal temperature) × 1 week) was 64.3%, evaluation was “△”, 25% CLD was 0.053 MPa, compression residual strain was 2.5%, evaluation was “◎”, initial moldability was poor, and overall evaluation was “x”. It is.

  Comparative Example 5 is an example in which no polymer polyol was contained, and 29.4 wt% of a normal polyethylene powder was added as a thermoplastic resin powder to make the total resin amount 29.4 wt%. In Comparative Example 5, the foaming state was “◎”, the initial moldability was 28.2%, the evaluation was “×”, the molding retention (normal temperature × 24 h) was 82.5%, the evaluation was “〇”, the molding retention (normal temperature) × 1 week) is 38.6%, evaluation is “×”, 25% CLD is 0.028 MPa, compression residual strain is 2.1%, evaluation is “◎”, initial moldability and mold retention (normal temperature × 1) Week) is poor, and the overall evaluation is “×”.

  Comparative Example 6 contains a polymer polyol, a polyamide resin powder was added as a thermoplastic resin powder, the solid content of the polymer polyol in the polyurethane reaction composition was 15 wt%, the addition amount of the polyamide resin powder was 18.1 wt%, and the total resin was used. This is an example in which the amount was 33.1 wt%. In Comparative Example 6, the foamed state was “◎”, the initial moldability was 31.8%, the evaluation was “×”, the molding retention (normal temperature × 24 h) was 78.8%, the evaluation was “〇”, the molding retention (normal temperature) × 1 week) was 69.5%, evaluation was “△”, 25% CLD was 0.103 MPa, compression residual strain was 7.1%, evaluation was “×”, initial moldability and compression residual strain were poor, and overall The evaluation is "x".

  Comparative Example 7 is the same as Comparative Example 6 except that a polyester resin powder was used as the thermoplastic resin powder. In Comparative Example 7, the foamed state was “◎”, the initial moldability was 30.4%, the evaluation was “×”, the molding retention (normal temperature × 24 h) was 78.2%, the evaluation was “〇”, the molding retention (normal temperature) × 1 week) was 69.4%, the evaluation was “△”, the 25% CLD was 0.048 MPa, the compression residual strain was 8.0%, and the evaluation was “×”. The initial moldability and compression residual strain were poor, and the overall The rating is "x"

  In Example 1, 55.9 parts by weight of a polyol 4 (POP) was added as a polymer polyol to 65.9 parts by weight of a polyol component, and 5 parts by weight of an acid-modified polyethylene powder was added as a thermoplastic resin powder. The content of the polymer polyol is 5.0 wt%, the solid content of the polymer polyol is 2.0 wt%, the addition amount of the acid-modified polyethylene powder in the polyurethane reaction composition is 5.0 wt%, and the total resin amount is 7.0 wt%. This is an example. In Example 1, the foamed state was “◎”, the initial moldability was 63.5%, the evaluation was “△”, the mold retention (normal temperature × 24 h) was 71%, the evaluation was “〇”, the mold retention (normal temperature × 1). Weekly) is 60.3%, the evaluation is “△”, the 25% CLD is 0.691 MPa, the compression residual strain is 3.7%, the evaluation is “◎”, and the overall evaluation is “△”. In Example 1, there was no "x" in all the evaluations, and all of the initial moldability, mold retention, and compression residual strain were good. Therefore, heat compression molding was possible, and the strain characteristics were good.

  Example 2 was the same as Example 1 except that polyol 4 (POP) was used as a polymer polyol in 65.9 parts by weight of a polyol component, and the content of the polymer polyol in the polyurethane reaction composition was reduced. This is an example in which 20.1 wt%, the solid content of the polymer polyol is 5.0 wt%, the addition amount of the acid-modified polyethylene powder in the polyurethane reaction composition is 5.0 wt%, and the total resin amount is 10.0 wt%. In Example 2, the foaming state was “◎”, the initial moldability was 97.9%, the evaluation was “◎”, the molding retention (normal temperature × 24 h) was 91.3%, the evaluation was “◎”, the molding retention (normal temperature) × 1 week) was 84.8%, the evaluation was “〇”, the 25% CLD was 0.715 MPa, the compression residual strain was 3.3%, the evaluation was “◎”, and the overall evaluation was “〇”. In Example 2, all the evaluations were “〇” or more, and all of the initial moldability, mold retention, and compression residual strain were good. Therefore, heat compression molding was possible, and the strain characteristics were good.

  Example 3 is the same as Example 1 except that the polyol 4 (POP) was used as the polymer polyol in 40 parts by weight and the acid-modified polyethylene powder was added in 10 parts by weight in 65.9 parts by weight of the polyol component. The content of the polymer polyol in the composition is 38.2 wt%, the solid content of the polymer polyol is 11.0 wt%, the addition amount of the acid-modified polyethylene powder in the polyurethane reaction composition is 9.6 wt%, and the total resin amount is This is an example of 20.6 wt%. In Example 3, the foamed state was “◎”, the initial moldability was 95.4%, the evaluation was “◎”, the molding retention (normal temperature × 24 h) was 92.2%, the evaluation was “◎”, the molding retention (normal temperature). × 1 week) is 88.5%, evaluation is “〇”, 25% CLD is 1.073 MPa, compression residual strain is 3.7%, evaluation is “◎”, and overall evaluation is “〇”. In Example 3, all evaluations were “〇” or more, and all of the initial moldability, mold retention and compression residual strain were good, so that heat compression molding was possible and the strain characteristics were good.

  Example 4 was the same as Example 1 except that 30 parts by weight of polyol 4 (POP) was added as the polymer polyol in 65.9 parts by weight of the polyol component, and 30 parts by weight of the acid-modified polyethylene powder was added. The content of the polymer polyol in the composition is 24.1 wt%, the solid content of the polymer polyol is 8.4 wt%, the addition amount of the acid-modified polyethylene powder in the polyurethane reaction composition is 24.1 wt%, and the total resin amount is This is an example of 32.5 wt%. In Example 4, the foamed state was “◎”, the initial moldability was 97.0%, the evaluation was “◎”, the molding retention (normal temperature × 24 h) was 96.8%, the evaluation was “◎”, the molding retention (normal temperature) × 1 week) is 95.2%, evaluation is “◎”, 25% CLD is 0.669 MPa, compression residual strain is 3.1%, evaluation is “◎”, and overall evaluation is “◎”. In Example 4, all evaluations were “◎”, and all of the initial moldability, mold retention and compression residual strain were good, so that heat compression molding was possible and the strain characteristics were good.

  Example 5 is an example in which the ratio of the polymer polyol to the acid-modified polyethylene powder was changed while maintaining the value of the total resin amount at 32.5 wt%, which was the same as in Example 4. Example 5 is the same as Example 4 except that 10 parts by weight of polyol 4 (POP) was added as the polymer polyol in 65.9 parts by weight of the polyol component and 40 parts by weight of the acid-modified polyethylene powder was added. The content of the polymer polyol in the composition is 7.4 wt%, the solid content of the polymer polyol is 2.8 wt%, the addition amount of the acid-modified polyethylene powder in the polyurethane reaction composition is 29.7 wt%, and the total resin amount is 32.5 wt%. In Example 5, the foaming state was “◎”, the initial moldability was 97.1%, the evaluation was “◎”, the molding retention (normal temperature × 24 h) was 98.1%, the evaluation was “◎”, the molding retention (normal temperature) × 1 week) is 97.2%, evaluation is “◎”, 25% CLD is 0.550 MPa, compression residual strain is 3.6%, evaluation is “◎”, and overall evaluation is “◎”. In Example 5, all evaluations were “◎”, and all of the initial moldability, mold retention and compression residual strain were good, so that heat compression molding was possible and the strain characteristics were good.

  Example 6 was the same as Example 5 except that the amount of the acid-modified polyethylene powder was increased to 50 parts by weight. The content of the polymer polyol in the polyurethane reaction composition was 6.9 wt%, and the solid content of the polymer polyol was In this example, 2.8 wt%, the amount of the acid-modified polyethylene powder in the polyurethane reaction composition was 34.6 wt%, and the total resin amount was 37.4 wt%. In Example 6, the foaming state was “◎”, the initial moldability was 97.7%, the evaluation was “◎”, the molding retention (normal temperature × 24 h) was 98.8%, the evaluation was “◎”, the molding retention (normal temperature) × 1 week) is 97.9%, the evaluation is “、”, the 25% CLD is 0.405 MPa, the compression residual strain is 4.6%, the evaluation is “◎”, and the overall evaluation is “◎”. In Example 6, all the evaluations were “A”, and all of the initial moldability, mold retention, and compression residual strain were good. Therefore, heat compression molding was possible, and the strain characteristics were good.

  Example 7 is the same as Example 3 except that an acid-modified polypropylene was added instead of the acid-modified polyethylene. The content of the polymer polyol in the polyurethane reaction composition was 38.2 wt%, and the solid content of the polymer polyol was Is 11 wt%, the amount of the acid-modified polypropylene powder in the polyurethane reaction composition is 9.6 wt%, and the total resin amount is 20.6 wt%. In Example 7, the foaming state was “◎”, the initial moldability was 94.2%, the evaluation was “◎”, the molding retention (normal temperature × 24 h) was 91.5%, the evaluation was “◎”, the molding retention (normal temperature). × 1 week) was 87.2%, the evaluation was “〇”, the 25% CLD was 1.082 MPa, the compression residual strain was 3.8%, the evaluation was “◎”, and the overall evaluation was “◎”. In Example 7, all evaluations were “◎”, and all of the initial moldability, mold retention and compression residual strain were good, so that heat compression molding was possible and the strain characteristics were good.

  As described above, the polyurethane foam of the present invention can be subjected to heat compression molding and has good distortion characteristics. Further, the molded article of the polyurethane foam of the present invention has good distortion characteristics capable of maintaining the surface irregularities formed by the hot compression molding.

10 Molded object of polyurethane foam 101, 103 Concave part 102, 104, 106 Convex part 107 General part without unevenness

The present invention relates to a polyurethane foam suitable for thermocompression molding, a molded article thereof, and a method for producing a molded article of a polyurethane foam .

The present invention has been made in view of the above points, and an object of the present invention is to provide a polyurethane foam that can be subjected to thermocompression molding and has good distortion characteristics, and a method for producing the molded article and the molded article of the polyurethane foam .

The invention according to claim 1 is a polyurethane foam obtained by a mechanical floss method from a polyurethane reaction composition containing a polyol component, a foam stabilizer, a catalyst, and an isocyanate component, and an inert gas, wherein the polyol component contains a polymer. A polyol; and the polyurethane reaction composition comprises an acid-modified polyolefin powder having a particle size of 5 to 250 μm .

According to a fifth aspect of the present invention, there is provided a molded article having irregularities formed by thermocompression molding on the surface of a polyurethane foam sheet, wherein the polyurethane foam is the polyurethane foam according to any one of the first to fourth aspects. It is characterized by being a body.
According to a sixth aspect of the present invention, there is provided a method for producing a molded article having irregularities formed by hot compression molding on the surface of a sheet of a polyurethane foam, wherein the polyurethane foam according to any one of claims 1 to 4 is used. The present invention relates to a method for producing a molded article of a polyurethane foam, wherein the irregularities are formed by pre-heating a sheet to be formed and then compressing the sheet at a temperature lower than the pre-heating temperature.

Claims (5)

Polyurethane reaction composition comprising a polyol component, a foam stabilizer, a catalyst, an isocyanate component, and an inert gas, and a polyurethane foam obtained by a mechanical floss method,
The polyol component includes a polymer polyol,
A polyurethane foam, wherein the polyurethane reaction composition contains an acid-modified polyolefin powder.   The polyurethane foam according to claim 1, wherein the acid-modified polyolefin powder is a polyolefin powder modified with maleic anhydride.   3. The polyurethane foam according to claim 1, wherein the total weight of the solid content of the polymer polyol and the acid-modified polyolefin powder is 5 to 40% by weight based on the weight of the polyurethane reaction composition. 4.   The polyurethane foam according to any one of claims 1 to 3, wherein the polyurethane foam has a residual compression set (based on JIS K6401) of 10% or less. In a molded article having irregularities formed by hot compression molding on the surface of a sheet of polyurethane foam,
A molded article of a polyurethane foam, wherein the polyurethane foam is the polyurethane foam according to any one of claims 1 to 4.

Images