Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step

Definitions

• the present invention relates to a polyurethane integral skin foam (hereinafter sometimes referred to as “ISF”) and a method for producing the ISF. More specifically, the present invention relates to a method for producing an ISF having high resilience in a wide temperature range and excellent in productivity and mechanical strength as a molded product.
• ISF polyurethane integral skin foam
• ISF is widely used as an interior part for automobiles, including materials for shoe soles and steering wheels, because of its good productivity, mechanical strength, and good touch, but it is suitable for high-performance shoe soles.
• ISF technology has been known which has a high rebound resilience in a normal temperature range and good mechanical strength.
• Patent Document 1 proposes a highly elastic flexible polyurethane foam having a relatively high density using diphenylmethane diisocyanate (hereinafter sometimes referred to as “MDI”).
• MDI diphenylmethane diisocyanate
• the polyurethane foam uses a cross-linking agent and realizes a high elastic modulus by increasing the amount of chemical cross-linking, and mechanical strength such as sufficient elongation and tear strength as a resin for shoe soles, etc. Cannot be realized.
• Patent Document 2 describes a method for providing a low-density polyurethane molded product as a shoe sole member, but it is a complicated process, and the disclosed elastic modulus is not sufficient.
• An object of the present invention is to provide an ISF having a high rebound resilience in a wide temperature range and excellent in mechanical strength and productivity and a method for producing the ISF.
• PTMEG polytetramethylene ether glycol
• the present invention includes the following embodiments (1) to (12).
• the organic polyisocyanate composition (A) is a urethane-modified product of diphenylmethane diisocyanate that is liquid at room temperature and polytetramethylene ether glycol having a number average molecular weight of 1,000 to 3,500, and has an isocyanate group content of 7
• the polyol component (B) contains polytetramethylene ether glycol (b1) having a number average molecular weight of 600 to 3,500, and the ratio of (b1) in the polyol component (B) is 50% by mass or more.
• the polyurethane integral skin foam according to any one of (1) to (3) above,
• the polyol component (B) includes a polyether polyol (b2) other than (b1), and (b2) is selected from the group consisting of a polymerization initiator having an average functional group number of 2 to 4, propylene oxide and ethylene oxide.
• a method for producing a polyurethane integral skin foam comprising reacting an organic polyisocyanate composition (A) with a polyol component (B) in the presence of a catalyst (C) and a foaming agent (D),
• the isocyanate composition (A) is an organic polyisocyanate (a1) having an isocyanate group content of 7 to 25% by mass obtained by urethane-modifying diphenylmethane diisocyanate with polytetramethylene ether glycol having a number average molecular weight of 1,000 to 3,500.
• Organic polyisocyanate composition (A) is a diphenylmethane diisocyanate that is liquid at normal temperature, urethane-modified with polytetramethylene ether glycol having a number average molecular weight of 1,000 to 3,500, and an isocyanate group content of 7 to 25 mass.
• the polyol component (B) contains polytetramethylene ether glycol (b1) having a number average molecular weight of 600 to 3,500, and the ratio of (b1) in the polyol component (B) is 50% by mass or more.
• the polyol component (B) includes a polyether polyol (b2) other than (b1), and (b2) is a polymerization initiator having an average functional group number of 2 to 4 from the group consisting of propylene oxide and ethylene oxide.
• the resilience modulus can be remarkably improved in a wide temperature range without deteriorating physical properties such as mechanical strength in ISF.
• the ISF produced according to the present invention can be widely used for materials that require high elastic performance such as a resin for shoe soles, and is very useful. Furthermore, high production stability in a general foaming apparatus can be realized during ISF production.
• the polyurethane integral skin foam of the present invention is a polyurethane integral skin foam using at least an organic polyisocyanate composition (A), a polyol component (B), a catalyst (C), and a foaming agent (D) as raw materials.
• the isocyanate composition (A) is an organic polyisocyanate (a1) having an isocyanate group content of 7 to 25% by mass obtained by urethane-modifying diphenylmethane diisocyanate with polytetramethylene ether glycol having a number average molecular weight of 1,000 to 3,500. It is characterized by that.
• the organic polyisocyanate composition (A) used in the present invention is an organic polyisocyanate (a1) obtained by urethane-modifying MDI with PTMEG or MDI that is liquid at room temperature (hereinafter referred to as “liquid MDI”).
• liquid MDI liquid at room temperature
• normal temperature is in accordance with JIS Z8703 (standard state of test place) and means 20 ° C. ⁇ 15 ° C.
• the isocyanate group content of the organic polyisocyanates (a1) and (a2) used in the present invention is 7 to 25% by mass, preferably 10 to 20% by mass.
• the isocyanate group content is below the lower limit, the viscosity of the organic polyisocyanate becomes very high, making it difficult to introduce into the foaming device, and mixing with the general foaming device with sufficient mixing ability of isocyanates and polyols. There is no problem.
• the isocyanate group content exceeds the upper limit, the reaction between the isocyanate and the polyol and the water as the blowing agent becomes random, and in particular, the resilience estimated due to the enlargement of the urea bond repeating unit caused by the reaction between the isocyanate and water. There is a noticeable drop in rate.
• the polyol for urethane modification of the organic polyisocyanates (a1) and (a2) used in the present invention is PTMEG having a number average molecular weight of 1,000 to 3,500, preferably a number average molecular weight of 1,500 to 3, 500 PTMEG. If the number average molecular weight is below the lower limit, the PTMEG chain will not function sufficiently as a soft segment, making it difficult to achieve the rebound elastic modulus target value. On the other hand, when the molecular weight is equal to or higher than the upper limit, hardness as an ISF suitable for uses such as shoe soles cannot be obtained, the crystallinity of the PTMEG chain is increased, and the low-temperature storage stability of the organic polyisocyanate is deteriorated. is there.
• the PTMEG for urethane modification of the organic polyisocyanates (a1) and (a2) has a number average molecular weight of 1,000 to 3,500, more preferably a number average molecular weight of 1,500 to 3,500 obtained by ring-opening polymerization of only tetrahydrofuran.
• a functional polyol is preferred from the standpoint of mechanical properties such as rebound resilience, elongation, and tear strength.
• the pre-polymerization monomer is in the range of up to 10 mol%, even if other ether units are introduced into the molecule, the effect of the present technology is not greatly impaired.
• 1,3-propanediol, 3-methyl-1,5-pentanediol, neopentyl glycol and the like for the purpose of liquefying PTMEG at room temperature can be introduced.
• the MDI used for the organic polyisocyanate (a1) is preferably mainly composed of 4,4'-MDI.
• MDI includes 2,2'-MDI and 2,4'-MDI as isomers.
• the content of these isomers in MDI is preferably 60% by mass or less.
• the MDI used in (a1) can contain polyphenylene polymethyl polyisocyanate (p-MDI) having a similar structure, but the ISF growth rate decreases due to the increase in the number of isocyanate functional groups, and the ISF derived from p-MDI. Since coloring or the like occurs, the content of p-MDI is preferably 10% by mass or less, and more preferably 5% by mass or less with respect to MDI used in the organic polyisocyanate (a1).
• p-MDI polyphenylene polymethyl polyisocyanate
• the liquid MDI used for the organic polyisocyanate (a2) is: (1) MDI is reacted at 200 ° C. or higher. (2) Add trimethyl phosphate, triethyl phosphate or the like as a catalyst to MDI and react at 170 ° C. or higher, or (3) Add a phospholene compound such as 3-methyl-1-phenyl-2-phospholene 1-oxide to MDI. After adding as a catalyst, react at 70 ° C. or higher, and add a reaction terminator at a predetermined reaction rate. It contains at least one selected from the group consisting of a partial carbodiimide and a partial uretonimine modified product of MDI obtained by the above method.
• the liquid MDI used in the present invention is preferably liquid MDI that has been reacted at a low temperature with a phospholene-based catalyst from the viewpoint of preventing the coloring of ISF.
• the total content of carbodiimide-modified MDI and uretonimine-modified MDI in the liquid MDI measured by a method that does not decompose the bond is preferably 5 to 40% by mass, more preferably 10 to 35% by mass.
• the total content of the carbodiimide-modified MDI and the uretonimine-modified MDI is within the above range, it is possible to obtain a suitable number of isocyanate functional groups, and the viscosity at the time of use can be made appropriate. Furthermore, when it is set to ISF, the elongation and strength can be satisfied.
• the liquid MDI used for the organic polyisocyanate (a2) is, as in (a1), the total content of 2,2′-MDI and 2,4′-MDI as MDI before carbodiimide modification or uretonimine modification is 60 mass. % Or less is preferable. This is for the same reason as in (a1).
• liquid MDI used for the organic polyisocyanate (a2) can contain a small amount of p-MDI in the MDI before carbodiimide modification or before uretonimine modification.
• (a2) compared with (a1), (a2) has a higher number of isocyanate average functional groups, and as MDI before carbodiimide modification or uretonimine modification, it is necessary to keep it at most 5% by mass, more preferably 3% by mass or less. is there.
• the polyol component (B) used in the present invention PTMEG having a number average molecular weight of 600 to 3,500 can be preferably used. More preferably, it is 1,000 to 3,500. Further, the content of (b1) in the polyol component (B) is preferably 50% by mass or more. More preferably, it is 60 to 90% by mass. Below the lower limit, the rebound resilience of the resulting ISF is not sufficiently high, and mechanical properties such as tear strength are reduced. Above the upper limit, the rebound resilience and mechanical properties at room temperature are improved, but the rebound resilience of ISF obtained from the crystallinity of PTMEG is greatly reduced in the low temperature range near 0 ° C.
• the polyol component (b2) other than (b1) used in the present invention includes a hydroxyl group equivalent obtained by polymerizing at least one selected from the group consisting of propylene oxide and ethylene oxide on a polymerization initiator having an average functional group number of 2 to 4.
• Polyether polyols generally used for the production of 1,000 to 3,000 flexible polyurethane foams can be used.
• an initiator water, ethylene glycol, propanediol, diethylene glycol, dipropylene glycol, butanediol, hexanediol, hydroquinone, glycerin, trimethylolpropane, hexanetriol, pentaerythritol, ethylenediamine, toluenediamine, methylenediphenyl
• EO ethylene oxide
• PO propylene oxide
• polymer polyol obtained by radical polymerization of a vinyl compound such as acrylonitrile or styrene in the polyol, or by generating a urea compound by a reaction between an amine and an isocyanate.
• various urethanization catalysts known in the art can be used.
• These catalysts can be used as a mixture of two or more if necessary. Further, these catalysts can be used by dissolving them in various solvents, polyols, plasticizers, etc. for reasons such as viscosity reduction, liquefaction, and volume increase for improving measurement accuracy of the molding machine.
• foaming agent (D) used in the present invention water is desirable, but known ones that do not significantly affect the global environment can be used as necessary.
• This known blowing agent has two types of inert low-boiling solvent and reactive blowing agent, the former being dichloromethane, hydrofluorocarbon, hydrofluoroolefin, acetone, methyl formate, hexane, pentane, isopentane, cyclopentane, etc.
• nitrogen gas, carbon dioxide gas, air, etc. can be mentioned. Examples of the latter include, for example, azo compounds and sodium bicarbonate, which decompose to generate gas at a temperature higher than room temperature.
• an auxiliary agent (E) may be used as necessary.
• auxiliaries (E) include foam stabilizers, thickeners, pigments or dyes, mica, reinforcing materials or fillers such as glass fibers, flame retardants, antioxidants, ultraviolet absorbers, and light stabilizers.
• An agent, an antifungal agent, an antibacterial agent, a VOC catcher agent and the like can be mentioned, and can be used as necessary.
• foam stabilizer examples include known ones that are generally used in the production of polyurethane foam.
• foam stabilizer examples include known ones that are generally used in the production of polyurethane foam.
• polydimethylsiloxane-polyalkylene oxide block polymer, vinylsilane-polyalkylene polyol polymer, and the like can be mentioned.
• the viscosity reducing agent (F) used in the present invention does not contain an active hydrogen group, a carbodiimide group, a formyl group, etc., which react with isocyanate groups, among liquid substances generally used for viscosity reduction of high viscosity liquids. Can be used.
• the viscosity at 25 ° C. is 100 mPa ⁇ s or less from the viewpoint of viscosity reduction effect
• the melting point is 0 ° C. or less from the handling aspect
• the flash point measured by the method of JIS K2265 is 70 ° C. or more from the safety aspect.
• diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dioctyl phthalate, diisononyl phthalate, diethyl adipate, dipropyl adipate, dibutyl adipate, dioctyl adipate, diisononyl adipate, diethyl maleate examples thereof include dipropyl maleate, dibutyl maleate, dioctyl maleate, tricresyl phosphate, tris ⁇ -chloropropyl phosphate, tributyl acetylcitrate, dibenzyl ether and the like.
• the content of the viscosity reducing agent (F) is preferably 25% by mass or less in the organic polyisocyanate composition.
• the ISF according to the present invention comprises, for example, an organic polyisocyanate composition (A) and a polyol component (B) in the presence of a catalyst (C), a foaming agent (D), and optionally an auxiliary agent (E). After stirring and mixing, it is produced as a molded foam obtained by pouring into a mold or a continuous sheet-like foam obtained by pouring on a conveyor having wall surfaces on the top, bottom, left and right.
• a component other than the organic polyisocyanate composition (A) is mixed in advance to prepare a polyol premix, and the two components (A) and this are mixed and foamed.
• a method of separately introducing into a mixing head of a stirring mixer and foaming is possible.
• the molar ratio (isocyanate group / NCO reactive group) of all isocyanate reactive groups in the isocyanate reactive compound containing water and all isocyanate groups in the organic polyisocyanate composition of the present invention is 0.5 to 1.2.
• Isocyanate index (NCO INDEX) 50 to 120
• 0.6 to 1.1 (NCO INDEX 60 to 110) is more preferable.
• the ISF of the present invention is not particularly limited in its use, but is usually a foamed resin used for a shoe sole having a rebound resilience of around 40%, a part of the shoe sole, a shoe insole, or the like.
• the mechanical strength of ISF required for such applications is an elongation of 200% or more and a tear strength of 25 N / cm or more.
• the density of the ISF according to the present invention is at least 150 kg. / M3 is required.
• the upper limit of the ISF density is preferably 500 kg / m 3 or less.
• Polyol 1 Propylene oxide addition polymer of glycerin, hydroxyl equivalent 1000
• Polyol 5 propylene oxide addition polymer of ethylene glycol, hydroxyl equivalent 3000
• Polyol 6 Propylene oxide addition polymer of glycerin, hydroxyl equivalent 500
• Polyol 7 propylene oxide addition polymer of ethylene glycol, hydroxyl equivalent 5000 Toyocat ET:
• An ISF was prepared using isocyanate prepolymers I-1 to I-18 and polyol premixes P-1 to P-18 as organic polyisocyanate compositions.
• each organic polyisocyanate composition adjusted to a temperature of 45 ° C. at a ratio shown in Tables 7 to 10 and a polyol premix were 7000 r. p. m. Were mixed and stirred by a tabletop mixer. After heating to 60 ° C. and applying a release agent, the mixture was poured into a dried metal mold of 300 mm ⁇ 300 mm ⁇ 5 mm size, then covered and cured for 7 minutes. After curing, the product was removed from the mold to obtain an ISF test piece (hereinafter abbreviated as TP). About obtained TP, density, hardness, mechanical physical properties, etc. were evaluated.
• TP ISF test piece
• Density is JIS K7222, Hardness (Asker C, surface hardness with skin), TB (Tensile strength, No. 3 dumbbell used), EB (Tensile elongation, No. 3 dumbbell used), TR (Tear strength, B-type dumbbell used) ),
• the impact resilience was measured according to JIS K7312. The rebound resilience at 0 ° C. was measured by the same method as at room temperature within 10 seconds after taking out a sample stored in a thermostatic chamber adjusted to 0 ⁇ 1 ° C. for 24 hours.
• Table 7 to Table 10 show the evaluation results of the produced ISF.
• the ISF obtained by the present invention has a high rebound resilience and excellent mechanical strength.
• ISF Examples 1 to 24 in which Asker C hardness was adjusted to about 20 to 60 were Comparative Examples 1, 3, 5 that could be molded among the Comparative Examples. Compared to the above, the rebound resilience is remarkably improved.
• Polyurethane integral skin foam with low density and high rebound resilience and good mechanical properties that are not available on the market according to the present invention is used in shoe soles, shoe insoles, parts of industrial machinery, toys, musical instruments, etc. This brings about excellent effects such as improvement of the weight and weight reduction.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Polyurethanes Or Polyureas (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=57127111

Family Applications (1)

Country Status (3)

Cited By (1)

Families Citing this family (6)

Citations (13)

• 2016
  • 2016-03-23 JP JP2016058313A patent/JP6759648B2/ja active Active
  • 2016-04-14 WO PCT/JP2016/061985 patent/WO2016167312A1/ja active Application Filing
  • 2016-04-15 TW TW105111777A patent/TW201710315A/zh unknown

Patent Citations (13)

Also Published As

Similar Documents

Legal Events