JP2000290344A - Energy absorbing soft polyurethane foamed article and manufacture thereof - Google Patents
Energy absorbing soft polyurethane foamed article and manufacture thereofInfo
- Publication number
- JP2000290344A JP2000290344A JP11099605A JP9960599A JP2000290344A JP 2000290344 A JP2000290344 A JP 2000290344A JP 11099605 A JP11099605 A JP 11099605A JP 9960599 A JP9960599 A JP 9960599A JP 2000290344 A JP2000290344 A JP 2000290344A
- Authority
- JP
- Japan
- Prior art keywords
- mgkoh
- less
- polyurethane foam
- flexible polyurethane
- hydroxyl value
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 229920002635 polyurethane Polymers 0.000 title 1
- 239000004814 polyurethane Substances 0.000 title 1
- 150000003077 polyols Chemical class 0.000 claims abstract description 52
- 229920005830 Polyurethane Foam Polymers 0.000 claims abstract description 49
- 239000011496 polyurethane foam Substances 0.000 claims abstract description 49
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 48
- 229920000570 polyether Polymers 0.000 claims abstract description 48
- 229920005862 polyol Polymers 0.000 claims abstract description 44
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 40
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 29
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 24
- 238000012644 addition polymerization Methods 0.000 claims abstract description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 19
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000004088 foaming agent Substances 0.000 claims abstract description 9
- 125000000524 functional group Chemical group 0.000 claims description 28
- -1 hydrogen compound Chemical class 0.000 claims description 19
- 230000006835 compression Effects 0.000 claims description 10
- 238000007906 compression Methods 0.000 claims description 10
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000004604 Blowing Agent Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 2
- 239000006260 foam Substances 0.000 description 25
- 239000003999 initiator Substances 0.000 description 18
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000005187 foaming Methods 0.000 description 4
- 239000013518 molded foam Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 201000004569 Blindness Diseases 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 101000835998 Homo sapiens SRA stem-loop-interacting RNA-binding protein, mitochondrial Proteins 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 208000004210 Pressure Ulcer Diseases 0.000 description 1
- 102100025491 SRA stem-loop-interacting RNA-binding protein, mitochondrial Human genes 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002323 Silicone foam Polymers 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 241001147388 Uncia Species 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- BRWZYZWZBMGMMG-UHFFFAOYSA-J dodecanoate tin(4+) Chemical compound [Sn+4].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O BRWZYZWZBMGMMG-UHFFFAOYSA-J 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 210000000497 foam cell Anatomy 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- 235000021552 granulated sugar Nutrition 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000013514 silicone foam Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical group NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は車両用内装材、家具
用クッション材、マットレス、医療用材料に広く使用さ
れる軟質ポリウレタン発泡体に関するものである。詳し
くは、耐久性が良好で、反発弾性が低い軟質ポリウレタ
ン発泡体及び、その製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flexible polyurethane foam widely used for interior materials for vehicles, cushion materials for furniture, mattresses, and medical materials. More specifically, the present invention relates to a flexible polyurethane foam having good durability and low rebound resilience, and a method for producing the same.
【０００２】[0002]
【従来技術】従来から、軟質ポリウレタン発泡体はその
高い反発弾性から車両用クッション、ヘッドレスト、イ
ンストゥルメントパネル（計器板）、ステアリングフォ
イール（ハンドル）、家具、寝具等の幅広い分野で使用
されてきた。最近になって、車両衝突時における安全性
確保の見地から、衝撃吸収材として低反発弾性軟質ポリ
ウレタン発泡体を車両用内装材（チャイルドシート、ヘ
ッドレスト、天井材、ピーラー材、計器板）へ適用する
ことが注目されている。また、マットレス、医療用の腰
枕、足枕、安眠用の枕に低反発弾性軟質ポリウレタン発
泡体を使用することで、就寝時の体圧分散を改良し、寝
心地性を向上する試みや、長時間の就寝による床ずれを
防止しようという試みがなされようとしている。さらに
は、車両用シートクッション材に低反発弾性の軟質ポリ
ウレタン発泡体を使用することで、長時間の着座による
疲労を低減しようとする提案もある（特開平２−５２６
０７号公報及び特開平１−２８０４１３）。これら低反
発弾性の軟質ポリウレタン発泡体を製造する方法として
は、特開平２−１７５７１３号公報に記載の、平均分子
量が４００以上、２０００以下であり、平均官能基数が
２以上、３．５以下のポリエーテルポリオールを用いる
ことで反発弾性２５％以下の軟質ポリウレタン発泡体を
製造する方法が、特開昭６２−７９２１７号公報に記載
の、粘着付与剤をポリオール１００に対して２５〜２０
０重量部使用し、可塑剤を粘着付与剤に対して０．２５
〜２使用する方法が開示されている。しかしながら、上
記公報に記載の方法で製造される軟質ポリウレタン発泡
体は低反発弾性ではあるが、乾熱残留歪み及び、湿熱残
留歪みの値が大きい（耐久性が悪い）といった物性上の
問題があった。一方、軟質ポリウレタン発泡体は製造方
法によりスラブフォーム、モールドフォームの２種類に
分類される。一つは自由発泡により製造されるスラブ式
であり、もう一つは閉鎖されたモールド内で過充眞によ
り製造されるモールド式である。高弾性軟質ポリウレタ
ン発泡体の製造において、スラブ式ではクラシングを実
施しなくとも収縮変形しないように配合調整して製造す
るのが一般的であるし、モールド式においては、発泡体
脱型後、速やかにクラシング（発泡体の体積を機械的に
１／２以下まで圧縮変形することで、セル膜を破壊して
独立気泡率を低下する方法。独立気泡率が高いままで、
発泡体セル内部の炭酸ガス温度が低下すると、炭酸ガス
の体積減少に伴い、発泡体樹脂が収縮変形する。）を行
い収縮変形を回避する製造方法が一般的である。従来の
低反発弾性軟質ポリウレタン発泡体においては、スラブ
フォームは製造可能であっても、モールドフォームはフ
ォーム脱型時の独立気泡率が高く、製造できない場合が
あった。例えば、特開平２−１７５７１３の方法では、
スラブフォームですら、その独立気泡率が高く、クラシ
ングが必要であるし、モールドフォームでは、その独立
気泡率がさらに大きくなり、クラシングを実施しても、
フォームに変形が残留してしまう問題があり、低反発弾
性軟質ポリウレタン発泡体を安定かつ高い生産性で、ス
ラブ式、モールド式で生産する方法が強く要望されてい
た。2. Description of the Related Art Conventionally, flexible polyurethane foams have been used in a wide range of fields such as vehicle cushions, headrests, instrument panels (instrument panels), steering wheels (handles), furniture, bedding, etc. due to their high resilience. Was. Recently, from the viewpoint of ensuring safety in the event of a vehicle collision, the application of low rebound resilient soft polyurethane foam as an impact absorbing material to vehicle interior materials (child seats, headrests, ceiling materials, peeler materials, instrument panels) Is attracting attention. Also, by using low-elasticity resilient soft polyurethane foam for mattresses, medical waist pillows, foot pillows, and pillows for sleep, attempts to improve body pressure distribution at bedtime and improve sleeping comfort, Attempts are being made to prevent bedsores due to bedtime. Further, there is a proposal to reduce fatigue caused by long-time seating by using a low-elasticity flexible polyurethane foam for a vehicle seat cushion material (Japanese Patent Laid-Open No. 2-526).
No. 07 and JP-A-1-280413). As a method of producing such a low-elasticity flexible polyurethane foam, an average molecular weight of 400 or more and 2000 or less and an average number of functional groups of 2 or more and 3.5 or less described in JP-A-2-175713. A method for producing a flexible polyurethane foam having a rebound resilience of 25% or less by using a polyether polyol is disclosed in JP-A-62-79217.
0 parts by weight, and the plasticizer is added to the tackifier in an amount of 0.25 parts by weight.
No. 2 to No. 2 are disclosed. However, although the flexible polyurethane foam produced by the method described in the above publication has low rebound resilience, it has physical property problems such as large values of dry heat residual distortion and wet heat residual distortion (poor durability). Was. On the other hand, flexible polyurethane foams are classified into two types, slab foams and mold foams, depending on the production method. One is a slab type manufactured by free foaming, and the other is a mold type manufactured by overfilling in a closed mold. In the production of high elasticity flexible polyurethane foam, it is common to adjust the composition so that it does not shrink and deform even without crushing in the slab type, and in the mold type, immediately after the foam is released from the mold, Classification (Method of mechanically compressing and deforming the volume of the foam to less than 1/2 to break the cell membrane and reduce the closed cell rate.
When the temperature of the carbon dioxide gas inside the foam cell decreases, the foam resin shrinks and deforms as the volume of the carbon dioxide gas decreases. ) To avoid shrinkage deformation. In the conventional low rebound resilient flexible polyurethane foam, even if a slab foam can be produced, a molded foam cannot be produced due to a high closed cell rate when the foam is released from the mold. For example, in the method of Japanese Patent Application Laid-Open No. 2-175713,
Even the slab foam has a high closed cell rate and requires crushing, and the molded foam has a higher closed cell rate even if crushing is performed.
There is a problem that deformation remains in the foam, and there has been a strong demand for a method for producing a low rebound resilient flexible polyurethane foam in a stable and high productivity manner by a slab type and a mold type.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は低反発
弾性（高い衝撃吸収性能、高い体圧分散性能を有す
る）、かつ高い耐久性（乾熱圧縮永久歪み及び、湿熱圧
縮永久歪みが小さい）を有する軟質ポリウレタン発泡体
及びその製造方法を提供することである。また、この軟
質ポリウレタン発泡体をクラシングレス（クラシング無
し）の条件下においていて、スラブ式及びモールド式の
製造方法で提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide low rebound resilience (having high shock absorbing performance and high body pressure dispersing performance) and high durability (low dry heat compression set and wet heat compression set). ) And a method for producing the same. Another object of the present invention is to provide the flexible polyurethane foam under crushing-less (no crushing) conditions by slab-type and mold-type manufacturing methods.
【０００４】[0004]
【課題を解決するための手段】本発明者等は、反発弾性
が２０％以下で、乾熱圧縮永久歪みが５％以下、湿熱圧
縮永久歪みが２％以下の軟質ポリウレタン発泡体をクラ
シングレスの条件下、スラブ式及びモールド式で製造す
る方法について鋭意研究した結果、特定の活性水素化合
物（B）と有機ポリイソシアネート（A）を使用すること
で、本発明の課題を解決することを見いだして発明を完
成させた。SUMMARY OF THE INVENTION The present inventors have developed a flexible polyurethane foam having a rebound resilience of 20% or less, a dry heat compression set of 5% or less, and a wet heat compression set of 2% or less under the condition of no crushing. As a result of intensive studies on the method of manufacturing by the slab method and the mold method, the inventors have found that the problem of the present invention can be solved by using a specific active hydrogen compound (B) and an organic polyisocyanate (A). Was completed.
【０００５】即ち本発明は下記（１）〜（１０）を提供
するものである。 （１） 有機ポリイソシアネート（Ａ）と、活性水素化
合物(Ｂ)と、発泡剤とから得られる軟質ポリウレタン発
泡体において、活性水素化合物（Ｂ）が（b1）水酸基価
が４０ｍｇＫＯＨ／ｇ以上１２０ｍｇＫＯＨ／ｇ以下
で、平均官能基数２以上４以下であり、炭素数３以上の
アルキレンオキシドとエチレンオキシドのモル付加重合
比率が５０／５０〜１０／９０であるポリエーテルポリ
オール、（b2）水酸基価が４１０ｍｇＫＯＨ／ｇ以上６
００ｍｇＫＯＨ／ｇ以下で、平均官能基数２以上８以下
であるポリエーテルポリオール、（b3）水酸基価が２０
ｍｇＫＯＨ／ｇ以上１７０ｍｇＫＯＨ／ｇ以下で、平均
官能基数２以上４以下であるポリエーテルポリオール、
（b1）、（b2）、（b3）の重量の総和を１００としたと
き各成分混合割合が（b1）３０〜８５、（b2）５〜５
０、（b3）１０〜４０である混合物又は該混合物から得
られるポリマーポリオールである軟質ポリウレタン発泡
体。 （２） 有機ポリイソシアネート（Ａ）がポリメチレン
ポリフェニルイソシアネート（a）である（１）記載の
軟質ポリウレタン発泡体。That is, the present invention provides the following (1) to (10). (1) In a flexible polyurethane foam obtained from an organic polyisocyanate (A), an active hydrogen compound (B), and a foaming agent, the active hydrogen compound (B) has (b1) a hydroxyl value of 40 mgKOH / g or more and 120 mgKOH / g. g, a polyether polyol having an average number of functional groups of 2 or more and 4 or less and a molar addition polymerization ratio of an alkylene oxide having 3 or more carbon atoms and ethylene oxide of 50/50 to 10/90, and (b2) a hydroxyl value of 410 mgKOH / g or more 6
A polyether polyol having an average functional group number of 2 or more and 8 or less at a concentration of 00 mg KOH / g or less, and (b3) a hydroxyl value of 20
a polyether polyol having an average functional group number of not less than 2 and not more than 4 at mgKOH / g or more and 170 mgKOH / g or less,
When the sum of the weights of (b1), (b2) and (b3) is 100, the mixing ratio of each component is (b1) 30 to 85, (b2) 5 to 5
0, (b3) a flexible polyurethane foam which is a mixture of 10 to 40 or a polymer polyol obtained from the mixture. (2) The flexible polyurethane foam according to (1), wherein the organic polyisocyanate (A) is polymethylene polyphenyl isocyanate (a).
【０００６】（３） （b1）のポリエーテルポリオール
の水酸基価が６１ｍｇＫＯＨ／ｇ以上８５ｍｇＫＯＨ／
ｇ以下で、平均官能基数２以上３以下であり、炭素数３
以上のアルキレンオキシドとエチレンオキシドのモル付
加重合比率が４０／６０〜１５／８５である１記載の軟
質ポリウレタン発泡体。 （４） （b2）のポリエーテルポリオールの水酸基価が
４１０ｍｇＫＯＨ／ｇ以上５００ｍｇＫＯＨ／ｇ以下で
平均官能基数２以上４以下である（１）記載の軟質ポリ
ウレタン発泡体。 （５） （b3）のポリエーテルポリオールの水酸基価が
２０ｍｇＫＯＨ／ｇ以上６０ｍｇＫＯＨ／ｇ以下で、平
均官能基数２以上４以下であり、炭素数３以上のアルキ
レンオキシドとエチレンオキシドのモル付加重合比率が
９０／１０〜８０／２０である（１）記載の軟質ポリウ
レタン発泡体。 （６） （b1）／（b2）／（b3）の混合重量比率が４０
〜６０／１０〜４０／２０〜４０である（１）記載の軟
質ポリウレタン発泡体。(3) The polyether polyol (b1) has a hydroxyl value of 61 mgKOH / g or more and 85 mgKOH / g or more.
g or less, the average number of functional groups is 2 or more and 3 or less, and the number of carbon atoms is 3 or less.
2. The flexible polyurethane foam according to 1, wherein the molar addition polymerization ratio between the alkylene oxide and ethylene oxide is 40/60 to 15/85. (4) The flexible polyurethane foam according to (1), wherein the polyether polyol (b2) has a hydroxyl value of 410 mgKOH / g or more and 500 mgKOH / g or less and an average functional group number of 2 or more and 4 or less. (5) The polyether polyol of (b3) has a hydroxyl value of from 20 mgKOH / g to 60 mgKOH / g, an average number of functional groups of from 2 to 4, and a molar addition polymerization ratio of alkylene oxide having 3 or more carbon atoms and ethylene oxide of 90. / 10/80/20, the flexible polyurethane foam according to (1). (6) The mixture weight ratio of (b1) / (b2) / (b3) is 40
The flexible polyurethane foam according to (1), which has a particle size of from 60/10 to 40/20 to 40.
【０００７】（７） 有機ポリイソシアネート（Ａ）
と、活性水素化合物(B)と、発泡剤とから軟質ポリウレ
タン発泡体を製造する方法において、活性水素化合物
（Ｂ）として（b1）水酸基価が４０ｍｇＫＯＨ／ｇ以上
１２０ｍｇＫＯＨ／ｇ以下で、平均官能基数２以上４以
下であり、炭素数３以上のアルキレンオキシドとエチレ
ンオキシドのモル付加重合比率が５０／５０〜１０／９
０であるポリエーテルポリオール、（b2）水酸基価が４
１０ｍｇＫＯＨ／ｇ以上６００ｍｇＫＯＨ／ｇ以下で、
平均官能基数２以上８以下であるポリエーテルポリオー
ル、（b3）水酸基価が２０ｍｇＫＯＨ／ｇ以上１７０ｍ
ｇＫＯＨ／ｇ以下で、平均官能基数２以上４以下である
ポリエーテルポリオール、（b1）、（b2）、（b3）の重
量の総和を１００としたとき各成分混合割合が（b1）３
０〜８５、（b2）５〜５０、（b3）１０〜４０である混
合物又は該混合物から得られるポリマーポリオールを用
いる軟質ポリウレタン発泡体の製造方法。(7) Organic polyisocyanate (A)
And a method for producing a flexible polyurethane foam from the active hydrogen compound (B) and a foaming agent, wherein the active hydrogen compound (B) has (b1) a hydroxyl value of 40 mgKOH / g to 120 mgKOH / g and an average number of functional groups 2 or more and 4 or less, and the molar addition polymerization ratio of alkylene oxide having 3 or more carbon atoms and ethylene oxide is 50/50 to 10/9.
A polyether polyol having a hydroxyl value of 0, (b2) a hydroxyl value of 4
10 mgKOH / g or more and 600 mgKOH / g or less,
Polyether polyol having an average number of functional groups of 2 or more and 8 or less, (b3) a hydroxyl value of 20 mgKOH / g or more and 170 m
When the total weight of polyether polyols (b1), (b2), and (b3) having a gKOH / g of not more than 2 and an average functional group number of not less than 2 and not more than 4 is 100, the mixing ratio of each component is (b1) 3
A method for producing a flexible polyurethane foam using a mixture of 0 to 85, (b2) 5 to 50, and (b3) 10 to 40, or a polymer polyol obtained from the mixture.
【０００８】（８） （７）記載の（b3）のポリエーテ
ルポリオールの水酸基価が２０ｍｇＫＯＨ／ｇ以上６０
ｍｇＫＯＨ／ｇ以下で、平均官能基数２以上４以下であ
り、炭素数３以上のアルキレンオキシドとエチレンオキ
シドのモル付加重合比率が９０／１０〜８０／２０であ
る軟質ポリウレタン発泡体の製造方法。 （９） 反発弾性が２０％以下で、乾熱圧縮永久歪みが
５％以下、湿熱圧縮永久歪みが２％以下の軟質ポリウレ
タン発泡体をクラシングすることなく製造する（７）記
載の軟質ポリウレタン発泡体の製造方法。 （１０） 発泡剤を活性水素化合物（Ｂ）１００重量部
当たり０．３〜５．０重量部使用する（７）ないし
（９）記載の軟質ポリウレタン発泡体の製造方法。(8) The polyether polyol of (b3) described in (7) has a hydroxyl value of not less than 20 mgKOH / g and not less than 60 mgKOH / g.
A method for producing a flexible polyurethane foam having a molar addition polymerization ratio of alkylene oxide having 3 or more carbon atoms and ethylene oxide of 90/10 to 80/20, which is not more than mgKOH / g, having an average functional group number of not less than 2 and not more than 4. (9) The flexible polyurethane foam according to (7), wherein the flexible polyurethane foam having a rebound resilience of 20% or less, a dry heat compression set of 5% or less, and a wet heat compression set of 2% or less is produced without crushing. Manufacturing method. (10) The method for producing a flexible polyurethane foam according to (7) to (9), wherein the foaming agent is used in an amount of 0.3 to 5.0 parts by weight per 100 parts by weight of the active hydrogen compound (B).
【０００９】[0009]
【発明の実施の形態】以下に本発明で使用される原料及
び製造方法について詳細に説明する。 [有機ポリイソシアネート(Ａ)]本発明で使用する有機ポ
リイソシアネート（Ａ）はポリメチレンポリフェニルイ
ソシアネート、トリレンジイソシアネート等を用いるこ
とができ、それぞれ単独でも複数を併用してもよい。こ
のなかでポリメチレンポリフェニルイソシアネートを用
いることが好ましい。 ポリメチレンポリフェニルイソシアネート(a) ポリメチレンポリフェニルイソシアネートは、例えば
４，４'−ＭＤＩ（以下ジフェニルメタンジイソシアネ
ートをＭＤＩと記す）を４０〜５０重量％、２，４’−
ＭＤＩを２〜１０重量％、２，２'−ＭＤＩを０〜３重
量％、３核体以上のメチレン架橋ポリフェニルポリフェ
ニルポリイソシアネートを５０〜６０重量％含有する粗
製ＭＤＩと、２，２’−ＭＤＩ及び２，４‘−ＭＤＩ異
性体混合物を０〜５０重量％、４，４’−ＭＤＩを５０
〜１００重量％含有する精製ジフェニルメタンジイソシ
アネート及び／またはその変性により製造されるカルボ
ジイミド基、アロファネート基、イソシアヌレート基、
ビウレット基、ウレタン基、ウレア基含有の変性ＭＤＩ
（精製ＭＤＩ及び／または変性ＭＤＩ）とからなり、粗
製ＭＤＩ／精製ＭＤＩ及び／または変性ＭＤＩの混合重
量比率が１００／０〜１０／９０である混合物が挙げら
れる。本発明においては２，４−及び／または２，６−
ＴＤＩ（以下トリレンジイソシアネートをＴＤＩと略記
する）を本発明の効果を阻害しない範囲で併用してもよ
り。例えば２，４−ＴＤＩ／２，６−ＴＤＩ−１００／
０〜６５／３５の範囲である。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the raw materials used in the present invention and the production method will be described in detail. [Organic polyisocyanate (A)] As the organic polyisocyanate (A) used in the present invention, polymethylene polyphenyl isocyanate, tolylene diisocyanate or the like can be used, and each may be used alone or in combination. Among these, it is preferable to use polymethylene polyphenyl isocyanate. Polymethylene polyphenyl isocyanate (a) Polymethylene polyphenyl isocyanate is, for example, 40 to 50% by weight of 4,4′-MDI (hereinafter diphenylmethane diisocyanate is referred to as MDI), 2,4′-MDI.
A crude MDI containing 2 to 10% by weight of MDI, 0 to 3% by weight of 2,2′-MDI, and 50 to 60% by weight of methylene-bridged polyphenyl polyphenyl polyisocyanate having three or more nuclei; 0 to 50% by weight of a mixture of -MDI and 2,4'-MDI isomer, and 50% of 4,4'-MDI
Carbodiimide group, allophanate group, isocyanurate group produced by purified diphenylmethane diisocyanate and / or its modification containing
Modified MDI containing biuret group, urethane group and urea group
(Purified MDI and / or modified MDI), and a mixture in which the mixing weight ratio of crude MDI / purified MDI and / or modified MDI is 100/0 to 10/90. In the present invention, 2,4- and / or 2,6-
TDI (hereinafter, tolylene diisocyanate is abbreviated as TDI) may be used in combination as long as the effects of the present invention are not impaired. For example, 2,4-TDI / 2,6-TDI-100 /
The range is from 0 to 65/35.
【００１０】[活性水素化合物(B)]本発明で有機ポリイ
ソシアネート（Ａ）と反応させる活性水素化合物（Ｂ）
は、下記のように特定の比率で混合された（b1）、（b
2）、（b3）の混合ポリエーテルポリオールである。[Active hydrogen compound (B)] The active hydrogen compound (B) to be reacted with the organic polyisocyanate (A) in the present invention.
Are mixed in specific ratios as follows (b1), (b
2) and (b3) are mixed polyether polyols.
【００１１】（b1）は、官能基数２〜４の開始剤に、従
来公知の方法により炭素数３以上のアルキレンオキシド
とエチレンオキシドをランダムまたはブロックで付加さ
せたものであり、炭素数３以上のアルキレンオキシドと
エチレンオキシドのモル付加重合比率が５０／５０〜１
０／９０である水酸基価が４０ｍｇＫＯＨ／ｇ以上１２
０ｍｇＫＯＨ／ｇ以下のポリエーテルポリオールであ
る。好ましくは、官能基数２〜３の開始剤に、従来公知
の方法により炭素数３以上のアルキレンオキシドとエチ
レンオキシドをランダムまたはブロックで付加させたも
のであり、炭素数３以上のアルキレンオキシドとエチレ
ンオキシドのモル付加重合比率が４０／６０〜１５／８
５である水酸基価が６１ｍｇＫＯＨ／ｇ以上８５ｍｇＫ
ＯＨ／ｇ以下のポリエーテルポリオールである。エチレ
ンオキシドのモル付加重合比率が小さすぎる場合には得
られる発泡体の独立気泡率が高くなり、収縮変形し易く
なるし、反発弾性が高くなる。(B1) is an initiator having 2 to 4 functional groups to which an alkylene oxide having 3 or more carbon atoms and ethylene oxide are added in a random or block manner by a conventionally known method. The molar addition polymerization ratio of oxide and ethylene oxide is 50/50 to 1
A hydroxyl value of 0/90 is 40 mgKOH / g or more and 12
It is a polyether polyol of 0 mgKOH / g or less. Preferably, an alkylene oxide having 3 or more carbon atoms and ethylene oxide are added to an initiator having 2 to 3 functional groups at random or in a block by a conventionally known method, and a mole of the alkylene oxide having 3 or more carbon atoms and ethylene oxide is used. The addition polymerization ratio is 40/60 to 15/8
The hydroxyl value of 5 is 61 mgKOH / g or more and 85 mgK
OH / g or less polyether polyol. If the molar addition polymerization ratio of ethylene oxide is too small, the foam obtained will have a high closed cell rate, will be easily contracted and deformed, and will have high rebound resilience.
【００１２】（b2）は、官能基数２〜８の開始剤に、従
来公知の方法により炭素数３以上のアルキレンオキシド
を付加させたものであり、水酸基価が４１０ｍｇＫＯＨ
／ｇ以上６００ｍｇＫＯＨ／ｇ以下のポリエーテルポリ
オールである。アルキレンオキシドは単独で用いても複
数を併用してもよく、必要に応じてエチレンオキサイド
を併用してもよい。好ましくは、官能基数２〜４の開始
剤に、従来公知の方法により炭素数３以上のアルキレン
オキシドを付加させたものであり、水酸基価が４１０ｍ
ｇＫＯＨ／ｇ以上５００ｍｇＫＯＨ／ｇ以下のポリエー
テルポリオールである。水酸基価が４１０ｍｇＫＯＨ／
ｇ以上とすることで発泡体の独立気泡率を抑制すること
ができ、収縮変形が発生しにくく、反発弾性を低く保つ
ことができるので好ましい。(B2) is obtained by adding an alkylene oxide having 3 or more carbon atoms to an initiator having 2 to 8 functional groups by a conventionally known method, and has a hydroxyl value of 410 mg KOH.
/ G to 600 mgKOH / g or less. Alkylene oxide may be used alone or in combination of two or more, and ethylene oxide may be used in combination as needed. Preferably, an initiator having 2 to 4 functional groups is added with an alkylene oxide having 3 or more carbon atoms by a conventionally known method, and has a hydroxyl value of 410 m.
It is a polyether polyol having a gKOH / g of 500 mgKOH / g or less. Hydroxyl value is 410mgKOH /
By setting it to g or more, the closed cell rate of the foam can be suppressed, shrinkage deformation is less likely to occur, and rebound resilience can be kept low.
【００１３】（b3）は、官能基数２〜４の開始剤に、従
来公知の方法により炭素数３以上のアルキレンオキシド
を付加させたものであり、水酸基価が２０ｍｇＫＯＨ／
ｇ以上１７０ｍｇＫＯＨ／ｇ以下のポリエーテルポリオ
ールである。この時炭素数３以上のアルキレンオキシド
と共にエチレンオキシドを付加させたものが好ましく、
炭素数３以上のアルキレンオキシドとエチレンオキシド
のモル付加重合比率が８０／２０以上であることが好ま
しく、更に好ましくは、官能基数２〜４の開始剤に、従
来公知の方法により炭素数３以上のアルキレンオキシド
を付加し、次にエチレンオキシドを付加させたものであ
り、炭素数３以上のアルキレンオキシドとエチレンオキ
シドのモル付加重合比率が９０／１０〜８０／２０であ
る水酸基価が２０ｍｇＫＯＨ／ｇ以上６０ｍｇＫＯＨ／
ｇ以下のポリエーテルポリオールである。水酸基価が１
７０ｍｇＫＯＨ／ｇを超える場合には、得られる発泡体
の独立気泡率が高くなり、収縮変形し易くなりクラシン
グが必要となる。(B3) is obtained by adding an alkylene oxide having 3 or more carbon atoms to an initiator having 2 to 4 functional groups by a conventionally known method, and having a hydroxyl value of 20 mgKOH /
g of polyether polyol of 170 mgKOH / g or less. At this time, those obtained by adding ethylene oxide together with an alkylene oxide having 3 or more carbon atoms are preferable,
The molar addition polymerization ratio of the alkylene oxide having 3 or more carbon atoms and ethylene oxide is preferably 80/20 or more, and more preferably, the alkylene oxide having 3 or more carbon atoms is added to the initiator having 2 to 4 functional groups by a conventionally known method. An oxide is added, followed by ethylene oxide. The hydroxyl value is 20 mgKOH / g or more and 60 mgKOH / g in which the molar addition polymerization ratio of alkylene oxide having 3 or more carbon atoms and ethylene oxide is 90/10 to 80/20.
g or less of a polyether polyol. Hydroxyl value is 1
When it exceeds 70 mgKOH / g, the closed cell rate of the obtained foam becomes high, so that the foam is easily contracted and deformed, so that crushing is required.
【００１４】上記ポリエーテルポリオールの混合重量比
率は（b1）／（b2）／（b3）＝３０〜８５／５〜５０／
１０〜４０の範囲であり、好ましくは（b1）／（b2）／
（b3）＝４０〜６０／１０〜４０／２０〜４０の範囲で
ある。The mixing weight ratio of the above polyether polyol is (b1) / (b2) / (b3) = 30 to 85/5 to 50 /
10 to 40, preferably (b1) / (b2) /
(B3) = 40-60 / 10-40 / 20-40.
【００１５】（開始剤）上記（b1）、（b2）、（b3）に
おいて、使用される官能基数２〜８の開始剤は当業界に
公知のものが使用できる。開始剤を例示するならば、エ
チレングリコール、ジエチレングリコール、グリセリ
ン、トリメチロールプロパン、ジグリセリン、トリエタ
ノールアミン、ペンタエリスリトール、ソルビトール、
エチレンジアミン、トリレンジアミン、グラニュウ糖等
があげられる。上記開始剤は２種以上併用してもよい。(Initiator) In the above (b1), (b2) and (b3), as the initiator having 2 to 8 functional groups, those known in the art can be used. Examples of the initiator include ethylene glycol, diethylene glycol, glycerin, trimethylolpropane, diglycerin, triethanolamine, pentaerythritol, sorbitol,
Examples include ethylenediamine, tolylenediamine, and granulated sugar. Two or more of the above initiators may be used in combination.
【００１６】（アルキレンオキシド）上記開始剤に付加
重合する炭素数３以上のアルキレンオキシドとしてはプ
ロピレンオキシド、ブチレンオキシド、スチレンオキシ
ド等があげられる。(Alkylene oxide) Examples of the alkylene oxide having 3 or more carbon atoms to be addition-polymerized to the above initiator include propylene oxide, butylene oxide and styrene oxide.
【００１７】（ポリマーポリオール）また、本発明の活
性水素化合物（Ｂ）には上記ポリエーテルポリオール
（b1）、（b2）、（b3）の存在下にアクリロニトリル、
スチレン等のエチレン性不飽和化合物を重合させ、ポリ
アクリロニトリル、ポリスチレン、またはコポリマー等
が上記ポリオールに分散させて得られる通称ポリマーポ
リオール（商品名）も好適に使用できる。このように、
ポリマーポリオールを使用する場合には、ポリアクリロ
ニトリル、ポリスチレン、またはそれらのコポリマー等
は単にポリエーテルポリオールの分散に使用されたもの
と考えられ、ポリエーテルポリオールにグラフトした量
は無視できる程度であるので、これらのポリマー分は除
外して、元のポリエーテルポリオール分についてのみ水
酸基価、エチレンオキシド含有量及び(b1)、(b2)、(b3)
の混合重量比率を考慮する。(Polymer Polyol) The active hydrogen compound (B) of the present invention may contain acrylonitrile, acrylonitrile in the presence of the above polyether polyols (b1), (b2) and (b3).
A commonly known polymer polyol (trade name) obtained by polymerizing an ethylenically unsaturated compound such as styrene and dispersing polyacrylonitrile, polystyrene, a copolymer, or the like in the above polyol can also be suitably used. in this way,
When using a polymer polyol, it is considered that polyacrylonitrile, polystyrene, or a copolymer thereof is simply used for dispersing the polyether polyol, and the amount grafted to the polyether polyol is negligible. Excluding these polymer components, only the original polyether polyol component had a hydroxyl value, ethylene oxide content and (b1), (b2), (b3)
Is considered.
【００１８】本発明に使用する発泡剤としては二酸化炭
素等公知の発泡剤であればいずれでも使用することがで
き、それぞれ単独でも複数を併用してもよい。その中で
も水が好ましい。発泡剤として水を使用する場合は水を
活性水素化合物（Ｂ）１００重量部あたり０．３〜５．
０重量部が好ましく、さらに好ましくは０．５〜３．５
重量部である。As the foaming agent used in the present invention, any known foaming agent such as carbon dioxide may be used, and each may be used alone or in combination. Among them, water is preferred. When water is used as the foaming agent, the water is used in an amount of 0.3 to 5.0 per 100 parts by weight of the active hydrogen compound (B).
0 parts by weight is preferred, and more preferably 0.5 to 3.5 parts.
Parts by weight.
【００１９】（その他添加剤等）本発明には、公知の触
媒、架橋剤、整泡剤、難燃剤、減粘剤、安定剤、充填
剤、着色剤が添加物として使用できる。触媒としては、
トリエチレンジアミン、ジメチルエタノールアミン等の
アミン系ウレタン化触媒、ラウリン酸錫、オクタン酸錫
等の有機金属系ウレタン化触媒があげられる。整泡剤と
しては東レ・ダウコーニング社製のＳＲＸ−２７４Ｃ、
日本ユニカ社製のＬ−５３０９、ゴールドシュミット社
製のＢ−４１１３等があげられる。架橋剤としてはトリ
エタノールアミン、ジエタノールアミン等があげられ
る。(Other Additives) In the present invention, known catalysts, crosslinking agents, foam stabilizers, flame retardants, viscosity reducing agents, stabilizers, fillers, and coloring agents can be used as additives. As a catalyst,
Examples include amine urethanization catalysts such as triethylenediamine and dimethylethanolamine, and organometallic urethanization catalysts such as tin laurate and tin octoate. As a foam stabilizer, SRX-274C manufactured by Dow Corning Toray,
Examples include L-5309 manufactured by Nippon Unica and B-4113 manufactured by Goldschmidt. Examples of the crosslinking agent include triethanolamine and diethanolamine.
【００２０】本発明を実施するには、通常、活性水素化
合物（Ｂ）、架橋剤、触媒、整泡剤、水、その他助剤
は、各々を所定量予め混合したレジンプレミクスとして
使用される。上記レジンプレミクスと有機ポリイソシア
ネート（A）とをウレタン発泡機を用い、両成分の混合
比がＮＣＯインデックス６０〜１１０、好ましくは６５
〜１００、さらに好ましくは７０〜９０となる比率で混
合し、所定の型内部（密閉系またはオープン系）に注入
発泡して軟質ポリウレタン発泡体をスラブ式、モールド
式で得る。In practicing the present invention, the active hydrogen compound (B), the crosslinking agent, the catalyst, the foam stabilizer, the water and other auxiliaries are usually used as a resin premix in which predetermined amounts of each are mixed in advance. . The above resin premix and the organic polyisocyanate (A) are mixed in a urethane foaming machine and the mixing ratio of both components is NCO index 60 to 110, preferably 65.
-100, more preferably 70-90, and the mixture is injected and foamed into a predetermined mold (closed system or open system) to obtain a flexible polyurethane foam by a slab type or a mold type.
【００２１】[0021]
【実施例】以下、本発明について実施例により説明する
が、本発明はこれらの実施例により制限されない。実施
例中の部及び％はそれぞれ「重量部」及び「重量％」を
示す。 （１）有機ポリイソシアネート（Ａ） 有機ポリイソシアネートa-1 コスモネートＭＣ−８３（ポリメチレンポリフェニルイ
ソシアネートからなり、ＮＣＯ％は２５％、三井化学社
製）を有機ポリイソシアネートa-1とした。 有機ポリイソシアネートa-2 コスモネートＴＭ−５０（ポリメチレンポリフェニルイ
ソシアネート／ＴＤＩ−８０＝５０／５０、ＮＣＯ％は
３９．７％、三井化学社製）を有機ポリイソシアネート
a-2とした。EXAMPLES Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. Parts and% in the examples indicate "parts by weight" and "% by weight", respectively. (1) Organic polyisocyanate (A) Organic polyisocyanate a-1 Cosmonate MC-83 (comprising polymethylene polyphenylisocyanate, NCO% 25%, manufactured by Mitsui Chemicals, Inc.) was used as organic polyisocyanate a-1. Organic polyisocyanate a-2 Cosmonate TM-50 (polymethylene polyphenyl isocyanate / TDI-80 = 50/50, NCO% is 39.7%, manufactured by Mitsui Chemicals, Inc.)
a-2.
【００２２】（２）活性水素化合物（Ｂ） １）ポリエーテルトリオール（b1-1） 開始剤にグリセリンを使用し、プロピレンオキサイドと
エチレンオキサイドのモル付加重合比率が２５／７５、
水酸基価が６２ｍｇＫＯＨ／ｇのポリエーテルトリオー
ル。 ２）ポリエーテルトリオール（b1-2） 開始剤にグリセリンを使用し、プロピレンオキサイドと
エチレンオキサイドのモル付加重合比率が３５／６５、
水酸基価が４９ｍｇＫＯＨ／ｇのポリエーテルトリオー
ル。 ３）ポリエーテルジオール（b1-3） 開始剤にジプロピレングリコールを使用し、プロピレン
オキサイドとエチレンオキサイドのモル付加重合比率が
６０／４０、水酸基価が７５ｍｇＫＯＨ／ｇのポリエー
テルジオール。 ４）ポリエーテルトリオール（b2-1） 開始剤にグリセリンを使用し、プロピレンオキサイドと
エチレンオキサイドのモル付加重合比率が１００／０、
水酸基価が４５０ｍｇＫＯＨ／ｇのポリエーテルトリオ
ール。 ５）ポリエーテルトリオール（b3-1） 開始剤にグリセリンを使用し、プロピレンオキサイドと
エチレンオキサイドのモル付加重合比率が１００／０、
水酸基価が１６８ｍｇＫＯＨ／ｇのポリエーテルトリオ
ール。 ６）ポリエーテルトリオール（b3-2） 開始剤にグリセリンを使用し、プロピレンオキサイドと
エチレンオキサイドのモル付加重合比率が８５／１５、
水酸基価が２８ｍｇＫＯＨ／ｇのポリエーテルトリオー
ル。 ７）ポリエーテルテトラオール（b3-3） 開始剤にペンタエリスリトールを使用し、プロピレンオ
キサイドとエチレンオキサイドのモル付加重合比率が８
５／１５、水酸基価が２４０ｍｇＫＯＨ／ｇのポリエー
テルテトラオール。(2) Active hydrogen compound (B) 1) Polyether triol (b1-1) Using glycerin as an initiator, the molar addition polymerization ratio of propylene oxide and ethylene oxide is 25/75,
Polyether triol having a hydroxyl value of 62 mgKOH / g. 2) Polyether triol (b1-2) Using glycerin as an initiator, the molar addition polymerization ratio of propylene oxide and ethylene oxide is 35/65,
Polyether triol having a hydroxyl value of 49 mgKOH / g. 3) Polyether diol (b1-3) Polyether diol using dipropylene glycol as an initiator, having a molar addition polymerization ratio of propylene oxide and ethylene oxide of 60/40 and a hydroxyl value of 75 mgKOH / g. 4) Polyether triol (b2-1) Using glycerin as an initiator, the molar addition polymerization ratio of propylene oxide and ethylene oxide is 100/0,
Polyether triol having a hydroxyl value of 450 mgKOH / g. 5) Polyether triol (b3-1) Using glycerin as an initiator, the molar addition polymerization ratio of propylene oxide and ethylene oxide is 100/0,
Polyether triol having a hydroxyl value of 168 mgKOH / g. 6) Polyether triol (b3-2) Using glycerin as an initiator, the molar addition polymerization ratio of propylene oxide and ethylene oxide is 85/15,
Polyether triol having a hydroxyl value of 28 mgKOH / g. 7) Polyethertetraol (b3-3) Pentaerythritol is used as the initiator and the molar addition polymerization ratio of propylene oxide and ethylene oxide is 8
5/15, polyethertetraol having a hydroxyl value of 240 mgKOH / g.
【００２３】（３）架橋剤 ＤＥＯＡ（ジエタノールアミン、三井化学社製） （４）シリコン整泡剤 Ｌ−５３０９（日本ユニカ社製） （５）アミン触媒 Ｌ−１０２０（活材ケミカル社製） Ａ−１（活材ケミカル社製）(3) Crosslinking agent DEOA (diethanolamine, manufactured by Mitsui Chemicals, Inc.) (4) Silicon foam stabilizer L-5309 (manufactured by Nippon Yunika) (5) Amine catalyst L-1020 (manufactured by Active Materials Chemical Co., Ltd.) 1 (Made by Active Materials Chemical Co., Ltd.)
【００２４】（６）軟質ポリウレタン発泡体（モールド
フォーム及びスラブフォーム）の作成活性水素化合物
（B）、架橋剤、シリコン整泡剤、アミン触媒、水を均
一に混合し、レジンプレミクスを調整し、２５℃に温調
した。これに２５℃に温調された有機ポリイソシアネー
トを所定のイソシアネートＩＮＤＥＸとなるように加
え、６秒間高速で攪拌混合し、６０℃に温調されたアル
ミ製モールド（２５０×２５０×５０ｍｍ）内に注入し
て発泡させた。所定時間金型内でキュアした後、モール
ドフォームが脱型可能になる時間をキュア時間とした。
また、モールドフォームを脱型してセル成形性（セルが
均一であるか、セル崩壊の有無の検査）を目視で評価
し、脱型から６時間、室温にて放置して、モールドフォ
ームの収縮変形の有無を目黙視で評価した。モールドフ
ォームに収縮変形が無い場合には、クラシングレス化を
可と評価し、脱型後２４時間経過後にフォーム物性を測
定（ＪＩＳＫ ６４００）、脱型から６時間、室温に放
置して、モールドフォームに収縮変形がある場合にはク
ラシングレス化を不可と評価し、再度、アルミ製モール
ドを使用して注入発泡を行い、脱型後すぐにクラシング
を行いモールドフォームを作成し直し、２４時間経過後
にフォーム物性を測定した。さらに、モールドフォーム
を作成する場合と同様にレジンプレミクスと有機ポリイ
ソシアネートを所定のＮＣＯインデックスで攪拌混合
し、５００×５００×５００ｍｍの上部解放容器中に投
入し、自由発泡させてスラブフォームを作成した。発泡
から２４時間経過後に目視によりフォームの収縮を評価
し、著しく収縮変形する場合はスラブ生産を否と評価し
た。(6) Preparation of a flexible polyurethane foam (mold foam and slab foam) An active hydrogen compound (B), a crosslinking agent, a silicone foam stabilizer, an amine catalyst, and water are uniformly mixed to adjust a resin premix. , 25 ° C. An organic polyisocyanate adjusted to 25 ° C. is added thereto so as to obtain a predetermined isocyanate INDEX, and mixed by stirring at a high speed for 6 seconds, and placed in an aluminum mold (250 × 250 × 50 mm) adjusted to 60 ° C. Injected and foamed. After curing in the mold for a predetermined time, the time during which the mold foam was able to be released was defined as cure time.
In addition, the mold foam was removed from the mold, and the cell formability (inspection of whether the cells were uniform or the cell collapsed) was visually evaluated. The presence or absence of the deformation was evaluated by blindness. If there is no shrinkage deformation in the mold foam, it is evaluated that no clashing is possible, and the properties of the foam are measured 24 hours after demolding (JISK 6400). If there is shrinkage deformation, it is evaluated that classlessness is not possible. Injection foaming is again performed using an aluminum mold. After demolding, classing is performed immediately, and a molded foam is created again. Was measured. Furthermore, the resin premix and the organic polyisocyanate are agitated and mixed at a predetermined NCO index in the same manner as in the case of forming a mold foam, and the mixture is poured into a 500 × 500 × 500 mm open top container, and freely foamed to form a slab foam. did. After 24 hours from the foaming, the shrinkage of the foam was visually evaluated.
【００２５】実施例１−７ （６）の軟質ポリウレタン発泡体の作成方法に従い、原
料組成を表１の通り変更して各々軟質ポリウレタンフォ
ームを作成し、その結果を表１に記した。実施例１〜７
においては反発弾性が２０％以下で、乾熱圧縮永久歪み
が５％以下、湿熱圧縮永久歪みが２％以下のモールドフ
ォームがノンクラシングで生産可能であることが分かっ
た。又スラブ生産も可能である。Examples 1-7 In accordance with the method for preparing a flexible polyurethane foam of (6), the raw material compositions were changed as shown in Table 1 to prepare flexible polyurethane foams, and the results are shown in Table 1. Examples 1 to 7
It was found that a molded foam having a rebound resilience of 20% or less, a dry heat compression set of 5% or less, and a wet heat compression set of 2% or less can be produced without classing. Slab production is also possible.
【００２６】[0026]
【表１】 [Table 1]
【００２７】比較例１−６ （６）の軟質ポリウレタン発泡体の作成方法に従い、原
料組成を表２の通り変更して各々軟質ポリウレタンフォ
ームを作成し、その結果を表２に記した。Comparative Examples 1-6 According to the method for preparing a flexible polyurethane foam of (6), the raw material compositions were changed as shown in Table 2 to prepare flexible polyurethane foams, and the results are shown in Table 2.
【００２８】[0028]
【表２】 [Table 2]
【００２９】[0029]
【発明の効果】本発明によれば特定の活性水素化合物を
使用することで、反発弾性が２０％以下で、かつ耐久性
の高い低反発弾性軟質ポリウレタン発泡体をスラブ式及
びモールド式で製造することが可能となる。According to the present invention, by using a specific active hydrogen compound, a durable, low-rebound resilient, flexible polyurethane foam having a rebound resilience of 20% or less and high durability is produced by a slab type and a mold type. It becomes possible.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 大久保 和彦 神奈川県横浜市栄区笠間町1190番地 三井 化学株式会社内 (72)発明者 笹岡 邦男 神奈川県横浜市栄区笠間町1190番地 三井 化学株式会社内 Ｆターム(参考） 4J034 AA04 BA03 DA01 DB03 DB07 DC50 DG03 DG04 DG05 DG09 DG12 DG14 DG18 HA01 HA02 HA06 HA07 HA11 HB05 HB06 HB07 HB08 HB09 HC12 HC73 KA01 KB02 KC17 KD12 KE02 NA01 NA03 NA05 QA02 QB14 QB15 QC01 RA02 RA12 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kazuhiko Okubo 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Chemicals Co., Ltd. (72) Inventor Kunio Sasaoka 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Chemicals F Terms (reference) 4J034 AA04 BA03 DA01 DB03 DB07 DC50 DG03 DG04 DG05 DG09 DG12 DG14 DG18 HA01 HA02 HA06 HA07 HA11 HB05 HB06 HB07 HB08 HB09 HC12 HC73 KA01 KB02 KC17 KD12 KE02 NA01 NA03 NA05 QA02 QB
Claims (10)
素化合物(Ｂ)と、発泡剤とから得られる軟質ポリウレタ
ン発泡体において、活性水素化合物（Ｂ）が（b1）水酸
基価が４０ｍｇＫＯＨ／ｇ以上１２０ｍｇＫＯＨ／ｇ以
下で、平均官能基数２以上４以下であり、炭素数３以上
のアルキレンオキシドとエチレンオキシドのモル付加重
合比率が５０／５０〜１０／９０であるポリエーテルポ
リオール、（b2）水酸基価が４１０ｍｇＫＯＨ／ｇ以上
６００ｍｇＫＯＨ／ｇ以下で、平均官能基数２以上８以
下であるポリエーテルポリオール、（b3）水酸基価が２
０ｍｇＫＯＨ／ｇ以上１７０ｍｇＫＯＨ／ｇ以下で、平
均官能基数２以上４以下であるポリエーテルポリオー
ル、（b1）、（b2）、（b3）の重量の総和を１００とし
たとき各成分混合割合が（b1）３０〜８５、（b2）５〜
５０、（b3）１０〜４０である混合物又は該混合物から
得られるポリマーポリオールであることを特徴とする軟
質ポリウレタン発泡体。1. A flexible polyurethane foam obtained from an organic polyisocyanate (A), an active hydrogen compound (B) and a foaming agent, wherein the active hydrogen compound (B) has (b1) a hydroxyl value of at least 40 mg KOH / g. A polyether polyol having an average functional group number of 2 to 4 at 120 mgKOH / g or less, a molar addition polymerization ratio of an alkylene oxide having 3 or more carbon atoms and ethylene oxide of 50/50 to 10/90, and (b2) a hydroxyl value of A polyether polyol having an average functional group number of 2 to 8 in the range of 410 mgKOH / g to 600 mgKOH / g, and (b3) a hydroxyl value of 2
When the total weight of the polyether polyols (b1), (b2), and (b3) having an average functional group number of 2 to 4 in the range of 0 mgKOH / g to 170 mgKOH / g is 100, the mixing ratio of each component is (b1 ) 30-85, (b2) 5
50, (b3) a flexible polyurethane foam, which is a mixture of 10 to 40 or a polymer polyol obtained from the mixture.
レンポリフェニルイソシアネート（a）であることを特
徴とする請求項１記載の軟質ポリウレタン発泡体。2. The flexible polyurethane foam according to claim 1, wherein the organic polyisocyanate (A) is polymethylene polyphenyl isocyanate (a).
価が６１ｍｇＫＯＨ／ｇ以上８５ｍｇＫＯＨ／ｇ以下
で、平均官能基数２以上３以下であり、炭素数３以上の
アルキレンオキシドとエチレンオキシドのモル付加重合
比率が４０／６０〜１５／８５であることを特徴とする
請求項第１項記載の軟質ポリウレタン発泡体。3. The polyether polyol (b1) has a hydroxyl value of from 61 mgKOH / g to 85 mgKOH / g, an average number of functional groups of from 2 to 3, and a mole addition polymerization ratio of alkylene oxide having 3 or more carbon atoms and ethylene oxide. 2. The flexible polyurethane foam according to claim 1, wherein the ratio is 40/60 to 15/85. 3.
価が４１０ｍｇＫＯＨ／ｇ以上５００ｍｇＫＯＨ／ｇ以
下で平均官能基数２以上４以下であることを特徴とする
請求項第１項記載の軟質ポリウレタン発泡体。4. The flexible polyurethane foam according to claim 1, wherein the hydroxyl value of the polyether polyol (b2) is from 410 mgKOH / g to 500 mgKOH / g and the average number of functional groups is from 2 to 4 inclusive. .
価が２０ｍｇＫＯＨ／ｇ以上６０ｍｇＫＯＨ／ｇ以下
で、平均官能基数２以上４以下であり、炭素数３以上の
アルキレンオキシドとエチレンオキシドのモル付加重合
比率が９０／１０〜８０／２０であることを特徴とする
請求項第１項記載の軟質ポリウレタン発泡体。5. The molar addition polymerization ratio of alkylene oxide having 3 or more carbon atoms and ethylene oxide having a hydroxyl value of the polyether polyol (b3) of 20 mgKOH / g or more and 60 mgKOH / g or less, and having an average number of functional groups of 2 or more and 4 or less. 2. The flexible polyurethane foam according to claim 1, wherein the ratio is 90/10 to 80/20.
４０〜６０／１０〜４０／２０〜４０であることを特徴
とする請求項第１項記載の軟質ポリウレタン発泡体。6. The flexible polyurethane foam according to claim 1, wherein the mixture weight ratio of (b1) / (b2) / (b3) is 40-60 / 10-40 / 20-40. .
素化合物(B)と、発泡剤とから軟質ポリウレタン発泡体
を製造する方法において、活性水素化合物（Ｂ）として
（b1）水酸基価が４０ｍｇＫＯＨ／ｇ以上１２０ｍｇＫ
ＯＨ／ｇ以下で、平均官能基数２以上４以下であり、炭
素数３以上のアルキレンオキシドとエチレンオキシドの
モル付加重合比率が５０／５０〜１０／９０であるポリ
エーテルポリオール、（b2）水酸基価が４１０ｍｇＫＯ
Ｈ／ｇ以上６００ｍｇＫＯＨ／ｇ以下で、平均官能基数
２以上８以下であるポリエーテルポリオール、（b3）水
酸基価が２０ｍｇＫＯＨ／ｇ以上１７０ｍｇＫＯＨ／ｇ
以下で、平均官能基数２以上４以下であるポリエーテル
ポリオール、（b1）、（b2）、（b3）の重量の総和を１
００としたとき各成分混合割合が（b1）３０〜８５、
（b2）５〜５０、（b3）１０〜４０である混合物又は該
混合物から得られるポリマーポリオールを用いることを
特徴とする軟質ポリウレタン発泡体の製造方法。7. A process for producing a flexible polyurethane foam from an organic polyisocyanate (A), an active hydrogen compound (B) and a blowing agent, wherein the active hydrogen compound (B) has (b1) a hydroxyl value of 40 mg KOH / g or more and 120 mgK
OH / g or less, polyether polyol having an average functional group number of 2 or more and 4 or less, and a molar addition polymerization ratio of alkylene oxide having 3 or more carbon atoms and ethylene oxide of 50/50 to 10/90, (b2) a hydroxyl value of 410mg KO
A polyether polyol having an average number of functional groups of 2 or more and 8 or less and H / g or more and 600 mg KOH / g or less, and (b3) a hydroxyl value of 20 mg KOH / g or more and 170 mg KOH / g.
In the following, the total weight of the polyether polyol having an average number of functional groups of 2 or more and 4 or less, (b1), (b2), and (b3) is 1
When it is set to 00, the mixing ratio of each component is (b1) 30 to 85,
(B2) A method for producing a flexible polyurethane foam, comprising using a mixture of 5 to 50, (b3) a mixture of 10 to 40, or a polymer polyol obtained from the mixture.
オールの水酸基価が２０ｍｇＫＯＨ／ｇ以上６０ｍｇＫ
ＯＨ／ｇ以下で、平均官能基数２以上４以下であり、炭
素数３以上のアルキレンオキシドとエチレンオキシドの
モル付加重合比率が９０／１０〜８０／２０であること
を特徴とする軟質ポリウレタン発泡体の製造方法。8. The polyether polyol according to claim 7, wherein the polyether polyol has a hydroxyl value of not less than 20 mgKOH / g and not more than 60 mgKOH.
OH / g or less, an average number of functional groups is 2 or more and 4 or less, and a molar addition polymerization ratio of alkylene oxide having 3 or more carbon atoms and ethylene oxide is 90/10 to 80/20. Production method.
みが５％以下、湿熱圧縮永久歪みが２％以下の軟質ポリ
ウレタン発泡体をクラシングすることなく製造すること
を特徴とする請求項第７項記載の軟質ポリウレタン発泡
体の製造方法。9. A flexible polyurethane foam having a rebound resilience of 20% or less, a dry heat compression set of 5% or less, and a wet heat compression set of 2% or less is produced without crushing. A method for producing a flexible polyurethane foam according to claim 7.
量部当たり０．３〜５．０重量部使用することを特徴と
する請求項第７ないし９記載の軟質ポリウレタン発泡体
の製造方法。10. The process for producing a flexible polyurethane foam according to claim 7, wherein the foaming agent is used in an amount of 0.3 to 5.0 parts by weight per 100 parts by weight of the active hydrogen compound (B).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09960599A JP3992869B2 (en) | 1999-04-07 | 1999-04-07 | Energy-absorbing flexible polyurethane foam and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09960599A JP3992869B2 (en) | 1999-04-07 | 1999-04-07 | Energy-absorbing flexible polyurethane foam and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000290344A true JP2000290344A (en) | 2000-10-17 |
| JP3992869B2 JP3992869B2 (en) | 2007-10-17 |
Family
ID=14251734
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09960599A Expired - Lifetime JP3992869B2 (en) | 1999-04-07 | 1999-04-07 | Energy-absorbing flexible polyurethane foam and method for producing the same |
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| Country | Link |
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| JP2003505570A (en) * | 1999-07-26 | 2003-02-12 | ハンツマン・インターナショナル・エルエルシー | Process for producing cold-cure flexible foams, polyol compositions and reaction systems useful therefor, foams obtained thereby |
| US6756415B2 (en) | 2001-11-29 | 2004-06-29 | Asahi Glass Company, Limited | Flexible polyurethane foam and method for its production |
| WO2005077998A1 (en) * | 2004-02-17 | 2005-08-25 | Bridgestone Corporation | Low-resilience highly air-permeable polyurethane foam and use thereof |
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| US11572433B2 (en) | 2021-03-12 | 2023-02-07 | Covestro Llc | In-situ formed polyols, a process for their preparation, foams prepared from these in-situ formed polyols and a process for their preparation |
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