JP2004238611A - Soft polyurethane foam having minute cell - Google Patents
Soft polyurethane foam having minute cell Download PDFInfo
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- JP2004238611A JP2004238611A JP2003365574A JP2003365574A JP2004238611A JP 2004238611 A JP2004238611 A JP 2004238611A JP 2003365574 A JP2003365574 A JP 2003365574A JP 2003365574 A JP2003365574 A JP 2003365574A JP 2004238611 A JP2004238611 A JP 2004238611A
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- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 49
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 49
- 229920005862 polyol Polymers 0.000 claims abstract description 72
- 150000003077 polyols Chemical class 0.000 claims abstract description 72
- 239000006260 foam Substances 0.000 claims abstract description 21
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 20
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 20
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- 238000005187 foaming Methods 0.000 claims abstract description 10
- 239000011358 absorbing material Substances 0.000 claims abstract description 7
- 239000004088 foaming agent Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 6
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 6
- 230000001588 bifunctional effect Effects 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000012948 isocyanate Substances 0.000 abstract description 7
- 150000002513 isocyanates Chemical class 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 230000009257 reactivity Effects 0.000 abstract description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 229920000570 polyether Polymers 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 229920005906 polyester polyol Polymers 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 150000002596 lactones Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000000644 propagated effect Effects 0.000 description 3
- OQXSRALAOPBHPM-UHFFFAOYSA-N 2-hydroxypropanoic acid;silver Chemical compound [Ag].CC(O)C(O)=O OQXSRALAOPBHPM-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 150000004072 triols Chemical class 0.000 description 2
- -1 Polypropylene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920002323 Silicone foam Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000013514 silicone foam Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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Abstract
Description
本発明は微細セル軟質ポリウレタンフォームに係り、特に、著しく微細なセル構造を有し、このため、吸音材用フォーム、電極材用フォーム、プリンターローラ用フォーム等として良好な性能を発揮することができる微細セル軟質ポリウレタンフォームに関する。また、本発明は、この微細セル軟質ポリウレタンフォームよりなる吸音材に関する。 The present invention relates to a fine cell flexible polyurethane foam, and in particular, has a remarkably fine cell structure. Therefore, it can exhibit good performance as a foam for a sound absorbing material, a foam for an electrode material, a foam for a printer roller, and the like. The present invention relates to a fine cell flexible polyurethane foam. The present invention also relates to a sound-absorbing material comprising this fine cell flexible polyurethane foam.
従来、ポリオールとポリイソシアネートとを反応させて得られたイソシアネート末端プレポリマーを原料とする軟質ポリウレタンフォームの製造方法は公知である。この方法では、比較的高分子量のポリオールの１種類をポリイソシアネートと反応させてプレポリマー化してなるイソシアネート末端プレポリマーに、触媒や発泡剤を添加混合して発泡硬化させることにより軟質ポリウレタンフォームが製造される。 Conventionally, a method for producing a flexible polyurethane foam using an isocyanate-terminated prepolymer obtained by reacting a polyol and a polyisocyanate as a raw material is known. In this method, a flexible polyurethane foam is produced by adding and mixing a catalyst and a foaming agent to an isocyanate-terminated prepolymer obtained by reacting one kind of a relatively high molecular weight polyol with a polyisocyanate to form a prepolymer. Is done.
このようにして製造される軟質ポリウレタンフォームの用途として、吸音材、電極材、プリンターローラ等がある。これらの用途において、軟質ポリウレタンフォームは、そのセル構造がより微細であることが、吸音材としての吸音性、電極材としての容量アップ、ローラ等としての機械的強度、耐久性等の面で重要である。 Applications of the flexible polyurethane foam thus produced include a sound absorbing material, an electrode material, and a printer roller. In these applications, the flexible polyurethane foam has a finer cell structure, which is important in terms of sound absorption as a sound absorbing material, increased capacity as an electrode material, mechanical strength as a roller, durability, etc. It is.
しかしながら、従来法で製造される軟質ポリウレタンフォームは、最も微細なフォームであってもセル径２５０μｍ程度が限度であり、より一層のセルの微細化が望まれている。 However, the flexible polyurethane foam produced by the conventional method has a cell diameter of about 250 μm even if it is the finest foam, and further cell miniaturization is desired.
本発明は、上記従来の実情に鑑みてなされたものであって、非常に微細なセル構造を持つ軟質ポリウレタンフォームを提供することを目的とする。 The present invention has been made in view of the above-described conventional situation, and an object thereof is to provide a flexible polyurethane foam having a very fine cell structure.
本発明の微細セル軟質ポリウレタンフォームは、イソシアネート末端プレポリマーに、架橋剤、及び発泡成分を添加して混合し、発泡硬化させて得られる微細セル構造ポリウレタンエラストマーであって、該イソシアネート末端プレポリマーは、数平均分子量が４００〜１０００の低分子量ポリオールの１種以上と数平均分子量が３０００〜１２０００の高分子量ポリオールの１種以上とを含むポリオール成分とポリイソシアネートとを反応させてなるものであることを特徴とする。 The fine-cell flexible polyurethane foam of the present invention is a fine-cell structure polyurethane elastomer obtained by adding a crosslinking agent and a foaming component to an isocyanate-terminated prepolymer, mixing and foam-curing, and the isocyanate-terminated prepolymer comprises: And a polyol component containing at least one low molecular weight polyol having a number average molecular weight of 400 to 1000 and one or more high molecular weight polyols having a number average molecular weight of 3000 to 12000 and a polyisocyanate. It is characterized by.
本発明では、分子量の異なる２種類以上のポリオールとポリイソシアネートとを反応させて得られたイソシアネート末端プレポリマーを用いることにより、低分子量ポリオール由来のイソシアネート末端プレポリマーと、高分子量ポリオール由来のイソシアネート末端プレポリマーとの反応性の差異を利用してセルの物理的会合を妨げ、微細セル構造の軟質ポリウレタンフォームを得ることができる。 In the present invention, by using an isocyanate-terminated prepolymer obtained by reacting two or more kinds of polyols having different molecular weights with a polyisocyanate, an isocyanate-terminated prepolymer derived from a low-molecular-weight polyol and an isocyanate-terminated terminal derived from a high-molecular-weight polyol are used. By utilizing the difference in reactivity with the prepolymer, physical association of the cells can be prevented and a flexible polyurethane foam having a fine cell structure can be obtained.
本発明において、プレポリマー化に用いるポリオール成分中の低分子量ポリオールの割合は、３０重量％以上、特に４０〜５０重量％であることが好ましく、ポリオール成分とポリイソシアネートとは１：０．１５〜０．５の重量比で反応させることが好ましい。 In the present invention, the proportion of the low molecular weight polyol in the polyol component used for prepolymerization is preferably 30% by weight or more, particularly preferably 40 to 50% by weight, and the polyol component and polyisocyanate are 1: 0.15 to The reaction is preferably carried out at a weight ratio of 0.5.
また、架橋剤としては、２官能以上の低分子量ポリオールを用いることが好ましく、このような低分子量ポリオールをイソシアネート末端プレポリマー１００重量部に対して３．０〜１０．０重量部用いることにより、架橋密度を上げ、より一層のセルの微細化を図ることができる。 Further, as the crosslinking agent, it is preferable to use a bifunctional or higher functional low molecular weight polyol, and by using such a low molecular weight polyol in an amount of 3.0 to 10.0 parts by weight with respect to 100 parts by weight of the isocyanate-terminated prepolymer, The crosslink density can be increased and further cell miniaturization can be achieved.
発泡成分は、水を主成分とする発泡剤と、触媒及び整泡剤とを含むものであり、イソシアネート末端プレポリマー１００重量部に対する発泡剤の添加量は、０．５〜２．０重量部とすることが好ましい。 A foaming component contains the foaming agent which has water as a main component, a catalyst, and a foam stabilizer, The addition amount of the foaming agent with respect to 100 weight part of isocyanate terminal prepolymers is 0.5-2.0 weight part. It is preferable that
イソシアネート末端プレポリマーのポリイソシアネートとしては、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート及びジフェニルメタン−４，４’−ジイソシアネートよりなる群から選ばれる１種又は２種以上が好適である。 As the polyisocyanate of the isocyanate-terminated prepolymer, one or more selected from the group consisting of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and diphenylmethane-4,4′-diisocyanate are suitable. .
本発明の微細セル軟質ポリウレタンフォームは、好ましくは密度が０．０５〜０．２５ｇ／ｃｍ３で、平均セル径が２０〜１００μｍの極微細セル軟質ポリウレタンフォームである。
Microcellular flexible polyurethane foam of the present invention are preferably a density of 0.05~0.25g / cm 3, average cell diameter is very fine cell
本発明によれば、非常に微細なセル構造を持つ軟質ポリウレタンフォームが提供される。 According to the present invention, a flexible polyurethane foam having a very fine cell structure is provided.
本発明の微細セル軟質ポリウレタンフォームは、その極めて微細なセル構造により吸音材用フォーム、電極材用フォーム、プリンターローラ用フォーム、その他緩衝材用フォーム、化粧用パフ材等として著しく良好な性能を発揮する。 The fine cell flexible polyurethane foam of the present invention exhibits extremely good performance as a sound absorbing material foam, an electrode material foam, a printer roller foam, a cushioning foam, a cosmetic puff material, etc. due to its extremely fine cell structure. To do.
以下に本発明の微細セル軟質ポリウレタンフォームの実施の形態を詳細に説明する。 Hereinafter, embodiments of the fine cell flexible polyurethane foam of the present invention will be described in detail.
まず、本発明で用いるイソシアネート末端プレポリマーについて説明する。 First, the isocyanate-terminated prepolymer used in the present invention will be described.
本発明で用いるイソシアネート末端プレポリマーは、数平均分子量が４００〜１０００の低分子量ポリオールの１種以上と数平均分子量が３０００〜１２０００の高分子量ポリオールの１種以上とを含むポリオール成分と、ポリイソシアネートとを反応させてなるものであり、本発明では、このように、分子量の異なる２種類以上のポリオールとポリイソシアネートとを反応させて得られたイソシアネート末端プレポリマーを用いることにより、低分子量ポリオール由来のイソシアネート末端プレポリマーと、高分子量ポリオール由来のイソシアネート末端プレポリマーとの反応性の差異を利用してセルの物理的会合を妨げ、微細セル構造の軟質ポリウレタンフォームを得ることができる。 The isocyanate-terminated prepolymer used in the present invention includes a polyol component containing at least one low molecular weight polyol having a number average molecular weight of 400 to 1,000 and at least one high molecular weight polyol having a number average molecular weight of 3000 to 12000, and a polyisocyanate. In the present invention, by using an isocyanate-terminated prepolymer obtained by reacting two or more kinds of polyols having different molecular weights with a polyisocyanate, it is derived from a low molecular weight polyol. By utilizing the difference in reactivity between the isocyanate-terminated prepolymer of the present invention and the isocyanate-terminated prepolymer derived from a high molecular weight polyol, physical association of the cells can be prevented, and a flexible polyurethane foam having a fine cell structure can be obtained.
本発明において、プレポリマー化に用いるポリオールは、ポリエステルポリオール、ポリエーテルポリオールのいずれであってもよく、これらの混合物であっても良い。 In the present invention, the polyol used for prepolymerization may be either a polyester polyol or a polyether polyol, or a mixture thereof.
ポリエーテルポリオールとしては、例えばプロピレングリコール、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、ヘキサントリオールなどを出発物質としてアルキレンオキシドを付加重合してなるものが好ましく、特にグリセリンにエチレンオキシド又はエチレンオキシドとプロピレンオキシドを付加重合させたものが好適である。ポリエステルポリオールとしては、ジカルボン酸とジオールやトリオールなどとの縮合により得られる縮合系ポリエステルポリオール、ジオールやトリオールをベースとしてラクトンの開環重合により得られるラクトン系ポリエステルポリオール、ポリエーテルポリオールの末端をラクトンでエステル変性したエステル変性ポリオールなどのポリオールが好ましく用いられる。 As the polyether polyol, for example, those obtained by addition polymerization of alkylene oxide using propylene glycol, ethylene glycol, glycerin, trimethylolpropane, hexanetriol or the like as a starting material are preferable. In particular, addition polymerization of ethylene oxide or ethylene oxide and propylene oxide to glycerin is preferable. What was made to be suitable is suitable. Polyester polyols include condensed polyester polyols obtained by condensation of dicarboxylic acids with diols and triols, lactone polyester polyols obtained by ring-opening polymerization of lactones based on diols and triols, and polyether polyols with lactones at the ends. A polyol such as an ester-modified polyol modified with an ester is preferably used.
低分子量ポリオールとしては、数平均分子量４００〜１０００好ましくは７００〜１０００で、水酸基価１５０〜５００のものが好ましく、高分子量ポリオールとしては、数平均分子量３０００〜１２０００好ましくは３０００〜９０００で、水酸基価１５〜６０のものが好ましい。 The low molecular weight polyol has a number average molecular weight of 400 to 1000, preferably 700 to 1000, and a hydroxyl value of 150 to 500, and the high molecular weight polyol has a number average molecular weight of 3000 to 12000, preferably 3000 to 9000, and a hydroxyl value. The thing of 15-60 is preferable.
プレポリマー化に用いるポリオール成分中の低分子量ポリオールの割合は、３０重量％以上、特に４０〜５０重量％であることが好ましい。ポリオール成分中の低分子量ポリオールの割合が３０重量％未満では、低分子量ポリオールと高分子量ポリオールとを併用することによる本発明の効果を十分に得ることができない。ポリオール中の低分子量ポリオールの割合が多過ぎても同様に低分子量ポリオールと高分子量ポリオールとを併用することによる本発明の効果を十分に得ることができない上にプレポリマーの粘度が高く、触媒等と均一に混ざらない等の問題が生じる。 The proportion of the low molecular weight polyol in the polyol component used for prepolymerization is preferably 30% by weight or more, particularly 40 to 50% by weight. When the ratio of the low molecular weight polyol in the polyol component is less than 30% by weight, the effect of the present invention by combining the low molecular weight polyol and the high molecular weight polyol cannot be sufficiently obtained. Even if the proportion of the low molecular weight polyol in the polyol is too large, the effect of the present invention due to the combined use of the low molecular weight polyol and the high molecular weight polyol cannot be sufficiently obtained, and the viscosity of the prepolymer is high, the catalyst, etc. Problems such as not being mixed uniformly.
一方、プレポリマー化に用いるポリイソシアネートとしては、２，４−トリレンジイソシアネート（２，４−ＴＤＩ）、２，６−トリレンジイソシアネート（２，６−ＴＤＩ）及びジフェニルメタン−４，４’−ジイソシアネート（ＭＤＩ）よりなる群から選ばれる１種又は２種以上（例えば２，４−ＴＤＩと２，６−ＴＤＩとの混合物）が好適である。 On the other hand, as polyisocyanate used for prepolymerization, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), and diphenylmethane-4,4′-diisocyanate One or more selected from the group consisting of (MDI) (for example, a mixture of 2,4-TDI and 2,6-TDI) is preferred.
上記ポリオール成分とポリイソシアネートとは、ポリオール成分：ポリイソシアネート＝１：０．１５〜０．５（重量比）で反応させることが好ましい。この範囲よりもポリイソシアネートが多いと得られるプレポリマー中のフリーのポリイソシアネート含有量が多くなり発泡剤との反応が速くなって得られるフォームのセル径及び形状が不均一なものとなる。逆に、この範囲よりも少ないとプレポリマー生成時の液の粘度が上昇して作業性が低下する。 The polyol component and the polyisocyanate are preferably reacted at a polyol component: polyisocyanate = 1: 0.15 to 0.5 (weight ratio). If the amount of polyisocyanate is larger than this range, the content of free polyisocyanate in the resulting prepolymer is increased, and the reaction with the foaming agent is accelerated, resulting in non-uniform cell diameter and shape of the foam. On the other hand, if it is less than this range, the viscosity of the liquid at the time of producing the prepolymer increases and the workability decreases.
本発明においては、このようにして分子量の異なる２種以上のポリオール成分とポリイソシアネートとを反応させて得られたイソシアネート末端プレポリマーに架橋剤、及び発泡成分の所定量を添加し、撹拌混合して発泡硬化させる。 In the present invention, a predetermined amount of a crosslinking agent and a foaming component is added to the isocyanate-terminated prepolymer obtained by reacting two or more polyol components having different molecular weights with polyisocyanate in this way, and the mixture is stirred and mixed. To foam and cure.
本発明で用いる架橋剤としては、２官能以上、特に３官能以上の低分子量ポリオールが好ましく、このような低分子量ポリオールをイソシアネート末端プレポリマー１００重量部に対して３．０〜１０．０重量部用いることにより、架橋密度を上げ、より一層のセルの微細化を図ることができる。 The cross-linking agent used in the present invention is preferably a bifunctional or higher, particularly a trifunctional or higher low molecular weight polyol, and such low molecular weight polyol is 3.0 to 10.0 parts by weight with respect to 100 parts by weight of the isocyanate-terminated prepolymer. By using it, the crosslink density can be increased and further cell miniaturization can be achieved.
このような低分子量ポリオールとしては、分子量１００〜３００のもの、具体的にはトリメチロールプロパン、トリメチロールプロパンのＰＯ変性物、その他のポリアルキレンポリオール、ポリエーテルポリオールが挙げられる。 Examples of such low molecular weight polyols include those having a molecular weight of 100 to 300, specifically, trimethylolpropane, PO-modified products of trimethylolpropane, other polyalkylene polyols, and polyether polyols.
架橋剤は、その添加量が少な過ぎると十分な架橋密度を得ることができず、多過ぎると正常なフォームを発泡させることが困難であることから、上記範囲とすることが好ましい。 When the amount of the crosslinking agent is too small, a sufficient crosslinking density cannot be obtained, and when it is too large, it is difficult to foam a normal foam.
なお、架橋剤としては、得られる軟質ポリウレタンフォームの架橋度を低下させない範囲で上記２官能、好ましくは３官能以上の低分子量ポリオールの他、エチレングリコール、プロピレングリコール等のジオールを併用しても良い。 In addition, as a crosslinking agent, diols such as ethylene glycol and propylene glycol may be used in combination with the above-mentioned bifunctional, preferably trifunctional or higher functional low molecular weight polyol as long as the degree of crosslinking of the resulting flexible polyurethane foam is not lowered. .
発泡成分は、水を主成分とする発泡剤と、触媒と整泡剤とを含むものであり、イソシアネート末端プレポリマー１００重量部に対する発泡剤の添加量は、０．５〜２．０重量部とすることが好ましい。 A foaming component contains the foaming agent which has water as a main component, a catalyst, and a foam stabilizer, and the addition amount of the foaming agent with respect to 100 weight part of isocyanate terminal prepolymers is 0.5-2.0 weight part. It is preferable that
触媒、整泡剤としては、軟質ポリウレタンフォームの製造に用いられている一般的なものを用いることができ、その添加量も、軟質ポリウレタンフォームの製造に通常採用される量で良い。本発明では、上記添加成分以外に、本発明の微細セル軟質ポリウレタンフォームの性能を損なわない範囲において、難燃剤、酸化防止剤、着色剤、紫外線吸収剤、その他の添加剤を添加しても良い。 As a catalyst and a foam stabilizer, the general thing used for manufacture of a flexible polyurethane foam can be used, and the addition amount may be the quantity normally employ | adopted for manufacture of a flexible polyurethane foam. In the present invention, in addition to the above-mentioned additive components, flame retardants, antioxidants, colorants, ultraviolet absorbers, and other additives may be added as long as the performance of the fine cell flexible polyurethane foam of the present invention is not impaired. .
このようにして製造される本発明の微細セル軟質ポリウレタンフォームは、好ましくは密度０．０５〜０．２５ｇ／ｃｍ３、平均セル径２０〜１２０μｍより好ましくは５０〜１２０μｍの微細セル構造の軟質ポリウレタンフォームであり、各種用途において良好な性能を発揮する。
Soft polyurethane of the thus microcellular flexible polyurethane foam of the present invention produced preferably has a density 0.05~0.25g / cm 3, more preferably an
以下に実施例及び比較例を挙げて本発明をより具体的に説明する。 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.
なお、以下の実施例及び比較例で用いた原料は次の通りである。
１）イソシアネート成分
２，４−ＴＤＩ／２，６−ＴＤＩの比率８０／２０：三井武田ケミカル社製
２）ポリオール成分
［低分子量ポリオール］
ａ）ポリエーテルポリオール：三井武田ケミカル社製 商品名「アクトコールＭＮ４０
０」（数平均分子量：４００，水酸基価：４１２）
ｂ）ポリエーテルポリオール：三井武田ケミカル社製 商品名「アクトコールＭＮ７０
０」（数平均分子量：７００，水酸基価：２３３）
ｃ）ポリプロピレンポリオール：三井武田ケミカル社製 商品名「アクトコール３２−
１６０」（数平均分子量：１０００，水酸基価：１６０）
［高分子量ポリオール］
ａ）ポリエーテルポリオール：三洋化成社製 商品名「サンニックスＧＳ−３０００」
（数平均分子量：３０００，水酸基価：５６）
ｂ）ポリオキシアルキレンポリオール：三井武田ケミカル社製 商品名「アクトコール
ＭＦ７８」（数平均分子量：４８００，水酸基価：３４）
ｃ）ポリアルキレンオキシドポリオール：三井武田ケミカル社製 商品名「アクトコー
ルＳＨＰ３９００」（数平均分子量：９０００，水酸基価：１９．４）
３）架橋剤（低分子量ポリオール）
ポリエーテルポリオール：三井武田ケミカル社製 商品名「アクトコールＴ８８０
」（数平均分子量：２２４，水酸基価：８８０）
４）発泡剤：水
５）触媒：トリエチレンジアミン（主成分）
東洋曹達社製 商品名「ＴＯＹＯＣＡＴ ＴＦ」
６）整泡剤（シリコーン整泡剤）：日本ユニカー社製 商品名「ＳＺ１１２７」
The raw materials used in the following examples and comparative examples are as follows.
1)
a) Polyether polyol: trade name “Actol MN40” manufactured by Mitsui Takeda Chemical Co., Ltd.
0 ”(number average molecular weight: 400, hydroxyl value: 412)
b) Polyether polyol: Trade name “Actocol MN70” manufactured by Mitsui Takeda Chemical Co., Ltd.
0 "(number average molecular weight: 700, hydroxyl value: 233)
c) Polypropylene polyol: manufactured by Mitsui Takeda Chemical Co., Ltd.
160 "(number average molecular weight: 1000, hydroxyl value: 160)
[High molecular weight polyol]
a) Polyether polyol: Sanyo Kasei Co., Ltd. trade name “SANNICS GS-3000”
(Number average molecular weight: 3000, hydroxyl value: 56)
b) Polyoxyalkylene polyol: manufactured by Mitsui Takeda Chemical Co., Ltd., trade name “Actol MF78” (number average molecular weight: 4800, hydroxyl value: 34)
c) Polyalkylene oxide polyol: manufactured by Mitsui Takeda Chemical Co., Ltd. Trade name “Act Call SHP3900” (number average molecular weight: 9000, hydroxyl value: 19.4)
3) Cross-linking agent (low molecular weight polyol)
Polyether polyol: manufactured by Mitsui Takeda Chemical Co., Ltd.
(Number average molecular weight: 224, hydroxyl value: 880)
4) Foaming agent: water 5) Catalyst: triethylenediamine (main component)
Product name “TOYOCAT TF” manufactured by Toyo Soda Co., Ltd.
6) Foam stabilizer (silicone foam stabilizer): Nippon Unicar Company Limited “SZ1127”
実施例１、比較例１
表１に示す配合でポリエーテルポリオール成分とポリイソシアネートとを反応させてイソシアネート末端プレポリマーを製造し、このイソシアネート末端プレポリマーに対して、表１に示す割合で発泡成分、架橋剤を添加し、混合撹拌させて軟質ウレタンフォームを製造した。
Example 1 and Comparative Example 1
A polyether polyol component and a polyisocyanate are reacted in the formulation shown in Table 1 to produce an isocyanate-terminated prepolymer, and a foaming component and a crosslinking agent are added to the isocyanate-terminated prepolymer at a ratio shown in Table 1, A flexible urethane foam was produced by mixing and stirring.
得られた軟質ウレタンフォームについて、下記方法で密度、平均セル径を調べ、結果を表１に示した。 For the obtained flexible urethane foam, the density and average cell diameter were examined by the following method, and the results are shown in Table 1.
［密度］
５０×３００×３００ｍｍのサンプルの重量を体積で除した（ＪＩＳ Ｋ ６４０１に準拠）。
［平均セル径］
ブロックの成長方向により水平裁断した試験片を実体顕微鏡により観察して測定し、２０点の測定値の平均値を求めた。
[density]
The weight of the sample of 50 × 300 × 300 mm was divided by the volume (according to JIS K 6401).
[Average cell diameter]
A test piece horizontally cut according to the growth direction of the block was observed and measured with a stereomicroscope, and an average value of 20 measured values was obtained.
表１より、本発明の軟質ポリウレタンフォームは、非常に微細なセル構造を有する軟質ポリウレタンフォームであることがわかる。 Table 1 shows that the flexible polyurethane foam of the present invention is a flexible polyurethane foam having a very fine cell structure.
実施例６
［１］ 配合を表１の実施例６としたこと以外は実施例１〜５と同様にして製造した軟質ポリウレタンフォームの吸音特性及びその温度依存性について測定した。
なお、一般に、高分子材料の弾性は、そのガラス転移点（Ｔｇ）付近で大きく変化するので、Ｔｇ付近で温度を変えて軟質ポリウレタンフォームの吸音特性を測定することにより、弾性と吸音特性との関係も、間接的に、測定されることになる。
Example 6
[1] The sound absorption characteristics and temperature dependence of flexible polyurethane foams produced in the same manner as in Examples 1 to 5 were measured except that the formulation was set to Example 6 in Table 1.
In general, the elasticity of a polymer material changes greatly in the vicinity of its glass transition point (Tg). Therefore, by measuring the sound absorption characteristics of a flexible polyurethane foam by changing the temperature in the vicinity of Tg, the elasticity and sound absorption characteristics can be reduced. The relationship will also be measured indirectly.
［２］試料特性
表１の通り、この実施例６の軟質ポリウレタンフォームの密度は０．１５、平均セル径は、１１５μｍであり、また周波数５０Ｈｚ、歪み０．２５％における複素剪断弾性率と温度との関係は図１の通りである。
この実施例６の軟質ポリウレタンフォームのＴｇは０℃である。
[2] Sample characteristics As shown in Table 1, the density of the flexible polyurethane foam of this Example 6 is 0.15, the average cell diameter is 115 μm, and the complex shear modulus and temperature at a frequency of 50 Hz and a strain of 0.25%. The relationship is as shown in FIG.
The Tg of the flexible polyurethane foam of this Example 6 is 0 ° C.
［３］測定方法
厚さ９．８ｍｍの試料をセットした音響管を恒温室内に設定し、室温を０〜５０℃までの範囲で１０℃間隔に変化させ、２００〜２０００Ｈｚにおける減衰、伝播速度、及び特性インピーダンスを測定した。
[3] Measurement method An acoustic tube on which a sample having a thickness of 9.8 mm is set is set in a thermostatic chamber, the room temperature is changed in a range of 0 to 50 ° C. at intervals of 10 ° C., attenuation at 200 to 2000 Hz, propagation speed, And the characteristic impedance was measured.
［４］測定結果
図２（ａ），（ｂ），（ｃ）に測定結果を示す。
[4] Measurement Results FIGS. 2 (a), (b) and (c) show the measurement results.
［５］考察
ａ．一般に、多孔質体中の縦波には、多孔質体内部の空気部によって伝搬される波と、マトリックス部によって伝搬される波とが存在する。この実施例６の軟質ポリウレタンフォームは、セルが微細であり、マトリックスによって伝搬される音波の割合が多く、従って、温度変化に伴う弾性変化の影響が顕著に生じるものと予測された。
[5] Discussion a. In general, the longitudinal wave in the porous body includes a wave propagated by the air part inside the porous body and a wave propagated by the matrix part. The flexible polyurethane foam of Example 6 had a fine cell and a large proportion of sound waves propagated by the matrix. Therefore, it was predicted that the influence of the elastic change accompanying the temperature change would be remarkable.
ｂ．実際に、図２（ａ），（ｂ），（ｃ）の通り、この試料は、温度変化に伴って音響特性が著しく変化している。 b. Actually, as shown in FIGS. 2 (a), 2 (b), and 2 (c), the acoustic characteristics of this sample change remarkably with changes in temperature.
特に、Ｔｇに近い０℃付近での音響変化特性が顕著である。図２（ａ）の通り、内部減衰は０℃の時、５００Ｈｚ以下の周波数で大きくなる傾向にあり、Ｔｇ近傍の減衰のｔａｎδの大きくなる領域と対応しており、ｔａｎδの増加が実効的な音波の減衰に寄与すると言える。 In particular, the acoustic change characteristic near 0 ° C. near Tg is remarkable. As shown in FIG. 2A, the internal attenuation tends to increase at a frequency of 500 Hz or less at 0 ° C., corresponding to a region where the attenuation tan δ increases in the vicinity of Tg, and the increase in tan δ is effective. It can be said that it contributes to the attenuation of sound waves.
ｃ．試料厚さ２０ｍｍに換算したときの音響透過損失の計算結果を図３に示す。 c. FIG. 3 shows the calculation result of sound transmission loss when converted to a sample thickness of 20 mm.
ｄ．図２，３から明らかな通り、この軟質ポリウレタンフォームは、温度変化に起因した弾性の変化に伴って遮音特性が変化する。そして、この実験結果からは、弾性率を高くすることにより５０〜１０００Ｈｚ又は、１ｋＨｚ以下の中・低周波数領域において、遮音特性が向上することが認められる。 d. As is apparent from FIGS. 2 and 3, the sound insulation characteristics of this flexible polyurethane foam change with changes in elasticity due to temperature changes. From this experimental result, it is recognized that the sound insulation property is improved in the middle / low frequency region of 50 to 1000 Hz or 1 kHz or less by increasing the elastic modulus.
Claims (9)
該イソシアネート末端プレポリマーは、数平均分子量が４００〜１０００の低分子量ポリオールの１種以上と数平均分子量が３０００〜１２０００の高分子量ポリオールの１種以上とを含むポリオール成分と、ポリイソシアネートとを反応させてなるものであることを特徴とする微細セル軟質ポリウレタンフォーム。 A microcellular polyurethane foam obtained by adding a crosslinking agent and a foaming component to an isocyanate-terminated prepolymer, mixing and foam-curing,
The isocyanate-terminated prepolymer reacts a polyisocyanate with a polyol component containing at least one low molecular weight polyol having a number average molecular weight of 400 to 1000 and at least one high molecular weight polyol having a number average molecular weight of 3000 to 12000. A fine cell flexible polyurethane foam characterized by being made.
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| WO2005047360A1 (en) * | 2003-11-12 | 2005-05-26 | Bridgestone Corporation | Flexible polyurethane foam inhibited from discoloring |
| JP2005325146A (en) * | 2004-05-12 | 2005-11-24 | Nippon Polyurethane Ind Co Ltd | Method for producing pad for railroad |
| JP2006089582A (en) * | 2004-09-24 | 2006-04-06 | Inoac Corp | Polyurethane foam |
| JP2011529108A (en) * | 2008-07-25 | 2011-12-01 | ビーエーエスエフ ソシエタス・ヨーロピア | Foamed elastomer with little creep tendency at high temperatures |
| WO2018181843A1 (en) * | 2017-03-31 | 2018-10-04 | 日本発條株式会社 | Urethane synthetic leather, production method for urethane synthetic leather, cosmetic puff, and member provided with synthetic leather |
| KR20220112070A (en) * | 2021-02-03 | 2022-08-10 | 주식회사 풍산 | Method for preparing polyurethane foam at room temperature by controlling the gelling reaction time |
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| JP2002268647A (en) * | 2001-03-09 | 2002-09-20 | Bridgestone Corp | Sound absorbing body |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005047360A1 (en) * | 2003-11-12 | 2005-05-26 | Bridgestone Corporation | Flexible polyurethane foam inhibited from discoloring |
| JP2005325146A (en) * | 2004-05-12 | 2005-11-24 | Nippon Polyurethane Ind Co Ltd | Method for producing pad for railroad |
| JP2006089582A (en) * | 2004-09-24 | 2006-04-06 | Inoac Corp | Polyurethane foam |
| JP2011529108A (en) * | 2008-07-25 | 2011-12-01 | ビーエーエスエフ ソシエタス・ヨーロピア | Foamed elastomer with little creep tendency at high temperatures |
| WO2018181843A1 (en) * | 2017-03-31 | 2018-10-04 | 日本発條株式会社 | Urethane synthetic leather, production method for urethane synthetic leather, cosmetic puff, and member provided with synthetic leather |
| JP2018172822A (en) * | 2017-03-31 | 2018-11-08 | 日本発條株式会社 | Urethane synthetic leather, manufacturing method of urethane synthetic leather, puff for makeup and component with synthetic leather |
| KR20220112070A (en) * | 2021-02-03 | 2022-08-10 | 주식회사 풍산 | Method for preparing polyurethane foam at room temperature by controlling the gelling reaction time |
| KR102577410B1 (en) | 2021-02-03 | 2023-09-13 | 주식회사 풍산 | Method for preparing polyurethane foam at room temperature by controlling the gelling reaction time |
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