WO1990010658A1 - Method of producing energy-absorbing polyurethane foam - Google Patents

Method of producing energy-absorbing polyurethane foam Download PDF

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Publication number
WO1990010658A1
WO1990010658A1 PCT/JP1990/000346 JP9000346W WO9010658A1 WO 1990010658 A1 WO1990010658 A1 WO 1990010658A1 JP 9000346 W JP9000346 W JP 9000346W WO 9010658 A1 WO9010658 A1 WO 9010658A1
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Prior art keywords
polyol
weight
parts
water
chain extender
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Application number
PCT/JP1990/000346
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French (fr)
Japanese (ja)
Inventor
Hiromichi Hotta
Kazuo Mizumura
Katsuji Kuribayashi
Original Assignee
Dow Mitsubishi Kasei Limited
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Publication of WO1990010658A1 publication Critical patent/WO1990010658A1/en

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    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/005—< 50kg/m3
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/0058—≥50 and <150kg/m3
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

Definitions

  • the present invention relates to a method for producing an impact energy absorbing polyurethane foam, particularly for an automobile bumper.
  • the present invention relates to the above-mentioned production method for obtaining a polyurethane foam. Background technology
  • the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, used a carbodiimide-modified diphenylmethanediisocyanate having an NC0 content of 2028% as a polyisocyanate, NC0Z 0H equivalent ratio 0.9.1.2, water content was found to be 13% by weight of the total raw material, and that the reaction could be carried out under excellent conditions to obtain an excellent polyurethane form that could solve the above problems.
  • NC0 content NC0 content of 2028%
  • NC0Z 0H equivalent ratio 0.9.1.2 water content was found to be 13% by weight of the total raw material, and that the reaction could be carried out under excellent conditions to obtain an excellent polyurethane form that could solve the above problems.
  • the gist of the present invention is a method for producing an energy-absorbing polyurethane form by reacting a raw material mainly composed of a polyisocyanate, a polyester, a chain extender, and a foaming agent.
  • the carbodimid-modified diphenyl methanediisocyanate having an NC0 content of 2028% is used as an isocyanate, and at least water is used as a foaming agent.
  • water content and performing a reaction under the conditions of 1 3 wt% against in the total feed, density is 0. lO g Z cm 3 compression strength at 50% during deformation have a restoring force in the following It is in the production method of energy absorbing polyurethane foam of 3 kg Z crf or more.
  • FIG. 1 is a representative example of a compressive strength-displacement curve in a compression test of an example.
  • W indicates strength at 50% compression.
  • Fig. 2 shows the area C and the area D when calculating the energy absorption efficiency from Fig. 1.
  • the polyisocyanate used in the present invention is a carbodiimide-modified diphenylmethandiocyanate having an NC0 content of 20 to 28%.
  • the pre-polymer of the above polysociate may be used. It may be a mixture of 1 to 15% by weight of other polysynthetic compounds of aliphatic, alicyclic, aromatic and heterocyclic types. If the NC0 content is more than 28%, the compressive strength at the time of 50% deformation is likely to decrease when the polyurethane foam is used, and it is difficult to obtain a compressive strength of 3 kgZcrf or more. When the NC0 content is less than 20%, blisters are generated in the molded product, and the filling property is deteriorated.
  • Such carbodimid-modified diphenylmethandiisocinate is reacted, for example, at 200 to 220 for 1 to 4 hours using diphenylmethandiisocyanoate as a catalyst and an organic phosphate ester. You can get it.
  • the polyol that reacts with the polyisocyanate is not particularly limited, but a polymer polyol is preferably used.
  • a copolymer was prepared by addition-polymerizing a vinyl compound such as styrene or acrylonitrile to a polyether type polyol, and a copolymer content of 5 to 30% by weight was obtained.
  • the polyol has a 0H value of 20 to 160 or an average molecular weight of 2000 to 12,000.
  • chain extenders include commonly used ones. For example, ethylene glycol, propylene glycol, Lin, Trim n — Leprono II. , Trimethylolethane, 1, 2, 6 —hexanetriol, pentaerythritol, ethylenediamine, tridienediamine, triethanolamine or triethanolamine These are adducts of lukyrenoxide and have an average molecular weight of 1000 or less. These are usually used in a proportion of 2 to 50 parts by weight based on 100 parts by weight of the polymer polyol.
  • the catalyst examples include amide compounds such as triethylenediamine, dimethyl morpholine, tetramethyl hexamethylenediamine, stanaoctetate, stanaolate, dibutyltin dilaurate. And the like. These are used alone or in combination, and are usually added in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the polyol.
  • foaming agents in addition to water, trichloro-mouth monofluoromethane, dichlorodifluoromethane, dichlorotetrafluorofluoroethane, monochlorodifluoromethane, methylylene chloride are also used. These are usually added in an amount of 2 to 30 parts by weight based on 100 parts by weight of the polyol. Other silicone-based foam stabilizers can be used.
  • the reaction is carried out using the above-mentioned raw materials under the conditions of an NC0Z0H equivalent ratio of 0.9 to 1.2 and in the presence of a water content of 1 to 3% by weight in all the raw materials.
  • NC0 / OH equivalent ratio is less than 0.9, the cells become closed cells and generate blisters. On the other hand, if the equivalent ratio exceeds 1.2, the form collapses, which is not preferable.
  • the reaction is carried out according to a conventionally known method, and can be carried out by mixing the polyisocyanate with a polyol, a chain extender, a foaming agent, and a catalyst.
  • Catalyst DABCO 33LV 1.0 Note (1) Tri-functional polyether polyol with molecular weight of 6000, 20% by weight of styrene and acrylonitrile monomer polymerized by graft polymerization
  • Dipropyl pyrene glycol solution Dipropyl pyrene glycol solution
  • the following polyisocyanate and the above polyol composition were mixed with a hand mixer at an NC0Z0H equivalent ratio of 1.05, and the liquid temperatures of the polyisonate and the polyol were both 25.
  • the mixture is charged into an aluminum mold (inside dimensions lOOWx 100H x 400L ⁇ , at a mold temperature of 45 to 50) to a density of 0.09gZcrf and reacted. After 3 minutes, the mold was removed and used as a test block. This test block was allowed to stand in an atmosphere for 23 days for 23 days, and a compression test (70% compression, compression speed 50 Zmin) was performed. Data analysis was performed as follows.
  • the strength at 50% deformation at 70% compression is W.
  • Polymeric MDI Polyunimetallic Polysocyanate
  • NC0 content 100 parts by weight of a mixture of 20 parts by weight Department
  • Table 1 shows the obtained foam physical properties and moldability.
  • the polyisocyanate As described in detail above, as the polyisocyanate, a diluent benzyldimethandiocyanate having an NC0 content of 20 to 28% is used, and at least water is used as a blowing agent on the polyol side.
  • the molding density is 0.1 lOg Zcrf or less, especially 0.06 to 0.09 g
  • An energy absorbing form that has a restoring force with Zcrf and a compressive strength of 3 kgZcrf or more and can sufficiently withstand light collision can be provided.
  • the present invention can be advantageously used for production of impact energy absorbing polyurethane foam.

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  • 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)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

An energy-absorbing polyurethane foam having a density of 0.10 g/cm3 or less, a restoring force and a compression strength of at least 3 kg/cm2 at 50 % deformation is produced by the reaction of raw material mainly comprising a polyisocyanate, a polyol, a chain extender, and a blowing agent, wherein carbodiimide-modified diphenylmethane diisocyanate of an NCO content of 20 to 28 % is used as the polyisocyanate and at least water is used as the blowing agent, while the reaction is conducted under the condition of an NCO to OH equivalent ratio of 0.9 to 1.2 and a water content of the raw material as a whole of 1 to 3 wt.%.

Description

明 細 書 エネルギー吸収ポ リ ウ レタ ンフ ォ 一厶の製造方法 技 術 分 野  Specification Manufacturing method of energy absorbing polyurethane film Technical field
本発明は、 特に自動車バンパー用衝撃エネルギー吸収性ポ リ ウレタ ンフ ォ一ムの製造方法に関するものである。  The present invention relates to a method for producing an impact energy absorbing polyurethane foam, particularly for an automobile bumper.
詳しくは全密度が 0.10g Zcnf以下で （ 1 ) 復元力があり、 ( 2 ) 50%変形時における圧縮強度が 3 kgZcnf以上であり、 ( 3 ) エネルギー吸収効率が大きいという、 優れた性質を有 するポリ ウレタ ンフ ォームを得るための前記の製造方法に関 する。 背 景 技 術  Specifically, it has excellent properties such as (1) a restoring force with a total density of 0.10 g Zcnf or less, (2) a compressive strength at 50% deformation of 3 kgZcnf or more, and (3) a large energy absorption efficiency. The present invention relates to the above-mentioned production method for obtaining a polyurethane foam. Background technology
従来衝擊吸収用ポリ ウ レタ ンフ ォ ームを製造する際、 全密 度として 0.12〜0.15g Zcrfで行われていたが、 車体重量軽減 を図るため、 圧縮強度を出すために鎖延長剤、 発泡剤を増加 させて全密度を 0.10g Zcri以下でポリ ウ レタ ンフ ォ ームを製 造する試みが行われている。  Conventionally, when manufacturing polyurethane foam for impact absorption, the total density was 0.12 to 0.15 g Zcrf, but in order to reduce the weight of the vehicle, a chain extender was used to increase the compressive strength, and foaming Attempts have been made to increase the number of agents to produce polyurethane foam with a total density of 0.10 g Zcri or less.
しかし従来の製法では圧縮強度を出すのが困難であり、 ま た圧縮強度が望ましい性質を示した場合でも成形性、 特にフ オ ームにフク レが発生したり、 歪の回復率が悪かったり、 ま た充塡性が悪く低密度の成形に問題があった。 発 明 の 開 示 However, it is difficult to obtain the compressive strength by the conventional manufacturing method. In addition, there was a problem with low-density molding due to poor filling properties. Disclosure of the invention
本発明者らは、 上記問題点を解決すベく鋭意検討を行った 結果、 ポリイ ソ シァネー ト として NC0 含有率が 20 28%のカ ルボジィ ミ ド変性ジフ ヱニルメ タ ンジイ ソ シァネー トを使用 し、 NC0Z 0H当量比 0. 9 1. 2、 水含量は、 全原料中 1 3 重量％の条件下に反応を行なうことによって上記問題点を解 決し得る優れたポリ ウレタ ンフ ォームが得られることを見出 し o  The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, used a carbodiimide-modified diphenylmethanediisocyanate having an NC0 content of 2028% as a polyisocyanate, NC0Z 0H equivalent ratio 0.9.1.2, water content was found to be 13% by weight of the total raw material, and that the reaction could be carried out under excellent conditions to obtain an excellent polyurethane form that could solve the above problems. Out o
すなわち本発明の要旨は、 ポリイ ソ シァネー ト、 ポ リ才 ル、 鎖延長剤、 および発泡剤を主体とする原料を反応させて エネルギー吸収ポリ ウ レタ ンフ ォームを製造する方法であつ て、 ポ リ イ ソ シァネー ト として NC0 含有率が 20 28%のカル ボジィ ミ ド変性ジフヱニルメ タ ンジイ ソ シァネー トを使用し、 且つ発泡剤として少なく とも水を用い、 NC0Z OH当量比 0. 9 〜； L 2、 水含量は全原料中に対し 1 3重量％の条件下に反 応を行うことを特徴とする、 密度が 0. lO g Z cm3以下で復元力 を有し 50%変形時における圧縮強度が 3 kg Z crf以上であるェ ネルギー吸収ポ リ ウレタ ンフ ォームの製法に存する。 図面の簡単な説明 That is, the gist of the present invention is a method for producing an energy-absorbing polyurethane form by reacting a raw material mainly composed of a polyisocyanate, a polyester, a chain extender, and a foaming agent. The carbodimid-modified diphenyl methanediisocyanate having an NC0 content of 2028% is used as an isocyanate, and at least water is used as a foaming agent. water content and performing a reaction under the conditions of 1 3 wt% against in the total feed, density is 0. lO g Z cm 3 compression strength at 50% during deformation have a restoring force in the following It is in the production method of energy absorbing polyurethane foam of 3 kg Z crf or more. BRIEF DESCRIPTION OF THE FIGURES
第 1図は実施例の圧縮試験における圧縮強度一変位曲線の 代表例である。 Wは 50%圧縮時における強度をあらわす。 第 2図は第 1図からエネルギー吸収効率を求める際の面積 C、 および面積 Dを表わす。 発明を実施するための最良の形態 FIG. 1 is a representative example of a compressive strength-displacement curve in a compression test of an example. W indicates strength at 50% compression. Fig. 2 shows the area C and the area D when calculating the energy absorption efficiency from Fig. 1. BEST MODE FOR CARRYING OUT THE INVENTION
以下本発明を詳細に説明する。  Hereinafter, the present invention will be described in detail.
本発明に用いられるポリ ィ ソ シァネ一 ト としては、 カルボ ジイ ミ ド変性ジフ ヱニルメ タ ンジイ ソシァネー トで NC0 含有 率が 20〜28%のものである。 また上記ポ リ イ ソシァネー トの プレボリマーでもさし支えない。 また脂肪族、 脂環式、 芳香 族、 複素環式の他のポリ ィ ソ シ了ネー トを 1〜15重量％混合 したものでもさし支えない。 NC0 含有率が 28%より多いとポ リ ウ レタ ンフ ォ ームにした場合 50%変形時における圧縮強度 が低下しやすく、 3 kgZcrf以上の圧縮強度を出すのが困難と なる。 また NC0 含有率が 20%より少ないと、 成形品にフクレ が発生したり、 充塡性が悪くなる。 このようなカルボジィ ミ ド変性ジフ エニルメ タ ンジイ ソ シ了ネー ト は例えば、 ジフ ェ ニルメ タ ンジイ ソ シアナ一トを触媒として有機リ ン酸エステ ルを用いて 200 ~ 220 で 1〜 4時間反応することで得るこ とが出来る。  The polyisocyanate used in the present invention is a carbodiimide-modified diphenylmethandiocyanate having an NC0 content of 20 to 28%. Also, the pre-polymer of the above polysociate may be used. It may be a mixture of 1 to 15% by weight of other polysynthetic compounds of aliphatic, alicyclic, aromatic and heterocyclic types. If the NC0 content is more than 28%, the compressive strength at the time of 50% deformation is likely to decrease when the polyurethane foam is used, and it is difficult to obtain a compressive strength of 3 kgZcrf or more. When the NC0 content is less than 20%, blisters are generated in the molded product, and the filling property is deteriorated. Such carbodimid-modified diphenylmethandiisocinate is reacted, for example, at 200 to 220 for 1 to 4 hours using diphenylmethandiisocyanoate as a catalyst and an organic phosphate ester. You can get it.
—方前記ポ リイ ソ シァネー トと反応を行うポリオールとし ては特に制限されないがポリマ一ポリオールが好ましく用い られる。 ポリマーポリオールとしては、 ポ リエーテル型ポリ オールにスチ レンあるいは、 ァク リ ロニ ト リ ルなどのビニル 化合物を付加重合させ共重合体をつく り共重合体含有量 5〜 30重量％、 得られたポリオールの 0 H価が 20〜： 160 またはそ の平均分子量が 2000〜： 12， 000のものである。  The polyol that reacts with the polyisocyanate is not particularly limited, but a polymer polyol is preferably used. As the polymer polyol, a copolymer was prepared by addition-polymerizing a vinyl compound such as styrene or acrylonitrile to a polyether type polyol, and a copolymer content of 5 to 30% by weight was obtained. The polyol has a 0H value of 20 to 160 or an average molecular weight of 2000 to 12,000.
鎖延長剤としては一般的に使用されるものが挙げられるが. 例えばエチレングリコール、 プロ ピレングリ コール、 グ II セ リ ン、 ト リ メ チ n —ルプロノヽ。ン、 ト リ メ チロールェタ ン、 1 , 2 , 6 —へキサン ト リ オール、 ペンタ エ リ ス リ ト ール、 ェチ レンジァ ミ ン、 ト リ レンジァ ミ ン、 ト リ エタ ノ ールア ミ ン又 はそれらの了ルキレンォキシド付加物等であり、 平均分子量 が 1000以下のものである。 これらは通常ポリマーポリオール 100重量部に対して 2 〜50重量部の割合で使用される。 Examples of chain extenders include commonly used ones. For example, ethylene glycol, propylene glycol, Lin, Trim n — Leprono II. , Trimethylolethane, 1, 2, 6 —hexanetriol, pentaerythritol, ethylenediamine, tridienediamine, triethanolamine or triethanolamine These are adducts of lukyrenoxide and have an average molecular weight of 1000 or less. These are usually used in a proportion of 2 to 50 parts by weight based on 100 parts by weight of the polymer polyol.
触媒としては、 ト リ エチ レンジァ ミ ン、 Ν—メ チルモルホ リ ン、 テ ト ラ メ チルへキサメ チ レ ンジア ミ ン等のア ミ ン化合 物、 スタナオク トェー ト、 スタナオ レー ト、 ジブチルスズジ ラウレー ト等のスズ化合物が使用される。 これらは単独或は 併用して使用され、 通常ポリオール 100重量部に対して 0. 1 〜 2重量部添加される。  Examples of the catalyst include amide compounds such as triethylenediamine, dimethyl morpholine, tetramethyl hexamethylenediamine, stanaoctetate, stanaolate, dibutyltin dilaurate. And the like. These are used alone or in combination, and are usually added in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the polyol.
発泡剤としては水の他に ト リ クロ口モノ フルォロメ タ ン、 ジク ロ ロ ジフルォロメ タ ン、 ジク ロ ロテ ト ラ フルォ ロ ェタ ン、 モノ ク ロ ロ ジフルォロ メ タ ン、 メ チレンク ϋ ラ イ ド等も使用 される。 これらはポリオール 100重量部に対して、 通常 2 〜 30重量部添加される。 その他シリ コーン系整泡剤を使用する ことができる。  As foaming agents, in addition to water, trichloro-mouth monofluoromethane, dichlorodifluoromethane, dichlorotetrafluorofluoroethane, monochlorodifluoromethane, methylylene chloride Are also used. These are usually added in an amount of 2 to 30 parts by weight based on 100 parts by weight of the polyol. Other silicone-based foam stabilizers can be used.
本発明では、 上記のような原料を使用し NC0Z 0H当量比 0. 9〜 1. 2の条件下に且つ全原料中の水含量 1 〜 3重量％の 存在下に反応を行う  In the present invention, the reaction is carried out using the above-mentioned raw materials under the conditions of an NC0Z0H equivalent ratio of 0.9 to 1.2 and in the presence of a water content of 1 to 3% by weight in all the raw materials.
NC0/ 0H当量比が 0. 9未満では独立気泡となりフクレを発 生させる。 一方当量比が 1. 2を超えるとフ ォ ームの陥没が起 き好ましくない。  If the NC0 / OH equivalent ratio is less than 0.9, the cells become closed cells and generate blisters. On the other hand, if the equivalent ratio exceeds 1.2, the form collapses, which is not preferable.
また水含量が 1重量％未満では充塡性が悪くなり、 密度 0. 10 g Zen?以下での成形が困難となる。 一方水含量が 3重量 %を超えるとフ ォ ームの陥没が起きやすく、 そのために表面 状態及び充填性が悪くなる。 反応は、 従来公知の方法に従つ て行われ、 ポリ イ ソ シァネー トとポリオール、 鎖延長剤、 発 泡剤、 触媒を混合することにより行うことが出来る。 If the water content is less than 1% by weight, the filling becomes poor, Molding with 0.1 g or less is difficult. On the other hand, if the water content exceeds 3% by weight, the foam is likely to collapse, which deteriorates the surface condition and the filling property. The reaction is carried out according to a conventionally known method, and can be carried out by mixing the polyisocyanate with a polyol, a chain extender, a foaming agent, and a catalyst.
以下に本発明を実施例により具体的に説明するが、 本発明 はその要旨を超えない限り以下の実施例に限定されるもので はない。  Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention.
実施例 1〜 2及び比較例 1〜 2 Examples 1-2 and Comparative Examples 1-2
下記に示した配合にしたがってポリオール組成物を調製し t― ο  Prepare a polyol composition according to the formulation shown below.
くポ リオール組成物の配合 >  Formulation of Polyol Composition>
量部 註（1)  Quantity Note (1)
ポ リオ一ル ポリマーポ リオール 100 鎖延長剤 エチ レ ング U コ ー レ 3. 5  Polyol Polyol 100 Chain extender Ethylene U Core 3.5
註（2)  Note (2)
グリ セ リ ンにエチレンォ 5. 0 キシドを付加したもの  Glycerin with ethylene oxide 5.0 oxide added
発泡剤 水 4. 0  Blowing agent Water 4.0
註（3)  Note (3)
触 媒 DABCO 33LV 1. 0 註（1) 分子量 6000の 3官能のポリエーテルポリォ —ルにスチ レン、 アク リ ロニ ト リ ルモノ マ 一を 20重量％グラフ ト重合させたもの  Catalyst DABCO 33LV 1.0 Note (1) Tri-functional polyether polyol with molecular weight of 6000, 20% by weight of styrene and acrylonitrile monomer polymerized by graft polymerization
( O H価 21. 0)  (OH value 21.0)
註（2) ◦ H価 540  Note (2) ◦ H value 540
註（3) ト リ エチ レンジア ミ ンの 33. 3%  Note (3) 33.3% of triethylene diamine
ジプロ ピレングリ コール溶液 次に下記に示したポリ イ ソ シァネー トと上記ポリオール組 成物とを NC0Z0H当量比 =1.05とし、 ポリ イ ソ シァネー トと ポリォ一ルの液温を共に 25でとしてハン ド ミキサ一で混合し， アルミ製金型 （内寸法 lOOWx 100H X 400L麵、 金型温度 45〜50で） にその混合物を密度 0.09gZcrfになるように仕込 み反応させる。 3分後脱型したものを試験ブロ ッ クとした。 この試験プロ ックを 2〜 3日間 23での雰囲気中に静置し圧縮 試験 （70%圧縮、 圧縮速度 50誦 Zmin)を行った。 データの解 析は以下のように行った。 Dipropyl pyrene glycol solution Next, the following polyisocyanate and the above polyol composition were mixed with a hand mixer at an NC0Z0H equivalent ratio of 1.05, and the liquid temperatures of the polyisonate and the polyol were both 25. Then, the mixture is charged into an aluminum mold (inside dimensions lOOWx 100H x 400L 麵, at a mold temperature of 45 to 50) to a density of 0.09gZcrf and reacted. After 3 minutes, the mold was removed and used as a test block. This test block was allowed to stand in an atmosphere for 23 days for 23 days, and a compression test (70% compression, compression speed 50 Zmin) was performed. Data analysis was performed as follows.
• 50%変形圧縮強度  • 50% deformation compressive strength
第 1図に示すように 70%圧縮した時の 50%変形時強度 を Wとする。  As shown in Fig. 1, the strength at 50% deformation at 70% compression is W.
•変形回復率  • Deformation recovery rate
圧縮試験前の高さと圧縮試験 30分後の高さの比をあら わし  Shows the ratio of the height before the compression test to the height after 30 minutes of the compression test.
圧縮後 （30分） の高さ  Height after compression (30 minutes)
X 100(%) であらわす。 試験前の高さ  X Expressed as 100 (%). Height before test
エネルギー吸収効率  Energy absorption efficiency
D  D
第 2図における Cと Dに関し X 100(%) で  X and 100% for C and D in Fig. 2.
C + D  C + D
あらわす。  It represents.
ふくれ  Blister
目視によりふくれのないものを〇、 あるものを Xとし •表面状態 〇 means no blistering visually, X means something •Surface condition
表面あれのないものを〇、 不良のものを Xとした。  Those with no rough surface are marked with 〇, and those with bad surface are marked with X.
<ポ リ イ ソ シァネー ト成分 > <Polysodium component>
<実施例 1 >  <Example 1>
NC0 含有率が 27. 7%のカルボジィ ミ ド変成ジフヱニルメ タ ンジイ ソ シァネー ト 104重量部  104 parts by weight of carbodimidated metamorphic diphenylmethane diisocyanate with an NC0 content of 27.7%
ぐ実施例 2 >  Example 2>
NC0 含有率が 26. 0%のカルボジィ ミ ド変成ジフヱニルメ タ ンジイ ソ シァネー ト 110重量部  110 parts by weight of carbodiimide-modified diphenylmethanediisopropyl succinate with an NC0 content of 26.0%
<比較例 1 >  <Comparative Example 1>
NC0 含有率が 29. 0%のカルボジィ ミ ド変成ジフヱニルメ タ ンジイ ソ シァネー ト 100重量部  100 parts by weight of carbodiimide-modified diphenyl methane succinate with an NC0 content of 29.0%
<比較例 2 >  <Comparative Example 2>
実施例 1 と同一のポ リ イ ソシ了ネー ト と NC0 含有率が 30. 5%のポ リ メ リ ッ ク M D I (ポ リ フユニルメ タ ンポ リ イ ソ シァネー ト） 20重量部の混合物 100重量部  Polymeric MDI (Polyunimetallic Polysocyanate) with the same polysodium as in Example 1 and 30.5% NC0 content 100 parts by weight of a mixture of 20 parts by weight Department
得られたフ ォ 一ム物性及び成形性について表一 1 に記す, Table 1 shows the obtained foam physical properties and moldability.
表一 Table
Figure imgf000010_0001
以上詳述した通り、 ポリ イ ソ シ了ネートとして NC0 含有率 が 20〜 28%の力ルボジィ ミ ド変性ジフ ヱニルメ タ ンジィ ソ シ アナー トを使用し且つポリオール側に発泡剤として少なく と も水を用いることで得られるポリ ウレタ ンフ ォー厶を自動車 バンパー等に用いられるエネルギー吸収フ オ ームと して用い た場合、 成形密度が 0. lO g Zcrf以下、 特に 0. 06〜0. 09 g Zcrf で復元力を有し且つ圧縮強度 3 kgZcrf以上で十分に軽衝突に 耐うるエネルギー吸収フ ォームを提供することができる。 産業上の利用可能性
Figure imgf000010_0001
As described in detail above, as the polyisocyanate, a diluent benzyldimethandiocyanate having an NC0 content of 20 to 28% is used, and at least water is used as a blowing agent on the polyol side. When the polyurethane foam obtained by using it is used as an energy absorbing foam used in automobile bumpers, etc., the molding density is 0.1 lOg Zcrf or less, especially 0.06 to 0.09 g An energy absorbing form that has a restoring force with Zcrf and a compressive strength of 3 kgZcrf or more and can sufficiently withstand light collision can be provided. Industrial applicability
本発明は、 衝擊エネルギー吸収性ポリ ウ レタ ンフ ォ ームの 製造に有利に利用することができる。  INDUSTRIAL APPLICABILITY The present invention can be advantageously used for production of impact energy absorbing polyurethane foam.

Claims

請 求 の 範 囲 The scope of the claims
1. ポリ イ ソ シァネー ト、 ポリオ一ル、 鎖延長剤および発 泡剤を主体とする原料を反応させて、 エネルギー吸収ポ リ ゥ レタ ンフ ォ ームを製造する方法であって、 ポ リ イ ソ シ了ネー ト と して NC0 含有率が 20〜28%のカルポジィ ミ ド変性ジフ ヱ ニルメ タ ンジイ ソ シァネー トを使用し、 且つ発泡剤として少 なく とも水を用い、 NCQZ 0H当量比 0. 9〜 1. 2、 全原料中の 水含量 1 〜 3重量％の条件下に反応を行うことを特徵とする、 密度が 0. lO g Z cnf以下で復元力を有し、 50%変形時における 圧縮強度が S kg Z crf以上であるエネルギー吸収ポリ ゥレ夕 ン フ ォ ームの製造方法。 1. A method of producing an energy-absorbing polyester foam by reacting a raw material mainly composed of a polyisocyanate, a polyol, a chain extender and a foaming agent. The carbohydrate-modified diphenylmethandiocyanate having an NC0 content of 20 to 28% is used as the socinate, and at least water is used as the foaming agent.The NCQZ0H equivalent ratio is 0. 9 ~ 1.2 、 Reacting under the condition of water content of 1 ~ 3wt% in all raw materials, with density less than 0.1Lg Z cnf A method for producing an energy-absorbing polypropylene foam having a compressive strength of S kg Z crf or more.
2. カルボジィ ミ ド変性ジフ エニルメ タ ンジイ ソ シァネー トが、 有機リ ン酸エステルを触媒として用い、 ジフ ヱニルメ タ ンジィ ソシアナ一トを 200 〜 220でで反応させて得られた ものである、 請求の範囲第 1項記載の方法。  2. The carbodimid-modified diphenylmethandiisocynate is obtained by reacting diphenylmethandithiocyanate with the organic phosphoric acid ester as a catalyst at 200 to 220. The method of claim 1, wherein
3. ポリオールがポリマーポリオールである、 請求の範囲 第 1項記載の方法。  3. The method according to claim 1, wherein the polyol is a polymer polyol.
4. 鎖延長剤がエチ レング リ コ ール、 プロ ピレングリ コ ー ル、 グ リ セ リ ン、 ト リ メ チ n —ルプロノ、0ン、 ト リ メ チロール ェタ ン、 1 , 2 , 6—へキサ ン ト リ オ一ル、 ペンタ エ リ ス リ ト ール、 エチレンジァ ミ ン、 ト リ レンジァ ミ ン、 ト リ エタノ —ルァミ ンおよびそれらのアルキレ ンォキシド付加物であつ て、 平均分子量が 1000以下のものから選ばれる、 請求の範囲 第 1項記載の方法。 4. The chain extender is ethylene glycol, propylene glycol, glycerin, trimethyl n-luprono, 0 , trimethylolethane, 1, 2, 6— Hexantriol, pentaerythritol, ethylenediamine, tolylenediamine, triethano-lamine and their alkylenoxide adducts with an average molecular weight of 1000 or less The method of claim 1, wherein the method is selected from the group consisting of:
5. 鎖延長剤がポリオール 100重量部に対して 2 〜50重量 部の量で用いられる、 請求の範囲第 4項記載の方法。 5. The method according to claim 4, wherein the chain extender is used in an amount of 2 to 50 parts by weight per 100 parts by weight of the polyol.
6. 発泡用触媒がポリオール 100重量部に対して 0. 1 ~ 2 重量部の量で添加される、 請求の範囲第 1項記載の方法。  6. The method according to claim 1, wherein the blowing catalyst is added in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the polyol.
7. 発泡用触媒がト リ エチレンジァ ミ ン、 N—メ チルモル ホ リ ン、 テ ト ラ メ チルへキサメ チレンジア ミ ン等のア ミ ン化 合物、 スタナスォク ト エー ト、 スタナオ レー ト、 ジブチルス ズジラウ レ一 ト等のスズ化合物から選ばれる、 請求の範囲第 6項記載の方法。  7. Foaming catalysts include amide compounds such as triethylenediamine, N-methylmorpholine, and tetramethylhexylenediamine, stannasoctate, stanaolate, and dibutyls sujilau. 7. The method according to claim 6, wherein the method is selected from tin compounds such as plates.
8. 発泡剤として、 水のほかに、 ト リ クロ口モノ フルォロ メ タ ン、 ジク ロ ロ ジフ レオロメ タ ン、 ジク ロ ロテ ト ラ フ レ才 ロ メ タ ン、 モノ ク ロ 口 ジフルォロメ タ ンまたはメ チ レンク ロ ライ ドが用いられる、 請求の範囲第 1項記載の方法。  8. In addition to water, as a blowing agent, trifluorene monofluorometane, dichlorodifluoromethane, dichlorotetrafluoromethane, monochloro difluoromethane or 2. The method according to claim 1, wherein methylene chloride is used.
9. 前記水以外の発泡剤がポリオール 100重量部に対して 2〜30重量部の量で用いられる請求の範面第 8項記載の方法,  9. The method according to claim 8, wherein the blowing agent other than water is used in an amount of 2 to 30 parts by weight based on 100 parts by weight of the polyol,
PCT/JP1990/000346 1989-03-15 1990-03-15 Method of producing energy-absorbing polyurethane foam WO1990010658A1 (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62141017A (en) * 1985-12-16 1987-06-24 Mitsui Toatsu Chem Inc Improvement of quality of rigid polyurethane foam
JPS63168424A (en) * 1986-12-29 1988-07-12 M D Kasei Kk Production of polyurethane molding

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62141017A (en) * 1985-12-16 1987-06-24 Mitsui Toatsu Chem Inc Improvement of quality of rigid polyurethane foam
JPS63168424A (en) * 1986-12-29 1988-07-12 M D Kasei Kk Production of polyurethane molding

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