JP3270555B2 - Method for producing semi-rigid polyurethane foam - Google Patents
Method for producing semi-rigid polyurethane foamInfo
- Publication number
- JP3270555B2 JP3270555B2 JP00396393A JP396393A JP3270555B2 JP 3270555 B2 JP3270555 B2 JP 3270555B2 JP 00396393 A JP00396393 A JP 00396393A JP 396393 A JP396393 A JP 396393A JP 3270555 B2 JP3270555 B2 JP 3270555B2
- Authority
- JP
- Japan
- Prior art keywords
- polyol
- rigid polyurethane
- polyurethane foam
- parts
- semi
- 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.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【0001】[0001]
【産業上の利用分野】本発明は、自動車内装材、例えば
インストルメントパネル、ドアートリムアッパー部、ア
ームレスト、ヘッドレスト等に用いられる半硬質ポリウ
レタンフォームの製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a semi-rigid polyurethane foam used for automobile interior materials, for example, instrument panels, door trim uppers, armrests, headrests and the like.
【0002】[0002]
【従来の技術】上記自動車内装材の製造方法としては、
軟質ポリ塩化ビニル表皮を下型に装着し、ASG樹脂、
ABS樹脂等の芯材を上型に装着して、表皮上に半硬質
ポリウレタンフォーム原液を注入して発泡硬化させる3
層構造一体成形法が行われている。上記内装材を車内に
装着し長期間使用していると、軟質ポリ塩化ビニル表皮
が変退色したり、劣化したりする現象を起こし、大きく
製品価値を損ねる。地域によっては、直射日光により車
内温度が120〜130℃に上がり、ウレタンフォーム
中のアミン触媒が軟質ポリ塩化ビニル表皮の脱HCLを
促進して変退色させ、同時に表皮中の可塑剤がウレタン
フォーム中に移行するため、表皮そのものが軟質系から
硬質系になり劣化現象を起こすと言われている。これら
表皮の変退色、劣化現象を改良するためには、ウレタン
フォーム中のアミン触媒を非反応型から反応型にして、
アミン触媒を表皮中に移行させないようにし、しかもア
ミン触媒濃度を低減すれば良い。しかしながら、アミン
触媒濃度を低減すると、ウレタンフォームの発泡硬化反
応が遅くなり、生産性が低下するので好ましくない。こ
のように、生産性を維持しながら表皮の変退色、劣化現
象を改良するには限界があった。2. Description of the Related Art As a method for manufacturing the above-mentioned automobile interior material,
Attaching the soft polyvinyl chloride skin to the lower mold, ASG resin,
A core material such as ABS resin is attached to the upper mold, and a semi-rigid polyurethane foam stock solution is injected onto the skin to foam and harden 3
A layer structure integral molding method is performed. If the interior material is mounted in a vehicle and used for a long period of time, a phenomenon occurs in which the soft polyvinyl chloride skin discolors or deteriorates, greatly reducing the product value. In some areas, the temperature inside the vehicle rises to 120 to 130 ° C. due to direct sunlight, and the amine catalyst in the urethane foam promotes dehydrochlorination of the soft polyvinyl chloride skin to cause discoloration, and at the same time, the plasticizer in the skin becomes urethane foam. It is said that the skin itself changes from a soft type to a hard type and causes a deterioration phenomenon. In order to improve the discoloration and discoloration of these skins and the deterioration phenomenon, the amine catalyst in the urethane foam is changed from a non-reactive type to a reactive type,
What is necessary is just to prevent the amine catalyst from migrating into the epidermis and to reduce the amine catalyst concentration. However, when the concentration of the amine catalyst is reduced, the foaming and curing reaction of the urethane foam is delayed, and the productivity is undesirably reduced. As described above, there is a limit in improving the discoloration and discoloration and deterioration of the epidermis while maintaining the productivity.
【0003】[0003]
【発明が解決しようとする課題】本発明は、ウレタンフ
ォーム中のアミン触媒濃度を低減して、表皮の変退色、
劣化現象を大巾に改良し、しかも生産性を損なわない、
半硬質ポリウレタンフォームの製造方法を提供すること
を目的とするものである。SUMMARY OF THE INVENTION The present invention reduces the concentration of an amine catalyst in urethane foam to reduce discoloration and discoloration of the epidermis.
Deterioration phenomena are greatly improved and productivity is not impaired.
It is an object of the present invention to provide a method for producing a semi-rigid polyurethane foam.
【0004】[0004]
【課題を解決するための手段】本発明者等は、上記問題
点を解決する目的で鋭意検討した結果、本発明に到達し
た。即ち本発明は、ポリイソシアネート、ポリオール、
水その他の助剤を反応させて半硬質ポリウレタンフォー
ムを製造する方法において、下記一般式(A)(化2)
で示される化合物を基剤として得られた水酸基価24〜
55mgKOH/grのポリエーテルポリオールを、ポ
リオールの総量100重量部中、5〜80重量部使用す
ることを特徴とする、半硬質ポリウレタンフォームの製
造方法である。Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is, the present invention is a polyisocyanate, a polyol,
In a method for producing a semi-rigid polyurethane foam by reacting water and other auxiliaries, the following general formula (A)
The hydroxyl value obtained from the compound represented by
A method for producing a semi-rigid polyurethane foam, comprising using 55 to 80 parts by weight of a polyether polyol of 55 mgKOH / gr based on 100 parts by weight of the total amount of polyol.
【化2】 (式中、R1 、R2 、R3 は炭素数1〜3の低級アルキ
ル基またはアルケニル基を、nは0または1〜3の整数
を表わす。)Embedded image (In the formula, R 1 , R 2 , and R 3 represent a lower alkyl group or an alkenyl group having 1 to 3 carbon atoms, and n represents 0 or an integer of 1 to 3. )
【0005】一般式(A)の化合物としては、ジメチル
エチレンジアミン、トリメチルジエチレントリアミン、
テトラメチルトリエチレンテトラミン、メチルエチルエ
チレンジアミン、トリエチルジエチレントリアミン、ジ
メチルイソプロピルジエチレントリアミン、トリメチル
エチルトリエチレンテトラミン等があり、特にトリメチ
ルジエチレントリアミンが最も好ましい。上記化合物に
プロピレンオキシド、エチレンオキシドを付加重合させ
て、水酸基価24〜55mgKOH/grのポリエーテ
ルポリオールを得ることができる。プロピレンオキシ
ド:エチレンオキシドの重量比率は、100:0〜6
0:40が適当で、特に80:20付近が好ましい。エ
チレンオキシドの重量比率が40%以上だと、得られた
フォームが収縮するので好ましくない。エチレンオキシ
ドの付加方法は、チップドタイプでもバランスタイプで
も良い。得られたポリエーテルポリオールの水酸基価が
24mgKOH/grより低いと粘度が高過ぎて使用し
難く、55mgKOH/grより高いとフォームが収縮
するので好ましくない。該ポリエーテルポリオールの使
用量は、ポリオールの総量100重量部中、5〜80重
量部が適当である。5重量部より少いとアミン触媒濃度
を低減することができず、本発明の目的を達成できな
い。逆に80重量部より多いとアミン触媒による反応制
御ができなくなり、ウレタン原液注入後の上型締めが間
に合わなくなり、空洞等の成形不良が発生し好ましくな
い。The compounds of the general formula (A) include dimethylethylenediamine, trimethyldiethylenetriamine,
Examples include tetramethyltriethylenetetramine, methylethylethylenediamine, triethyldiethylenetriamine, dimethylisopropyldiethylenetriamine, and trimethylethyltriethylenetetramine, with trimethyldiethylenetriamine being most preferred. Polyether polyol having a hydroxyl value of 24 to 55 mgKOH / gr can be obtained by subjecting the above compound to addition polymerization of propylene oxide and ethylene oxide. The weight ratio of propylene oxide: ethylene oxide is from 100: 0 to 6
0:40 is appropriate, and particularly preferably around 80:20. If the weight ratio of ethylene oxide is 40% or more, the obtained foam shrinks, which is not preferable. The method of adding ethylene oxide may be a chipped type or a balanced type. If the hydroxyl value of the obtained polyether polyol is lower than 24 mgKOH / gr, the viscosity is too high to use, and if it is higher than 55 mgKOH / gr, the foam shrinks, which is not preferable. An appropriate amount of the polyether polyol is 5 to 80 parts by weight based on 100 parts by weight of the total amount of the polyol. If the amount is less than 5 parts by weight, the amine catalyst concentration cannot be reduced, and the object of the present invention cannot be achieved. Conversely, if the amount is more than 80 parts by weight, the reaction control by the amine catalyst cannot be performed, the upper mold clamping after the injection of the urethane stock solution cannot be performed in time, and molding defects such as cavities occur, which is not preferable.
【0006】本発明のポリエーテルポリオール以外のポ
リオールとしては、公知のものが使用可能であるが、特
に好ましいものは、水又はエチレングリコール、プロピ
レングリコール、ジエチレングリコール、グリセリン、
ペンタエリスリトール、ソルトール、ショ糖等のポリヒ
ドロキシ化合物にエチレンオキシド、プロピレンオキシ
ド、ブチレンオキシド等の1種または2種以上を付加重
合して得られるポリエーテルポリオールであって、官能
基数は2〜4、水酸基価24〜55mgKOH/grの
ものである。また、ポリエステルポリオールも用いら
れ、例えば、各種グリコール類とアジピン酸とから得ら
れるポリエステルポリオールがあげられる。アクリルポ
リオール等も同様に使用できる。As the polyol other than the polyether polyol of the present invention, known polyols can be used, and particularly preferred are water or ethylene glycol, propylene glycol, diethylene glycol, glycerin,
Polyether polyol obtained by addition polymerization of one or more of ethylene oxide, propylene oxide, butylene oxide and the like to a polyhydroxy compound such as pentaerythritol, solitol, sucrose, etc., having 2 to 4 functional groups and a hydroxyl group With a value of 24 to 55 mg KOH / gr. Polyester polyols are also used, for example, polyester polyols obtained from various glycols and adipic acid. Acrylic polyol and the like can be used similarly.
【0007】ポリイソシアネートとしては、公知のもの
が使用可能であるが、特に好ましいものはポリメチレン
ポリフェニルポリイソシアネート(粗MDI、ポリメリ
ックMDI等と呼称されるもので、その製法を問わな
い。)、あるいは、ポリメチレンポリフェニルポリイソ
シアネートとポリオールを反応させて得られる末端イソ
シアナト基のプレポリマーである。As the polyisocyanate, known ones can be used, and particularly preferable ones are polymethylene polyphenyl polyisocyanate (what is called crude MDI, polymeric MDI, etc., regardless of the production method), Alternatively, it is a prepolymer having terminal isocyanate groups obtained by reacting polymethylene polyphenyl polyisocyanate with a polyol.
【0008】整泡剤としては、有機ケイ素化合物が好ま
しく、例えば、日本ユニカー社製のL−5305、L−
3600、L−3601、L−5309、トーレシリコ
ン社製のSRX−274C、SF−2961、SF−2
962等がある。As the foam stabilizer, an organosilicon compound is preferable. For example, L-5305 and L-L manufactured by Nippon Unicar Co., Ltd.
3600, L-3601, L-5309, SRX-274C, SF-2961, SF-2 manufactured by Toray Silicon Co., Ltd.
962 and the like.
【0009】触媒としては、主にアミン系の触媒が適当
である。例えばトリエチレンジアミン、トリメチルアミ
ノエタノール、N−メチルモルフォリン、テトラメチル
ヘキサメチレンジアミン等があり、通常ポリオール10
0重量部に対し、0.25〜1.00重量部使用される
が、本発明により、この使用量を大巾に低減することが
できる。As the catalyst, mainly an amine catalyst is suitable. For example, there are triethylenediamine, trimethylaminoethanol, N-methylmorpholine, tetramethylhexamethylenediamine and the like.
It is used in an amount of 0.25 to 1.00 part by weight with respect to 0 part by weight. However, according to the present invention, this amount can be greatly reduced.
【0010】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、ポリオール100重量部に対
して0.03〜3.0重量部使用される。As a crosslinking agent, triethanolamine,
Diethanolamine or the like is used in an amount of 0.03 to 3.0 parts by weight based on 100 parts by weight of the polyol.
【0011】半硬質ポリウレタンフォーム製造時のイソ
シアナト基と水酸基の当量比(NCO/OH)は、0.
85〜1.30、より好ましくは0.95〜1.10が
適当である。本発明の半硬質ポリウレタンフォームは、
手作業による方法、いわゆるハンドミックス法、また
は、機械を用いる方法により製造することができる。機
械による場合は、いわゆる高圧発泡機または低圧発泡機
によることができる。また、本発明の半硬質ポリウレタ
ンフォームは、モールドへ注入する方法により製造でき
る。この場合モールドの温度は35〜45℃が好まし
い。The equivalent ratio (NCO / OH) of the isocyanato group to the hydroxyl group during production of the semi-rigid polyurethane foam is 0.1%.
It is suitably from 85 to 1.30, more preferably from 0.95 to 1.10. The semi-rigid polyurethane foam of the present invention,
It can be manufactured by a manual method, a so-called hand mixing method, or a method using a machine. When using a machine, a so-called high-pressure foaming machine or low-pressure foaming machine can be used. Further, the semi-rigid polyurethane foam of the present invention can be produced by a method of injecting into a mold. In this case, the temperature of the mold is preferably 35 to 45 ° C.
【0012】[0012]
【実施例】以下、本発明を更に具体的に説明するため、
実施例及び比較例をあげて説明する。結果をまとめて表
−1に示す。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to the following Examples.
An example and a comparative example will be described. The results are summarized in Table 1.
【0013】[0013]
【表1】 [Table 1]
【0014】実施例及び比較例で使用したポリオール、
ポリイソシアネート、触媒及び架橋剤は次の通りであ
る。 ポリオール−A;トリメチルジエチレントリアミンにプ
ロピレンオキシドとエチレンオキシドを80:20の比
で付加して得た水酸基価28mgKOH/grのポリエ
ーテルポリオール。 ポリオール−B;トリメチルジエチレントリアミンにプ
ロピレンオキシドとエチレンオキシドを80:20の比
で付加して得た水酸基価60mgKOH/grのポリエ
ーテルポリオール。 ポリオール−C;プロピレングリコールにプロピレンオ
キシドとエチレンオキシドを80:20比で付加して得
た水酸基価28mgKOH/grのポリエーテルポリオ
ール。 ポリイソシアネート;ポリメリックMDI(三井東圧化
学社製コスモネートM−200) 触媒−A;トリメチルアミノエタノール 触媒−B;トリエチレンジアミンの33%ジプロピレン
グリコール溶液 架橋剤−A;ジエタノールアミンThe polyols used in the examples and comparative examples,
The polyisocyanate, catalyst and crosslinking agent are as follows. Polyol-A: a polyether polyol having a hydroxyl value of 28 mgKOH / gr obtained by adding propylene oxide and ethylene oxide to trimethyldiethylenetriamine at a ratio of 80:20. Polyol-B: a polyether polyol having a hydroxyl value of 60 mgKOH / gr, obtained by adding propylene oxide and ethylene oxide to trimethyldiethylenetriamine at a ratio of 80:20. Polyol-C: a polyether polyol having a hydroxyl value of 28 mgKOH / gr, obtained by adding propylene oxide and ethylene oxide to propylene glycol at a ratio of 80:20. Polyisocyanate; Polymeric MDI (Cosmonate M-200 manufactured by Mitsui Toatsu Chemicals, Inc.) Catalyst-A; Trimethylaminoethanol Catalyst-B; 33% dipropylene glycol solution of triethylenediamine Crosslinker-A; Diethanolamine
【0015】実施例1 ポリオール−A 50部、ポリオール−C 50部、水
2.4部、架橋剤−A 2.0部、触媒−A 0.2
部及び触媒−B 0.1部を混合し、ポリオール成分と
した。 ポリオール成分をポリイソシアネートと混合
し、自由発泡及びモールド発泡を行った。自由発泡で
は、発泡が開始する時間(以下クリームタイム 略号
CTという)、フォームに棒を突き刺し、棒を引き上げ
た時フォームが糸を引く時間(ゲルタイム 略号G
T)、及び発泡が終了するまでの時間(ライタイム 略
号RT)を測定した。また発泡1時間後のフォーム状態
を観察した。モールド発泡では、予め40℃に調整した
平均厚み10mmのアルミ製テストモールドの下型に軟
質ポリ塩化ビニル表皮を装着し、その上にウレタン原液
を注入し、上型を締めて室温で6分間放置した後、得ら
れた2層一体成形品をモールドより取り出し、軟質ポリ
塩化ビニル表皮上にアスカー−C硬度計を当てて、脱型
硬度を測定した。さらに、フォームの成形状態を観察し
た。1日後、2層成形品を110℃のオーブンに400
時間放置した後、軟質ポリ塩化ビニル表皮の変退色△E
値を、(株)東京電色製の色差計で測定した。また、表
皮の伸び値(EL)を測定し、劣化状況を調べた。結果
は表−1の通りで、比較例1に比べて触媒量を半減して
いるわりには、脱型硬度が十分高く、キュアー性が良好
であり、表皮の変退色、劣化も殆んどなく良好であっ
た。Example 1 50 parts of polyol-A, 50 parts of polyol-C, 2.4 parts of water, 2.0 parts of crosslinking agent-A, 0.2 parts of catalyst-A
Parts and 0.1 part of Catalyst-B were mixed to obtain a polyol component. The polyol component was mixed with polyisocyanate, and free foaming and mold foaming were performed. In free foaming, the time when foaming starts (hereinafter referred to as cream time abbreviation CT), the time when the foam is pulled by sticking a stick into the foam and the rod is pulled up (gel time abbreviation G)
T), and the time until foaming was completed (a lime time RT). Further, the state of the foam one hour after foaming was observed. In mold foaming, a soft polyvinyl chloride skin is attached to the lower mold of an aluminum test mold with an average thickness of 10 mm that has been adjusted to 40 ° C in advance, and a urethane stock solution is poured thereon, and the upper mold is closed and left at room temperature for 6 minutes. After that, the obtained two-layer integrally molded product was taken out of the mold, and the demold hardness was measured by applying an Asker-C hardness meter on the soft polyvinyl chloride skin. Further, the molded state of the foam was observed. One day later, the two-layer molded article is placed in an oven at 110 ° C. for 400 minutes.
After standing for a long time, discoloration and fading of the soft polyvinyl chloride epidermis
The values were measured with a color difference meter manufactured by Tokyo Denshoku Co., Ltd. Further, the elongation value (EL) of the epidermis was measured, and the state of deterioration was examined. The results are as shown in Table 1. Although the amount of the catalyst is reduced by half compared to Comparative Example 1, the demolding hardness is sufficiently high, the curing property is good, and the skin is hardly discolored or deteriorated. It was good.
【0016】実施例2 実施例1のポリオール−Aの使用量を50部から70部
にすると、触媒量がさらに減り、3分で脱型でき、表皮
の変退色、劣化もなく良好であった。Example 2 When the amount of the polyol-A used in Example 1 was changed from 50 parts to 70 parts, the amount of the catalyst was further reduced, the mold could be removed in 3 minutes, and the skin was good without discoloration and deterioration of the skin. .
【0017】比較例1〜2 実施例1において、ポリオール−Aを省略した場合、触
媒の使用量が増え、表皮の変退色、劣化がひどくなっ
た。Comparative Examples 1-2 In the case of Example 1, when the polyol-A was omitted, the amount of the catalyst used was increased, and the discoloration and discoloration and deterioration of the skin became severe.
【0018】比較例3 実施例1のポリオール−Aをポリオール−Bにした場合
は、触媒の使用量は減るが、フォームが収縮した。Comparative Example 3 When polyol-A in Example 1 was replaced with polyol-B, the amount of catalyst used was reduced, but the foam shrank.
【0019】比較例4〜5 実施例1のポリオール−A使用量が3部の場合、アミン
触媒の使用量を減らすことができず、表皮の変退色、劣
化が改良されない。また、ポリオール−A使用量が90
部だと、アミン触媒の使用量は0となるが、反応が速す
ぎるため、型締めが間に合わず空洞が多発した。Comparative Examples 4 and 5 When the amount of the polyol-A used in Example 1 was 3 parts, the amount of the amine catalyst used could not be reduced, and discoloration and deterioration of the skin and deterioration were not improved. Further, when the amount of the polyol-A used is 90,
In this case, the amount of the amine catalyst used was 0, but the reaction was too fast, and the mold was not closed in time, and cavities occurred frequently.
【0020】[0020]
【発明の効果】本発明の方法によれば、ウレタンフォー
ム中のアミン触媒濃度を低減して、表皮の変退色、劣化
現象を大巾に改良し、しかも生産性を維持した半硬質ポ
リウレタンフォームが得られる。According to the method of the present invention, a semi-rigid polyurethane foam which reduces the concentration of an amine catalyst in a urethane foam, significantly improves the discoloration and discoloration of the skin and the phenomenon of deterioration, and maintains the productivity can be obtained. can get.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭59−25810(JP,A) (58)調査した分野(Int.Cl.7,DB名) C08G 18/00 - 18/87 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-59-25810 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08G 18/00-18/87
Claims (1)
の他の助剤を反応させて得られる半硬質ポリウレタンフ
ォームにおいて、下記一般式(A)(化1)で示される
化合物を基剤として得られ水酸基価24〜55mgKO
H/grのポリエーテルポリオールをポリオールの総量
100重量部中、5〜80重量部使用することを特徴と
する半硬質ポリウレタンフォームの製造方法。 【化1】 (式中、R1 、R2 、R3 は炭素数1〜3の低級アルキ
ル基またはアルケニル基を、nは0または1〜3の整数
を表わす。)1. A semi-rigid polyurethane foam obtained by reacting a polyisocyanate, a polyol, water and other auxiliaries, and having a hydroxyl value of 24 based on a compound represented by the following general formula (A) (formula 1). ~ 55mgKO
A method for producing a semi-rigid polyurethane foam, comprising using 5 to 80 parts by weight of H / gr polyether polyol in 100 parts by weight of the total amount of polyol. Embedded image (In the formula, R 1 , R 2 , and R 3 represent a lower alkyl group or an alkenyl group having 1 to 3 carbon atoms, and n represents 0 or an integer of 1 to 3. )
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP00396393A JP3270555B2 (en) | 1993-01-13 | 1993-01-13 | Method for producing semi-rigid polyurethane foam |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP00396393A JP3270555B2 (en) | 1993-01-13 | 1993-01-13 | Method for producing semi-rigid polyurethane foam |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH06206969A JPH06206969A (en) | 1994-07-26 |
JP3270555B2 true JP3270555B2 (en) | 2002-04-02 |
Family
ID=11571742
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP00396393A Expired - Lifetime JP3270555B2 (en) | 1993-01-13 | 1993-01-13 | Method for producing semi-rigid polyurethane foam |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3270555B2 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TR200201955T2 (en) * | 2000-02-10 | 2002-12-23 | Dow Global Technologies Inc. | Low emission polyurethane polymers made with autocatalytic polyols. |
EP2674238B1 (en) | 2012-06-15 | 2017-09-27 | Agie Charmilles New Technologies SA | Laser machine comprising a tool holder with guiding and locking system |
JP6121159B2 (en) * | 2012-12-26 | 2017-04-26 | コベストロ、ドイチュラント、アクチエンゲゼルシャフトCovestro Deutschland Ag | Foamed polyurethane molded product reinforced with vegetable fiber and method for producing the same |
-
1993
- 1993-01-13 JP JP00396393A patent/JP3270555B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPH06206969A (en) | 1994-07-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1770117B1 (en) | Silanol-Functionalized compounds for the preparation of polyurethane foams | |
EP2787016B1 (en) | Fast demold/extended cream time polyurethane formulations | |
JP3605154B2 (en) | Method for producing foamed polyurethane molded article without using CFC | |
JP2001501241A (en) | Light-stable elastomeric polyurethane molded article and method for producing the same | |
EP1219654B1 (en) | Process for producing polyurethane foam | |
DE3202327C2 (en) | ||
JP2876018B2 (en) | Method for producing urethane foam | |
JPH08169928A (en) | Linear hdi urethane prepolymer for rim | |
JPH04227619A (en) | Production of flexible polyurethane foam excellent in gas diffusibility | |
JPS6084319A (en) | Resin composition | |
JP3270555B2 (en) | Method for producing semi-rigid polyurethane foam | |
JP2001518402A (en) | Improved internal release agent for producing polyurethane moldings | |
JPH05170864A (en) | Preparation of urethane group-containing polyurea elastomer | |
US4766167A (en) | Hydroxy acid ester plasticized urethane elastomers | |
KR930010564B1 (en) | Production of high-density elastic polyurethane | |
JP2001172349A (en) | Process for preparing polyurethane foam | |
JPS6259623A (en) | Polyurethane-base forming plastics, preparation and shoe bottom | |
JP3831149B2 (en) | Process for producing polyurethane reaction injection molded foam | |
JP3901513B2 (en) | Method for producing semi-rigid polyurethane foam | |
JPH08143637A (en) | Semi-hard polyurethane foam | |
JP4301432B2 (en) | Method for producing polyurethane foam molded article | |
JP3165142B2 (en) | Manufacturing method of rigid urethane foam with skin material | |
JP3046343B2 (en) | Catalyst for polyurethane production | |
JP3229630B2 (en) | Three-layer integrated molding using semi-rigid polyurethane foam and molding method | |
JPH03179017A (en) | Production of semirigid polyurethane foam |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090118 Year of fee payment: 7 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100118 Year of fee payment: 8 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110118 Year of fee payment: 9 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120118 Year of fee payment: 10 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120118 Year of fee payment: 10 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130118 Year of fee payment: 11 |
|
EXPY | Cancellation because of completion of term |