JP4647265B2 - Water repellent polyurethane resin foam - Google Patents
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Description
本発明は、軽量な撥水性ポリウレタン樹脂発泡体に関する。 The present invention relates to a lightweight water-repellent polyurethane resin foam.
撥水性ポリウレタン樹脂発泡体は、自動車、家電、住宅等、種々の分野で広く用いられている。従来、撥水性ポリウレタン樹脂発泡体としては、フッ素系撥水剤を含浸させたものや、配合物の原料配合を調整して発泡させたものなどが知られている。また、撥水性ポリウレタン樹脂発泡体は、用途によっては軽量なものが求められている。 Water-repellent polyurethane resin foams are widely used in various fields such as automobiles, home appliances, and houses. Conventionally, as a water-repellent polyurethane resin foam, one impregnated with a fluorine-based water repellent or one prepared by adjusting the raw material composition of the blend is known. Further, the water-repellent polyurethane resin foam is required to be lightweight depending on the application.
従来における軽量な撥水性ポリウレタン樹脂発泡体としては、ポリオールとしてＰＰＧ系ポリオール１００重量部に対して、イソシアネートとしてＭＤＩ系イソシアネートを６０重量部以上用い、整泡剤としてイソシアネート又はポリオールと反応性の基を有するシリコーンを、触媒として有機金属触媒を、架橋剤としてイソシアネート基と反応する活性水素を有するものを使用し、さらに発泡剤として水を３重量部以上用いるものがある。 As a conventional lightweight water-repellent polyurethane resin foam, 60 parts by weight or more of MDI-based isocyanate is used as isocyanate with respect to 100 parts by weight of PPG-based polyol as polyol, and isocyanate or polyol and reactive groups are used as foam stabilizers. There are those having an organometallic catalyst as a catalyst, those having an active hydrogen that reacts with an isocyanate group as a crosslinking agent, and those using 3 parts by weight or more of water as a blowing agent.
しかし、従来の軽量な撥水性ポリウレタン樹脂発泡体にあっては、密度が３５ｋｇ／ｍ３以上と高く、撥水性ポリウレタン樹脂発泡体の用途によってはさらに軽量性が求められている。
本発明は前記の点に鑑みなされたものであって、軽量性に優れしかも良好な撥水性を発揮する撥水性ポリウレタン樹脂発泡体を提供する。 This invention is made | formed in view of the said point, Comprising: The water-repellent polyurethane resin foam which is excellent in lightweight property and exhibits favorable water repellency is provided.
請求項１の発明は、ポリオール、発泡剤、触媒、撥水剤及びイソシアネートを含む配合物を発泡してなる撥水性ポリウレタン樹脂発泡体であって、前記ポリオールとしてポリエステルポリオールとポリエステルポリエーテルポリオールを含み、前記ポリオールを１００重量部とした場合に前記発泡剤として水を２．５〜６重量部含み、前記撥水性ポリウレタン樹脂発泡体の密度が１０〜３０ｋｇ／ｍ ３ であり、前記撥水剤は、炭素数１４〜３６のモノアルコールと、炭素数１５〜３６の脂肪族あるいは脂環族ジカルボン酸との結合体からなるエステルであり、
前記ポリオールを１００重量部とした場合に、前記ポリエステルポリオールは３〜６０重量部、前記ポリエステルポリエーテルポリオールは４０〜９７重量部、前記撥水剤は２５〜８０重量部であることを特徴とする。
The invention of claim 1 is a water-repellent polyurethane resin foam obtained by foaming a blend containing a polyol, a foaming agent, a catalyst, a water repellent and an isocyanate, and the polyester includes a polyester polyol and a polyester polyether polyol. see, water comprises 2.5 to 6 parts by weight as the foaming agent when the polyol is 100 parts by weight, the density of the water-repellent polyurethane resin foam is 10 to 30 kg / m 3, the water repellent Is an ester comprising a conjugate of a monoalcohol having 14 to 36 carbon atoms and an aliphatic or alicyclic dicarboxylic acid having 15 to 36 carbon atoms,
When the polyol is 100 parts by weight, the polyester polyol is 3 to 60 parts by weight, the polyester polyether polyol is 40 to 97 parts by weight, and the water repellent is 25 to 80 parts by weight. .
本発明によれば、ポリエステルポリオールを使用することによって、撥水剤の分散性が優れ、配合物の粘度調整が可能となって発泡体が低密度となり、また、ポリエステルポリエーテル共重合ポリオールを使用することによって、発泡体の強度が増大し耐加水分解性が改善され、良好な撥水性を発揮する。 According to the present invention, by using a polyester polyol, the dispersibility of the water repellent is excellent, the viscosity of the compound can be adjusted, the foam becomes low density, and the polyester polyether copolymer polyol is used. By doing so, the strength of the foam is increased, the hydrolysis resistance is improved, and good water repellency is exhibited.
本発明においてポリオールは、ポリエステルポリオールとポリエステルポリエーテルポリオールが併用される。 In the present invention, as the polyol, a polyester polyol and a polyester polyether polyol are used in combination.
ポリエステルポリオールは、ポリウレタン樹脂発泡体用として知られているものが用いられる。例えば、マロン酸、コハク酸、アジピン酸等の脂肪族カルボン酸やフタル酸等の芳香族カルボン酸と、エチレングリコール、ジエチレングリコール、プロピレングリコール、ブタンジオール、１，６−ヘキサンジオール、２，５−ヘキサンジオール、３−メチル−１，５−ペンタンジオール、ネオペンチルグリコール、グリセリン、トリメチロールエタン、トリメチロールプロパン、ペンタエリスリトール、ジグリセリン、ソルビトール、ショ糖などのポリオールとから重縮合して得られたものや、ラクトン系ポリオール等を挙げることができる。本発明では、ポリエステルポリオールを用いることによって、撥水剤の分散性が良好となり、配合物の粘度調整が可能となり、発泡体を低密度にすることができる。 As the polyester polyol, those known for polyurethane resin foams are used. For example, aliphatic carboxylic acids such as malonic acid, succinic acid and adipic acid, and aromatic carboxylic acids such as phthalic acid, ethylene glycol, diethylene glycol, propylene glycol, butanediol, 1,6-hexanediol, 2,5-hexane Obtained by polycondensation with polyols such as diol, 3-methyl-1,5-pentanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, diglycerin, sorbitol, sucrose And lactone polyols. In the present invention, by using the polyester polyol, the dispersibility of the water repellent is improved, the viscosity of the blend can be adjusted, and the foam can be made to have a low density.
ポリエステルポリエーテルポリオールは、公知のものを用いることができる。例えば、脂肪族ジカルボン酸またはそのエステル形成誘導体と低分子ジオールを用いてエステル化反応またはエステル交換反応を行い、さらには重縮合反応を行うことにより、あるいはポリエステルポリオールとポリテトラメチレングリコールをエステル交換反応させることにより得られたものなどを挙げることができる。本発明では、ポリエステルポリエーテルポリオールを用いることによって、発泡体の強度が増大し、耐加水分解性が改善され、良好な撥水性を発揮する。 Known polyester polyether polyols can be used. For example, an esterification reaction or transesterification reaction is performed using an aliphatic dicarboxylic acid or an ester-forming derivative thereof and a low-molecular diol, and a polycondensation reaction is performed, or a polyester polyol and polytetramethylene glycol are transesterified. What was obtained by making it to be mentioned can be mentioned. In the present invention, the use of the polyester polyether polyol increases the strength of the foam, improves the hydrolysis resistance, and exhibits good water repellency.
前記ポリエステルポリオールとポリエステルポリエーテルポリオールは、ポリオールを１００重量部とした場合に、ポリエステルポリオールについては３〜６０重量部、より好ましくは１５〜３５重量部とされ、また、ポリエステルポリエーテルポリオールについては４０〜９７重量部、より好ましくは６５〜８５重量部とされる。ポリオールを１００重量部とした場合においてポリエステルポリオールが６０重量部よりも多くなると、ポリウレタン架橋体中のエーテル鎖が少なくなるため、発泡体の強度、加水分解性が悪くなる。それに対し、ポリエステルポリオールが３重量部よりも少なくなると、撥水剤とポリエステルポリオールの相溶性が悪くなって良好な発泡体が得られなくなる。 When the polyol is 100 parts by weight, the polyester polyol and the polyester polyether polyol are 3 to 60 parts by weight, more preferably 15 to 35 parts by weight for the polyester polyol, and 40 for the polyester polyether polyol. It is made into -97 weight part, More preferably, it is 65-85 weight part. When the amount of the polyol is 100 parts by weight, when the amount of the polyester polyol is more than 60 parts by weight, the number of ether chains in the polyurethane crosslinked body is reduced, and the strength and hydrolyzability of the foam are deteriorated. On the other hand, when the amount of the polyester polyol is less than 3 parts by weight, the compatibility between the water repellent and the polyester polyol is deteriorated and a good foam cannot be obtained.
発泡剤としては、水が好適である。水の量は、ポリオールを１００重量部とした場合、２．５〜６重量部が好ましい。また、本発明においては、メチレンクロライド等の発泡助剤を用いる必要がない。 As the foaming agent, water is suitable. The amount of water is preferably 2.5 to 6 parts by weight when the polyol is 100 parts by weight. In the present invention, it is not necessary to use a foaming aid such as methylene chloride.
触媒としては、トリエチルアミンやテトラメチルグアニジン等のアミン系触媒や、スタナスオクトエート等の錫触媒やフェニル水銀プロピオン酸塩あるいはオクテン酸鉛等の金属触媒（有機金属触媒とも称される。）を用いることができる。触媒の一般的な量は、ポリオールを１００重量部とした場合、０．０１〜２．０重量部である。 As the catalyst, an amine catalyst such as triethylamine or tetramethylguanidine, a tin catalyst such as stannous octoate, or a metal catalyst (also referred to as an organometallic catalyst) such as phenylmercurypropionate or lead octenoate is used. be able to. The general amount of the catalyst is 0.01 to 2.0 parts by weight when the polyol is 100 parts by weight.
撥水剤としては、エステルが用いられる。前記エステルとしては、炭素数１４〜３６のモノアルコールと、炭素数１５〜３６の脂肪族あるいは脂環族ジカルボン酸との結合体が好ましい。前記炭素数１４〜３６のモノアルコールとしては、ミリスチルアルコール、セチルアルコール、ステアリルアルコール、エイコシルアルコール、セリルアルコール及びイソステアリルアルコール等の飽和モノアルコール、オレイルアルコール等の不飽和モノアルコール等が挙げられる。また、炭素数１５〜３６の脂肪族あるいは脂環族ジカルボン酸としては、タブシン酸等の脂肪族ジカルボン酸や、ダイマー酸等の脂環族ジカルボン酸等を挙げることができる。前記モノアルコールの炭素数を１４〜３６及び前記脂肪族あるいは脂環族ジカルボン酸の炭素数を１５〜３６の範囲とすることによって、得られる発泡体の撥水性が、一層良好となる。また、撥水剤の量は、ポリオールを１００重量部とした場合に２５〜８０重量部、より好ましくは３０〜５０重量部である。撥水剤の量がポリオール１００重量部当たり２５重量部よりも少ないと、十分な撥水効果が得られなくなり、また撥水剤の量が８０重量部よりも多いと、撥水剤が可塑剤として作用し、発泡体の形成が難しくなる。 As the water repellent, an ester is used. The ester is preferably a conjugate of a monoalcohol having 14 to 36 carbon atoms and an aliphatic or alicyclic dicarboxylic acid having 15 to 36 carbon atoms. Examples of the C14-36 monoalcohol include myristyl alcohol, cetyl alcohol, stearyl alcohol, eicosyl alcohol, saturated monoalcohol such as seryl alcohol and isostearyl alcohol, and unsaturated monoalcohol such as oleyl alcohol. Examples of the aliphatic or alicyclic dicarboxylic acid having 15 to 36 carbon atoms include aliphatic dicarboxylic acids such as tabic acid and alicyclic dicarboxylic acids such as dimer acid. By setting the carbon number of the monoalcohol to 14 to 36 and the aliphatic or alicyclic dicarboxylic acid to a carbon number of 15 to 36, the water repellency of the obtained foam is further improved. The amount of the water repellent is 25 to 80 parts by weight, more preferably 30 to 50 parts by weight when the polyol is 100 parts by weight. If the amount of water repellent is less than 25 parts by weight per 100 parts by weight of polyol, sufficient water repellent effect cannot be obtained, and if the amount of water repellent exceeds 80 parts by weight, the water repellent is a plasticizer. It becomes difficult to form a foam.
本発明における撥水剤として特に好ましいエステルとして、ダイマー酸ジステアリルを挙げることができる。前記ダイマー酸ジステアリルの合成は次のようにして行われる。まず、ダイマー酸とステアリルアルコールを１：２のモル比で混合し、窒素ガスを反応容器に導入しながら撹拌して１５０〜１８０℃まで温度を上げ、その状態で放置する。その際、反応容器内を２０ｍｍＨｇに減圧して水分を除去する。１時間半経過後、ｐ−トルエンスルホン酸、酢酸カルシウム、オクチル酸カルシウム、ジブチル錫ジラウレート、オクチル酸第１錫から選択した触媒をダイマー酸１モル当たり０．２〜０．８ｇ添加する。前記放置後約２時間後に反応生成物の酸価が５．０以下となった時点を反応終了時点とし、その後常温まで温度を下げることによりダイマー酸ジステアリルを得る。 As a particularly preferable ester as the water repellent in the present invention, dimer acid distearyl can be mentioned. The dimer acid distearyl is synthesized as follows. First, dimer acid and stearyl alcohol are mixed at a molar ratio of 1: 2, stirred while introducing nitrogen gas into the reaction vessel, the temperature is raised to 150 to 180 ° C., and the mixture is left in that state. At that time, the inside of the reaction vessel is depressurized to 20 mmHg to remove moisture. After one and a half hours, 0.2 to 0.8 g of a catalyst selected from p-toluenesulfonic acid, calcium acetate, calcium octylate, dibutyltin dilaurate and stannous octylate is added per mole of dimer acid. About 2 hours after the standing, when the acid value of the reaction product becomes 5.0 or less, the reaction is completed, and then the temperature is lowered to room temperature, thereby obtaining distearyl dimer acid.
ポリイソシアネートとしては、イソシアネート基を２以上有する脂肪族系または芳香族系ポリイソシアネート、それらの混合物、およびそれらを変性して得られる変性ポリイソシアネートを使用することができる。脂肪族系ポリイソシアネートとしては、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキサメタンジイソシアネート等を挙げることができ、芳香族ポリイソシアネートとしては、トルエンジイソシアネート（ＴＤＩ）、ジフェニルメタンジイソシアネート、ナフタレンジイソシアネート、キシリレンジイソシアネート、ポリメリックポリイソシアネート（クルードＭＤＩ）等を挙げることができる。なお、その他プレポリマーも使用することができる。また、その他、整泡剤や、着色剤、難燃剤等、適宜助剤が添加されてもよい。 As the polyisocyanate, aliphatic or aromatic polyisocyanates having two or more isocyanate groups, mixtures thereof, and modified polyisocyanates obtained by modifying them can be used. Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, isophorone diisocyanate, and dicyclohexamethane diisocyanate. Examples of the aromatic polyisocyanate include toluene diisocyanate (TDI), diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, Examples thereof include polymeric polyisocyanate (crude MDI). Other prepolymers can also be used. In addition, auxiliary agents such as foam stabilizers, colorants, flame retardants and the like may be added as appropriate.
前記撥水性ポリウレタン樹脂発泡体は、前記各原料を所要量配合した配合物を攪拌機で混合して反応させる公知の発泡方法によって製造される。撥水性ポリウレタン樹脂発泡体の密度は１０〜３０ｋｇ／ｍ３である。 The water-repellent polyurethane resin foam is produced by a known foaming method in which a mixture containing the required amounts of the respective raw materials is mixed and reacted with a stirrer. The density of the water repellent polyurethane resin foam is 10 to 30 kg / m 3 .
以下、本発明の実施例について具体的に説明する。表１に示す配合からなる配合物を、定法に従って攪拌混合し、発泡させることにより実施例１〜５の撥水性ポリウレタン樹脂発泡体を製造した。表１において、ポリエステルポリオールは三洋化成工業株式会社製、ＡＨ−４０５、ポリエステルポリエーテルポリオールは三井武田ケミカル株式会社製、Ｌ−５０、撥水剤はダイマー酸ジステアリル、アミン系触媒は日本乳化剤株式会社製、Ｎ，Ｎ−ジメチルアミノエタノール（ＤＭＡＥ）、金属触媒は有機酸金属錫塩（スタナスオクトエート）、整泡剤はトーレ・シリコーン株式会社製、ＳＨ−１９３、ポリイソシアネートは日本ポリウレタン株式会社製、Ｔ−８０を用いた。 Examples of the present invention will be specifically described below. The water repellent polyurethane resin foams of Examples 1 to 5 were produced by stirring and mixing the blends composed of the blends shown in Table 1 according to a conventional method and foaming. In Table 1, polyester polyol is Sanyo Chemical Industries, AH-405, polyester polyether polyol is Mitsui Takeda Chemical Co., Ltd., L-50, water repellent is distearyl dimer acid, amine catalyst is Japan Emulsifier Stock N, N-dimethylaminoethanol (DMAE) manufactured by company, metal catalyst is organic acid metal tin salt (stannas octoate), foam stabilizer is manufactured by Torre Silicone Co., Ltd., SH-193, polyisocyanate is Nippon Polyurethane Co., Ltd. Company-made T-80 was used.
また比較のため、表２に示すように、ポリエステルポリオールとポリエステルポリエーテルポリオールの量が請求項１の量から外れる比較例１及び比較例２、撥水剤の量が請求項１の量から外れる比較例３及び比較例５、水の量が請求項１の量から外れる比較例４を実施例と同様にして製造した。なお、比較例３については、正常に発泡せず、発泡体が得られなかった。 For comparison, as shown in Table 2, Comparative Example 1 and Comparative Example 2 in which the amounts of the polyester polyol and the polyester polyether polyol deviate from those of Claim 1, and the amount of the water repellent deviates from the amount of Claim 1. Comparative Example 3 and Comparative Example 5 and Comparative Example 4 in which the amount of water deviates from the amount of Claim 1 were produced in the same manner as the Example. In Comparative Example 3, foaming did not occur normally and a foam was not obtained.
このようにして製造した実施例１〜５及び比較例１，２，４，５の発泡体についてＪＩＳ Ｋ ６４００に従い、密度、２５％硬さ、引張強度、伸びを測定した。また撥水性試験を次のようにして行った。まず、実施例及び比較例の発泡体から、３００×７０×３０（厚み）ｍｍの試験片を裁断し、その試験片の重量（ａ）を測定した。次いで、図１に示すように、試験片を水槽の底面に配置して下方が開口した金網を試験片の上方から被せ、さらに金網上に重しを乗せた後、水槽に水を深さ１５０ｍｍとなるように注入した。この状態で２４時間放置した後、試験片を水槽から取り出し、金網に乗せて試験片の水切りを行い、試験片に含まれる水が自然流下しなくなった時点で試験片の重量を測定し、撥水試験前の試験片の重量（ａ）との差が、前記（ａ）の値以下の場合に撥水性を良好（○）とした。各測定結果を、表１及び表２に示す。また、良好な発泡体が得られたか否か及び、発泡体表面に撹拌不良による縞が見られたか否かについても判断し、併せて表１及び表２に示した。 The foams of Examples 1 to 5 and Comparative Examples 1, 2, 4, and 5 thus produced were measured for density, 25% hardness, tensile strength, and elongation according to JIS K 6400. The water repellency test was conducted as follows. First, a 300 × 70 × 30 (thickness) mm test piece was cut from the foams of Examples and Comparative Examples, and the weight (a) of the test piece was measured. Next, as shown in FIG. 1, the test piece is placed on the bottom of the water tank, and a metal mesh having an opening at the bottom is covered from above the test piece, and a weight is placed on the metal mesh. It was injected so that After leaving in this state for 24 hours, remove the test piece from the water tank, place it on a wire mesh, drain the test piece, measure the weight of the test piece when the water contained in the test piece stops flowing down, and repel the water. When the difference from the weight (a) of the test piece before the water test was equal to or less than the value (a), the water repellency was evaluated as good (O). Tables 1 and 2 show the measurement results. Further, whether or not a good foam was obtained and whether or not streaks due to poor stirring were observed on the foam surface were also shown in Tables 1 and 2.
実施例１〜５は、いずれも成形性及び撹拌混合性が良好であり、さら軽量性及び撥水性も良好であった。それに対して、比較例１及び比較例２はポリエステルポリオールの量が少なくポリエステルポリエーテルポリオールが多いことから撥水性に劣り、また撹拌不良が発生した。比較例３は撥水剤の量が多いことから成形不良を生じて発泡体が得られなかった。また、比較例４は水の量が少ないことから密度が高く、軽量性に劣っていた。比較例５は撥水剤の量が少ないことから撥水性が劣っていた。 In each of Examples 1 to 5, the moldability and stirring and mixing properties were good, and the lightness and water repellency were also good. On the other hand, Comparative Example 1 and Comparative Example 2 were inferior in water repellency due to the small amount of polyester polyol and a large amount of polyester polyether polyol, and poor stirring occurred. In Comparative Example 3, since the amount of the water repellent was large, molding failure occurred and a foam was not obtained. Moreover, since the comparative example 4 had little quantity of water, its density was high and it was inferior to the lightweight property. Comparative Example 5 was inferior in water repellency due to the small amount of water repellent.
Claims (1)
前記ポリオールを１００重量部とした場合に前記発泡剤として水を２．５〜６重量部含み、前記撥水性ポリウレタン樹脂発泡体の密度が１０〜３０ｋｇ／ｍ ３ であり、
前記撥水剤は、炭素数１４〜３６のモノアルコールと、炭素数１５〜３６の脂肪族あるいは脂環族ジカルボン酸との結合体からなるエステルであり、
前記ポリオールを１００重量部とした場合に、前記ポリエステルポリオールは３〜６０重量部、前記ポリエステルポリエーテルポリオールは４０〜９７重量部、前記撥水剤は２５〜８０重量部であることを特徴とする撥水性ポリウレタン樹脂発泡体。 Polyols, blowing agent, catalyst, a water repellent polyurethane foam obtained by foaming a formulation comprising a water repellent agent and a polyisocyanate, seen including a polyester polyol and a polyester polyether polyol as the polyol,
When the polyol is 100 parts by weight, the foaming agent contains 2.5 to 6 parts by weight of water, and the density of the water-repellent polyurethane resin foam is 10 to 30 kg / m 3 ,
The water repellent is an ester composed of a combination of a monoalcohol having 14 to 36 carbon atoms and an aliphatic or alicyclic dicarboxylic acid having 15 to 36 carbon atoms,
When the polyol is 100 parts by weight, the polyester polyol is 3 to 60 parts by weight, the polyester polyether polyol is 40 to 97 parts by weight, and the water repellent is 25 to 80 parts by weight. Water repellent polyurethane resin foam.
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