JP3563715B2 - Polymer polyol composition, method for producing the same, and method for producing a polyurethane resin - Google Patents

Description

【００６５】
［式中、Ｚはｈ価の（ｆ）の残基（ただしｈは２以上の整数）；Ｔは（ｅ）の残基（ただし、重合性不飽和基を有する。）；Ａ_１ はｑ_１ 価のポリオール〔（ａ）、または（ａ）と（ｆ）からのＯＨプレポリマー〕の残基、Ａ_２ はｑ_２ 価のポリオール〔（ａ）、または（ａ）と（ｆ）からのＯＨプレポリマー〕の残基（ただ

Ｔ’はＨまたは炭素数１〜１２のアルキル基；ｇは１またはそれ以上の整数；ｊは１以上の整数である。ただしｑ_１ −ｇ≧０、ｈ−ｊ−１≧０である。なお、ＯＨ基の合計は２以上である。］
【００６６】
すなわち、１個の（ａ）と１個の（ｅ）が１個の（ｆ）を介して結合したもの、複数の（ｅ）が各々１個の（ｆ）を介して１個の（ａ）と結合したもの、複数の（ｆ）を介して合計３個以上の（ａ）および（ｅ）が結合したものなどを含有する。また、これら以外の副生物として、（ａ）同志が（ｆ）を介して結合したもの（不飽和基を持たない含窒素結合含有ポリオール）、（ｅ）同志が（ｆ）を介して結合したもの（水酸基を持たない含窒素結合含有不飽和化合物）が形成されることがあり、未反応の（ａ）や（ｅ）を含むこともある。
この混合物はそのまま分散剤として使用し得るが、不飽和基を持たない含窒素結合含有ポリオールや水酸基を持たない含窒素結合含有不飽和化合物の含量が少ないものが好ましく、さらに除去しうるこれらの不純物を除去した後に適用することもできる。
また、（Ｄ１）中の不飽和基は、ポリオールの分子鎖の末端または末端近傍に位置しているため、モノマーと共重合しやすい。
【００６７】
本第３および第６発明に用いる（Ｄ１１）は、下記式（４）によって求められる、１分子中の（ｆ）のＮＣＯ基に由来する含窒素結合に対する不飽和基数の比の平均値：Ｋが０．１〜０．４となるような割合で、（ａ）、（ｅ）および（ｆ）を反応させたものである。
Ｋ＝［（ｅ）のモル数×（ｅ）の不飽和基数］／［（ｆ）のモル数×（ｆ）のＮＣＯ基数］−−−−（４）
Ｋの値は、さらに好ましくは０．１〜０．３であり、とくに好ましくは０．２〜０．３である。Ｋの値が上記範囲内であると、ポリマーポリオールの分散安定性がとくに良好となる。
【００６８】
ポリマーポリオール作成時のポリオール（Ａ）と反応性分散剤（Ｄ１）の構成比は、好ましくは、（Ａ）１００質量部に対して（Ｄ１）を０．５〜５０質量部使用する［本第２および第５発明］。さらに好ましくは（Ａ）１００部に対して、（Ｄ１）が０．８〜１５部、とくに好ましくは１〜１０部である。（Ｄ１）が５０質量部以下であるとポリマーポリオールの粘度が上昇せず、０．５質量部以上であると分散性が良好である。
（Ｄ１１）の場合は、分散安定性に優れるため、その使用割合を広範囲〔例えば（Ａ）１００質量部に対して０．１〜８０質量部〕に変えることができるが、上記範囲が好ましい。
【００６９】
本第２、第３、第５および第６発明の反応性分散剤（Ｄ１）および（Ｄ１１）は、それを用いて得られるポリマーポリオール組成物の分散安定性が極めて良好となるので、エチレン性不飽和化合物として、従来のモノマー（ｂ２）のみを用いるポリマーポリオール組成物の製造に用いることができるが、本第１および第４発明の、特定のエチレン性不飽和基含有化合物（ｂ１）を用いるポリマーポリオール組成物の製造にとくに好適に用いられ、より低粘度のポリマーポリオール組成物を得ることができる。
【００７０】
次に、（ｂ）の重合に用いるラジカル重合開始剤としては、遊離基を生成して重合を開始させるものが使用でき、例えば、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、２，２’−アゾビス（２−メチルブチロニトリル）、１，１’−アゾビス（シクロヘキサン−１−カルボニトリル）、２，２’−アゾビス（２，４，４−トリメチルペンタン）、ジメチル２，２’−アゾビス（２−メチルプロピオネイト）、２，２’−アゾビス［２−（ヒドロキシメチル）プロピオニトリル］および１，１’−アゾビス（１−アセトキシ−１−フェニルエタン）等のアゾ化合物；ジベンゾイルパーオキサイド、ジクミルパーオキサイド、ビス（４−ｔ−ブチルシクロヘキシル）パーオキシジカーボネート、ベンゾイルパーオキサイド、ラウロイルパーオキサイドおよび過コハク酸等の有機過酸化物；過硫酸塩および過ホウ酸塩等の無機過酸化物等が挙げられる。なお、これらは２種以上を併用することができる。
【００７１】
ラジカル重合開始剤を用いる場合の使用量は、（ｂ）の使用量に基づいて、通常０．０５〜２０質量％、好ましくは０．１〜１５質量％、特に好ましくは０．２〜１０質量％である。重合開始剤の使用量が０．０５〜２０質量％の範囲では、ポリマーポリオール中の（ｂ）の重合率が十分高くなり、また、分子量も大きくなるため、ウレタンフォームにした際に十分なフォーム圧縮硬さが得られる面で優れている。
【００７２】
ラジカル重合以外の重合法における重合開始剤の例としては、配位アニオン重合では、周期律表の第Ｉ、ＩＩ、ＩＩＩ 族の各種金属の有機アルキル化合物と、第ＩＶ〜ＶＩＩ 族の金属塩の組み合わせからなる開始剤が挙げられる。また、メタセシス重合では、ＷＣｌ_６ や ＭｏＣｌ_５ と有機アルミニウムの組み合わせからなる開始剤が挙げられる。
【００７３】
ラジカル重合に用いる希釈剤（Ｃ）としては、例えば、トルエン、キシレンなどの芳香族炭化水素系溶剤；ヘキサン、ヘプタンなどの炭素数５〜１５の飽和脂肪族炭化水素系溶剤；オクテン、ノネン、デセンなどの炭素数５〜３０の不飽和脂肪族系炭化水素系溶剤；メタノール、イソプロパノール、ｎ−ブタノールなどのアルコール系溶剤；ジオキサンなどのエーテル系溶剤；酢酸エチルなどのエステル系溶剤；アセトニトリルなどのニトリル系溶剤；Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミドなどのアミド系溶剤；が挙げられる。（Ｃ）として好ましいものは、得られるポリマーポリオール組成物の粘度が低くなることから、芳香族炭化水素系溶剤であり、さらに好ましくはキシレンである。
希釈剤の使用量は、（ｂ）の使用量に基づいて、好ましくは０〜５０質量、さらに好ましくは１〜４０質量％である。
【００７４】
用いた（Ｃ）は、重合反応後に減圧ストリッピング等により除去するのが好ましいが、必要によりポリマーポリオール組成物（Ｉ）中に（Ｃ）を残存させて、あるいは新たに添加して、（Ｉ）をさらに低粘度とすることもできる。（Ｉ）中に含有させる（Ｃ）としては、上記不飽和脂肪族系炭化水素系溶剤；芳香族系溶剤；および低粘度（１００ｍＰａ・ｓ／２５℃以下）の難燃剤、例えばトリス（クロロエチル）ホスフェート、トリス（クロロプロピル）ホスフェート；などを挙げることができる。
（Ｉ）中の（Ｃ）の含有量は、好ましくは３質量％以下、さらに好ましくは２質量％以下、とくに好ましくは１質量％以下である。
【００７５】
連鎖移動剤としては、例えば、ドデシルメルカプタンおよびメルカプトエタノール等のアルキルメルカプタン類；イソプロピルアルコール、メタノール、２−ブタノールおよびアリルアルコール等のアルコール類；四塩化炭素、四臭化炭素およびクロロホルム等のハロゲン化炭化水素等が挙げられる。
連鎖移動剤の使用量は、（ｂ）の使用量に基づいて、通常０〜２質量％である。
【００７６】
本第１〜第３発明のポリマーポリオール組成物中の、（Ａ）中に分散されたポリマー粒子（Ｂ）の含量は、とくに（ｂ）が（ｂ１）からなるとき、好ましくは３５〜７５質量％、さらに好ましくは４５〜７５質量％である。（Ｂ）の含量が３５質量％以上では、十分なフォーム圧縮硬さが得られ、７５質量％以下であると、ポリマー粒子の凝集、沈降を防止でき、取り扱い性が良好なポリマーポリオールとすることができ、好ましい。
【００７７】
本第４〜第６発明の製法で得られた本第１〜第３発明のポリマーポリオール組成物（Ｉ）は、（Ｂ）の含有量が（Ｉ）の質量に基づいて３５〜７５質量％であり、とくに（ｂ）が（ｂ１）からなるとき、（Ａ）に溶解している可溶性ポリマー（Ｐ）の量を（Ａ）の質量に基づいて５質量％以下とすることができる。（Ｐ）の量は、好ましくは３質量％以下である。（Ｐ）の量が５質量％以下であると、ポリマーポリオール組成物の粘度が低く取り扱いが容易であり、発泡したフォームの硬度が高くなる。分散剤（Ｄ）を用いて得られたポリマーポリオール組成物（Ｉ）の場合は、（Ｐ）の含量は５質量％以下であることが好ましいが、１０質量％以下であってもよい。
ここで、ポリオール（Ａ）に溶解している可溶性ポリマー（Ｐ）とは、ポリマーポリオール組成物（Ｉ）から、（Ａ）に不溶なポリマー粒子（Ｂ）と（Ａ）（少量の低分子量副生物を含む）を除いたものであり、通常ポリオール（Ａ）よりも高分子量の化合物である。
【００７８】
ポリマー粒子（Ｂ）の含量および可溶性ポリマー（Ｐ）量の測定は以下の方法にて行う。
５ｇの（Ｉ）にメタノール２０ｇを加え、１００ｃｃのステンレス製チューブに入れて、温度２０℃で１８０００ｒｐｍ×６０分間、遠心分離して（Ｂ）を凝集させ、上澄みの透明溶液を得る。得られた（Ｂ）の質量の（Ｉ）に対する比率（％）を（Ｂ）の含量とする。この溶液から減圧乾燥機によりメタノールを除去した後、分取液体クロマトグラフィーにて、ポリオール（Ａ）（少量の低分子量副生物を含む）と、（Ａ）に可溶性のポリマー（Ｐ）（重量平均分子量４０００以上、通常はクロマトグラフィーにおける（Ａ）のピークより高分子量側にピークが出現する。）とを分取し、その質量比から求める。（Ｐ）の重量平均分子量（ＧＰＣによる）は、通常６０００〜３００００であるが、さらに高分子量のものが含まれることがある。
なお、可溶性ポリマー（Ｐ）がポリオール（Ａ）と分取液体クロマトグラフィーで分離出来ない場合（分子量が重なる場合）は、上記と同様に遠心分離して（Ｂ）を凝集させ、上澄みの透明溶液を得る。この溶液から減圧乾燥機によりメタノールを除去した後、ジエチルエーテルを投入し、沈殿物を濾別し乾燥することで、可溶性ポリマー（Ｐ）を（Ａ）から分離することができる。
【００７９】
また、本第４〜第６発明の製法で得られた本第１〜第３発明のポリマーポリオール組成物（Ｉ）は、（Ｂ）の含有量が（Ｉ）の質量に基づいて３５〜７５質量％であり、とくに（ｂ）が（ｂ１）からなるとき、（Ｉ）の２５℃でのブルックフィールド型粘度計による粘度Ｖ（ｍＰａ・ｓ）が下記式（１）の範囲内、好ましくは下記式（２）および（３）の両方を満足する範囲内にあるポリマーポリオール組成物とすることができる。
Ｖ≦（Ｖａ−Ｖａ×Ｃ／１０）＾〔ｅ＾ｘ〕 （１）
Ｖ≦（Ｖａ−Ｖａ×Ｃ／１０）＾〔ｅ＾ｙ〕 （２）
Ｖ≧０．５×（Ｖａ−Ｖａ×Ｃ／１０）＾〔ｅ＾ｙ〕 （３）
ただし、ｘ＝０．００１０３５４×Ｂｐ＾１．５
ｙ＝０．０００９５１４×Ｂｐ＾１．５
Ｖａ：（Ａ）の２５℃でのブルックフィールド型粘度計による粘度（ｍＰ
ａ・ｓ）。
Ｃ ：（Ｉ）中の（Ｃ）の含有量（質量％）
Ｂｐ：（Ｉ）中の（Ｂ）の含有量（質量％）
＾ ：べき乗を示す。
ｅ ：自然対数の底。
【００８０】
ただし、ＶおよびＶａの測定は下記条件による。

上記式（１）の範囲内では、ポリマーポリオール組成物（Ｉ）と他の原料との混合性がより良好で、取扱い性も良好なポリマーポリオール組成物となる。
【００８１】
本第７発明のポリウレタン樹脂の製造方法は、ポリオール成分の少なくとも一部として、上記の第１〜第３発明のいずれかのポリマーポリオール組成物（Ｉ）を用いることからなるポリウレタン樹脂の製造方法である。
ポリオール成分とポリイソシアネート成分を、必要により発泡剤、触媒、整泡剤、その他の添加剤の存在下に反応させてポリウレタン樹脂を製造する方法において、ポリオール成分として、本発明のポリマーポリオール組成物以外に、必要により公知の他の活性水素原子含有化合物と併用することができる。他の活性水素原子含有化合物としては、ポリウレタンの製造に普通に用いられている他の高分子ポリオールもしくはモノオール（Ｔ）、低分子活性水素原子含有化合物（Ｕ）が使用できる。
【００８２】
他の高分子ポリオールもしくはモノオール（Ｔ）としては、ポリエーテルポリオール、ポリエステルポリオール、これら以外の各種ポリオールもしくはモノオール、およびこれらの混合物が使用できる。
ポリエーテルポリオールとしては、前記のポリオール（Ａ１）の項で例示したポリエーテルポリオールと同様ものが挙げられる。
ポリエステルポリオールとしては、前記（Ａ２）のポリエステルポリオールとして例示したものなどが挙げられる。
これら以外の各種ポリオールもしくはモノオールとしては、ポリブタジエンポリオール等のジエン系ポリオールおよびその水素添加物；アクリル系ポリオール等の水酸基含有ビニル重合体；ヒマシ油等の天然油系ポリオール；天然油系ポリオールの変性物；国際公開ＷＯ９８／４４０１６号公報に記載の末端ラジカル重合性官能基含有活性水素化合物（モノオールも含む）；本発明以外のポリマーポリオールなども使用できる。
【００８３】
これらの他の高分子ポリオールもしくはモノオール（Ｔ）は、好ましくは２〜８個、さらに好ましくは３〜８個の水酸基と、通常２００以上、好ましくは３００〜４０００、さらに好ましくは４００〜３０００の水酸基当量を有している。
特に好ましいものはポリエーテルポリオールである。
【００８４】
低分子活性水素原子含有化合物（Ｕ）としては、少なくとも２個（好ましくは２〜３個、とくに好ましくは２個）の活性水素原子（水酸基、アミノ基、メルカプト基など、好ましくは水酸基）を有する活性水素原子１個当たりの当量が２００未満（好ましくは３０〜１８０）の化合物が挙げられる。（Ｕ）の分子量は、好ましくは５００以下、さらに好ましくは６０〜４００である。
（Ｕ）としては、たとえば低分子ポリオール、アミノアルコールが挙げられる。
【００８５】
低分子ポリオールとしては、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、ジプロピレングリコール、１，４−ブタンジオール、ネオペンチルグリコール、ヘキサンジオールなどの２価アルコール；グリセリン、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、α−メチルグルコシド、ソルビトール、キシリトール、マンニトール、ジペンタエリスリトール、グルコース、フルクトース、ショ糖などの３〜８価またはそれ以上の多価アルコール；低分子量（たとえば分子量２００〜４００）の多価アルコールアルキレンオキサイド付加物（ポリエチレングリコール、ポリプロピレングリコールなど）；環構造を有する低分子ジオール類、例えばビスフェノールＡのプロピレンオキサイド付加物等が挙げられる。
アミノアルコールとしては、モノ−またはジアルカノールアミン類（モノエタノールアミン、ジエタノールアミン、モノプロパノールアミンなど）が挙げられる。
これらのうちで好ましいのは、低分子ポリオール、特にジオールであり、具体的にはエチレングリコール、１，４−ブタンジオール、ネオペンチルグリコール、１，６−ヘキサンジオールおよびこれらの２種以上の混合物である。
【００８６】
ポリウレタン樹脂の製造に用いるポリオール成分（Ｚ）〔（Ｉ）並びに必要により（Ｔ）および／または（Ｕ）〕中の本発明のポリマーポリオール組成物（Ｉ）の量は、好ましくは５質量％以上、より好ましくは１０質量％以上、とくに好ましくは２０質量％以上である。５質量％以上であると、ウレタンフォームとした場合のフォームの圧縮硬さが出やすい。
また、（Ｚ）中の（Ｂ）の含量は、好ましくは５〜７５質量％、さらに好ましくは７〜５５質量％である。上記範囲内では、フォームの硬さと液流れ性が共に良好である。
【００８７】
また、（Ｔ）の含量は、好ましくは０〜９５質量％、より好ましくは０〜８０質量％である。（Ｔ）が９５質量％以下であると、フォームの圧縮硬さがでやすい。
（Ｕ）の含量は、好ましくは０〜３０質量％、さらに好ましくは０〜１０質量％である。（Ｕ）が３０質量％以下であると、反応時の発熱温度が高くなりすぎず、スコーチが発生する恐れがない。
【００８８】
本第７発明のポリウレタン樹脂を製造する際に使用されるポリイソシアネート成分としては、従来からポリウレタン樹脂の製造に使用されている公知の有機ポリイソシアネートが使用できる。
このようなポリイソシアネートとしては、前記のポリイソシアネート（ｆ）として例示したものが挙げられる。
これらのうちで好ましいものは、２，４−および２，６−ＴＤＩ、これらの異性体の混合物、粗製ＴＤＩ；４，４’−および２，４’−ＭＤＩ、これらの異性体の混合物、粗製ＭＤＩ；およびこれらのポリイソシアネート類より誘導されるウレタン基、カルボジイミド基、アロファネート基、ウレア基、ビューレット基、イソシアヌレート基を含有する変性ポリイソシアネート類である。
【００８９】
ポリウレタン樹脂の製造に際してのイソシアネート指数［（ＮＣＯ基／活性水素原子含有基）の当量比×１００］は、通常８０〜１４０、好ましくは８５〜１２０、とくに好ましくは９５〜１１５である。またイソシアネート指数を上記範囲より大幅に高くして（たとえば３００〜１０００）ポリウレタン中にポリイソシアヌレート基を導入することもできる。
【００９０】
ポリウレタン樹脂の製造に際しては、反応を促進させるため、ポリウレタン反応に通常使用される触媒を使用してもよい。たとえばアミン系触媒〔トリエチレンジアミン、Ｎ−エチルモルホリン、ビス−２−ジメチルアミノエチルエーテルなどの３級アミン；１，８−ジアザ−ビシクロ［５．４．０］ウンデセン−７（サンアプロ社製、ＤＢＵ）；等〕、錫系触媒（オクタン酸第１スズ、ジブチルチンジラウレートなど）、その他の金属触媒（オクタン酸鉛など）および米国特許４，２９９，９２４号明細書に記載のイソシアヌレート化触媒が挙げられる。これらの中では、アミン系触媒および／または錫系触媒が好ましい。
触媒を用いる場合の使用量は、反応混合物の質量に基づいて、好ましくは０．００１〜５質量％である。
【００９１】
本発明の製造法においては、必要によりポリウレタン反応に通常使用される発泡剤を使用し、ポリウレタンフォーム（好ましくは発泡倍率が５〜１００倍）とすることができる。
発泡剤としては、水素原子含有ハロゲン化炭化水素、水、低沸点炭化水素、液化炭酸ガスなどから選ばれる少なくとも１種以上が用いられる。
水素原子含有ハロゲン化炭化水素の具体例としては、
ＨＣＦＣ（ハイドロクロロフルオロカーボン）タイプのもの（例えば、ＨＣＦＣ−１２３、ＨＣＦＣ−１４１ｂ、ＨＣＦＣ−２２およびＨＣＦＣ−１４２ｂ）
ＨＦＣ（ハイドロフルオロカーボン）タイプのもの（例えば、ＨＦＣ−１３４ａ、ＨＦＣ−１５２ａ、ＨＦＣ−３５６ｍｆｆ、ＨＦＣ−２３６ｅａ、ＨＦＣ−２４５ｃａ、ＨＦＣ−２４５ｆａおよびＨＦＣ−３６５ｍｆｃ）
などが挙げられる。
これらのうち好ましいものは、ＨＣＦＣ−１４１ｂ、ＨＦＣ−１３４ａ、ＨＦＣ−３５６ｍｆｆ、ＨＦＣ−２３６ｅａ、ＨＦＣ−２４５ｃａ、ＨＦＣ−２４５ｆａ、ＨＦＣ−３６５ｍｆｃおよびこれらの２種以上の併用である。
低沸点炭化水素は、沸点が通常−５〜７０℃の炭化水素であり、その具体例としてはブタン、ペンタン、シクロペンタンおよびこれらの混合物が挙げられる。
【００９２】
水素原子含有ハロゲン化炭化水素化合物を用いる場合の使用量は、ポリオール成分（Ｚ）１００質量部当たり、通常５０質量部を越えない量、好ましくは５〜４５質量部である。
低沸点炭化水素を用いる場合の使用量は、（Ｚ）１００質量部当たり、通常４５質量部を越えない量、好ましくは５〜４０質量部である。
液化炭酸ガスを用いる場合の使用量は、（Ｚ）１００質量部当たり、通常３０質量部を越えない量、好ましくは５〜２５質量部である。
水素原子含有ハロゲン化炭化水素と水とを併用する場合、水素原子含有ハロゲン化炭化水素の使用量は、（Ｚ）１００質量部当たり、通常４５質量部を越えない量、好ましくは５〜４０質量部であり、水の使用量は（Ｚ）１００質量部当たり、通常１０質量部を越えない量、好ましくは０．５〜８質量部である。
低沸点炭化水素と水とを併用する場合、低沸点炭化水素の使用量は、（Ｚ）１００質量部当たり、通常４０質量部を越えない量、好ましくは２〜３５質量部であり、水の使用量は（Ｚ）１００質量部当たり、通常１０質量部を越えない量、好ましくは０．５〜８質量部である。
液化炭酸ガスと水とを併用する場合、液化炭酸ガスの使用量は、（Ｚ）１００質量部当たり、通常２５質量部を越えない量、好ましくは０．１〜２０質量部であり、水の使用量は（Ｚ）１００質量部当たり、通常１０質量部を越えない量、好ましくは０．５〜８質量部である。
発泡剤に水のみを単独で用いる場合、水の使用量は、（Ｚ）１００質量部当たり、通常０．１〜３０質量部、好ましくは１〜２０質量部である。
【００９３】
本発明のポリウレタン樹脂またはその発泡体の製造方法においては、必要により、さらに以下に述べるような、整泡剤やその他の添加剤を用い、その存在下で反応させてもよい。
整泡剤としては、通常のポリウレタンフォームの製造に用いられるものはすべて使用でき、例として、ジメチルシロキサン系整泡剤［例えば、トーレダウコーニングシリコーン（株）製の「ＳＲＸ−２５３」、信越化学工業（株）製の「Ｆ−１２２」等］、ポリエーテル変性ジメチルシロキサン系整泡剤［例えば、日本ユニカー（株）製の「Ｌ−５３０９」、「Ｌ−３６０１」、「ＳＺ−１３１１」等］、信越化学工業（株）製の「Ｆ−２４２Ｔ」等］等のシリコーン整泡剤が挙げられる。
さらに、着色剤（染料、顔料、カーボンブラックなど）、可塑剤（フタル酸エステル、アジピン酸エステルなど）、有機充填剤（合成短繊維、熱可塑性もしくは熱硬化性樹脂からなる中空微小球など）、無機充填剤〔無機塩（炭酸カルシウム、硫酸バリウムなど）、無機繊維（ガラス繊維、炭素繊維など）、ウィスカー（チタン酸カリウムウィスカーなど）など〕、難燃剤（リン酸エステル類、ハロゲン化リン酸エステル類、メラミン類、ホスファゼン誘導体類など）、老化防止剤（トリアゾール系、ベンゾフェノン系など）、抗酸化剤（ヒンダードフェノール系、ヒンダードアミン系など）、接着剤（変性ポリカプロラクトンポリオールなど）、内部離型剤、殺菌剤などの公知の添加剤の存在下で反応させることができる。
【００９４】
ポリオール成分（Ｚ）１００質量部に対するこれらの添加剤の使用量に関しては、整泡剤は、好ましくは１０質量部以下、さらに好ましくは０．２〜５質量部である。着色剤は、好ましくは１質量部以下である。可塑剤は、好ましくは１０質量部以下、さらに好ましくは５質量部以下である。有機充填剤は、好ましくは５０質量部以下、さらに好ましくは３０質量部以下である。無機充填剤は、好ましくは５０質量部以下、さらに好ましくは３０質量部以下である。難燃剤は、好ましくは２０質量部以下、さらに好ましくは５〜１５質量部である。老化防止剤は、好ましくは１質量部以下、さらに好ましくは０．０１〜０．５質量部である。抗酸化剤は、好ましくは１質量部以下、さらに好ましくは０．０１〜０．５質量部である。これら以外の上記添加剤は、好ましくは１質量部以下である。
【００９５】
ポリウレタン樹脂の製造は通常の方法で行うことができ、ワンショット法、セミプレポリマー法、プレポリマー法等の公知の方法により行うことができる。
ポリウレタン樹脂の製造には、通常用いられている製造装置を用いることができる。無溶媒の場合はたとえばニーダーやエクストルーダーのような装置を用いることができる。例えば、閉鎖モールドあるいは開放モールド内で各種の非発泡あるいは発泡のポリウレタン樹脂の製造を行うことができる。閉鎖モールドを用い発泡ポリウレタン樹脂を製造する場合のパック率〔（モールド発泡時の密度／フリー発泡時の密度）×１００〕は、好ましくは１１０〜２００％である。
ポリウレタン樹脂の製造は普通低圧あるいは高圧の機械装置を用いて原料を混合反応させることにより行われる。さらには、原料混合前後（とくに原料混合前）、原料中の溶存空気あるいは混合時に混入した空気などのガスを真空法により除去することによりポリウレタン樹脂の製造を行うこともできる。
【００９６】
本発明の製法により得られたポリマーポリオールは、ポリウレタンフォーム、とくに軟質モールドフォームおよびスラブフォームの製造に有用である。またＲＩＭ（反応射出成形）法による成形にも適用できる。
本発明のポリマーポリオール組成物を用いて製造されたポリウレタン樹脂は、例えば、ポリウレタンフォームとして、自動車の内装部品や、家具等の室内調度に用いられる。また、シーラントや合成皮革の材料としても用いられる。
【００９７】
【実施例】
以下に本発明を実施例によりさらに具体的に説明するが、本発明はこれに限定されるものではない。なお、以下において部、％および比は、それぞれ質量部、質量％および質量比を示す。
【００９８】
下記製造例に用いた原料の組成、記号等は次の通りである。
（１）不飽和単官能活性水素化合物（ｅ）
ＨＥＭＡ：２−ヒドロキシエチルメタクリレート
ＨＥＡ ：２−ヒドロキシエチルアクリレート
（２）反応性分散剤製造用触媒
ＴＢＴ ：テトラブチルチタネート〔ナカライテスク（株）社製〕
（３）反応性分散剤製造用ポリイソシアネート（ｆ）
ＴＤＩ ：コロネートＴ−８０〔日本ポリウレタン（株）社製〕
（４）ポリオール（ａ）
ポリオール（ａ−１）：ペンタエリスリトールにＰＯを平均１０４モル付加し次いでＥＯを平均１９モル付加させて得られた、ＥＯ含量１２％、水酸基価３２のポリオール。
【００９９】
＜製造例１＞反応性分散剤（Ｄ１）の製造−１
温度調節器、撹拌翼、滴下ロートを備えた５００ｍＬ容量の四つ口フラスコに、ＴＤＩを２８部（０．１６モル）、ＴＢＴを０．０１部入れ、３０℃に冷却し、続いてＨＥＭＡ９部（０．０７モル）を２時間で滴下した。その間反応温度を４０〜５０℃に保った。その反応液を温度調節器、撹拌翼、滴下ロートを備えた１Ｌ容量の四つ口フラスコにあらかじめ入れておいたポリオール（ａ−１）９６３部（０．１４モル）中に入れ、反応温度８０〜９０℃で４時間撹拌した。赤外吸収スペクトルにおいて未反応のイソシアネート基が存在しないことを確認して、反応性分散剤（Ｄ１−１）を得た。
（Ｄ１−１）の水酸基価は２０、粘度は２００００ｍＰａ・ｓ／２５℃、不飽和基数／含窒素結合の数の比は０．２２であった。
【０１００】
＜製造例２＞反応性分散剤（Ｄ１）の製造−２
ＨＥＭＡ９部をＨＥＡ８部（０．０７モル）に、ポリオール（ａ−１）９６３部を９６４部（０．１４モル）に代える以外は製造例１と同様にして、反応性分散剤（Ｄ１−２）を得た。
（Ｄ１−２）の水酸基価は２０、粘度は１９５００ｍＰａ・ｓ／２５℃、不飽和基数／含窒素結合の数の比は０．２２であった。
【０１０１】
下記実施例および比較例に使用した原料の組成、記号等は次の通りである。
（５）ポリオール（Ａ）
Ｇ５０ ：グリセリンにＰＯを平均５０モルを付加させて得られた数平均分子量（以下Ｍｎと記載）３，０００、水酸基価５６のポリオール、粘度５００ｍＰａ・ｓ（２５℃）。
ポリオールＡ１１−１：グリセリンにＰＯを平均６４モル付加し次いでＥＯを平均１５モル付加させて得られた、ＥＯ含量１５％、水酸基価３７．５のポリオール。
ポリオールＡ１１−２：ペンタエリスリトールにＰＯを平均１０４モル付加し次いでＥＯを平均１９モル付加させて得られた、ＥＯ含量１２％、水酸基価３２のポリオール。
ポリオールＡ１１−３：ペンタエリスリトールにＰＯを平均１１８モル付加し次いでＥＯを平均２５モル付加させて得られた、ＥＯ含量１４％、水酸基価２８のポリオール。
ポリオールＡ１１−４：ペンタエリスリトールにＰＯを平均８３モル付加し次いでＥＯを平均２４モル付加させて得られた、ＥＯ含量１８％、水酸基価３７．５のポリオール。
【０１０２】
ポリオールＡ１２−１：グリセリンにＰＯを平均３５モル、ＥＯを平均１１１モルランダム付加させて得られた、ＥＯ含量７０％、水酸基価２４のポリオール。
ポリオールＡ１２−２：グリセリンにＰＯを平均６モル、ＥＯを平均２４モルランダム付加させて得られた、ＥＯ含量７０％、水酸基価１１２のポリオール。
（６）エチレン性不飽和化合物（ｂ２）
ＡＮ ：アクリロニトリル
Ｓｔ ：スチレン
【０１０３】
（７）分散剤（Ｄ）
ＳＡＮ ：アクリロニトリル／スチレン＝８０／２０質量％共重合体（Ｍｎ＝５，０００）
ＧＭＡＰ：ポリプロピレングリコール（Ｍｎ＝３，０００）のグリシジルメタクリレート等モル付加物
反応性分散剤（Ｄ１−１）：製造例１で作成のもの
反応性分散剤（Ｄ１−２）：製造例２で作成のもの
（８）重合開始剤
ＡＶＮ ：２，２’−アゾビス（２，４−ジメチルバレロニトリル）
（９）有機ポリイソシアネート
ＴＤＩ−８０：コロネートＴ−８０〔日本ポリウレタン工業（株）製〕
ＴＭ−２０：ＣＥ−７２９〔ＴＤＩ／ポリメリックＭＤＩ＝８０／２０質量％；日本ポリウレタン（株）社製〕
（１０）触媒
触媒Ａ ：ネオスタンＵ−２８（オクタン酸第１スズ）〔日東化成（株）製〕
触媒Ｂ ：ＤＡＢＣＯ（トリエチレンジアミン）〔日本乳化剤（株）製〕
触媒Ｃ ：ＴＥＤＡＬ−３３〔トリエチレンジアミン／ジプロピレングリコール＝３３／６７質量％溶液；東ソー（株）社製〕
触媒Ｄ ：ＴＯＹＯＣＡＴ ＥＴ〔ビス−２−ジメチルアミノエチルエーテル／ジプロピレングリコール＝３３／６７質量％溶液：東ソー（株）社製〕
（１１）整泡剤
Ｆ−２４２Ｔ：ポリエーテルシロキサン重合体〔信越化学工業（株）製〕
ＳＺ−１３１１：ポリエーテルシロキサン重合体〔日本ユニカー（株）社製〕
Ｌ−５３０９ ：ポリエーテルシロキサン重合体〔日本ユニカー（株）社製〕
【０１０４】
また、数平均分子量、不飽和度、粘度、ポリオール可溶性ポリマー、分散安定性、重合体粒子径は以下のように測定した。

【０１０５】
＜不飽和度＞
ＪＩＳ Ｋ−１５５７に規定された測定法に準拠して測定。
＜粘度＞
機種 ：ＢＬ型粘度計（ＴＯＫＩＭＥＣ社製）
測定温度 ：２５℃
ローターＮｏ：Ｎｏ３またはＮｏ４
回転数 ：測定粘度により、前記粘度Ｖ（ｍＰａ・ｓ）式（１）の説明で前記した回転数による。
【０１０６】
＜ポリオール可溶性ポリマー＞
前記の方法による。ただし分取液体クロマトグラフは、以下に記載のものを用いた。

【０１０７】
＜分散安定性▲１▼＞
１４０ｍｌガラス製密閉容器（サンプルびん）に入れたポリマーポリオール組成物を５０℃の恒温槽に３０日間放置する。放置後、分散安定性を目視で確認した。
評価基準
○ 沈降物がなく、均一分散状態であった。
△ 沈降物が有り、サンプルびんを５回転倒した後、均一再分散した。
× 沈殿物が有り、サンプルびんを５回転倒した後、再分散しなかった。
＜分散安定性▲２▼＞
１４０ｍｌガラス製密閉容器（サンプルびん）に入れたポリマーポリオール組成物を７０℃の恒温槽に３０日間放置する。放置後、分散安定性を目視で確認した。
評価基準
◎ 沈降物がなく、均一分散状態であった。
○ 沈降物が有り、サンプルびんを５回転倒した後、均一再分散した。
× 沈殿物が有り、サンプルびんを５回転倒した後、再分散しなかった。
【０１０８】
＜重合体粒子径＞
ポリマーポリオールを、レーザー光の透過率が７０〜９０％となるように、それに用いたポリオールＡ１１で希釈し、粒度分布測定装置（レーザー回折／散乱式粒度分布測定装置 ＬＡ−７００；堀場製作所製）にて測定した。体積基準粒度分布の累積分布５０％に相当する粒子径を重合体粒子径（μｍ）とした。
【０１０９】
＜実施例１＞ポリマーポリオール組成物の製造−１
温度調節器、バキューム撹拌翼、滴下ポンプ、減圧装置、ジムロート冷却管、窒素流入口および流出口を備えた４口フラスコに、ＳＡＮ：１０部およびＧ５０：４４０部を投入し、窒素置換後、窒素雰囲気下（重合終了まで）で撹拌しながら１３０℃に昇温した。次いで、アリルアルコールプロピレンオキサイド２．２モル付加物（Ｍｎ＝１８６、ＳＰ＝１０．２）：２５０部とＡＮ：１５０部、Ｓｔ：１００部を予め混合した原料、並びに、予め、Ｇ５０：５０部およびＡＶＮ：１部を混合した原料を、各々同時に滴下ポンプを用いて１時間かけて連続的に滴下し、１３０℃で２時間重合させた。さらに未反応モノマーを減圧下ストリッピングして、ポリマー粒子含量５０％、粘度４０００ｍＰａ・ｓ（２５℃）のポリマーポリオール組成物（Ｆ−１）を得た。
【０１１０】
＜実施例２＞ポリマーポリオール組成物の製造−２
実施例１と同様の４口フラスコに、ＳＡＮ：１０部およびＧ５０：４４０部を投入し、窒素置換後、窒素雰囲気下（重合終了まで）で撹拌しながら１３０℃に昇温した。次いで、下記式〔６〕のアセトアセチル基を有する化合物（Ｍｎ＝２１５、ＳＰ＝１１．５）：２００部とＡＮ：１５０部、Ｓｔ：１５０部を予め混合した原料、並びに、予め、Ｇ５０：５０部およびＡＶＮ：１部を混合した原料を、各々同時に滴下ポンプを用いて１時間かけて連続的に滴下し、１３０℃で２時間重合させた。さらに未反応モノマーを減圧下ストリッピングして、ポリマー粒子含量５０％、粘度４０００ｍＰａ・ｓ（２５℃）のポリマーポリオール組成物（Ｆ−２）を得た。
ＣＨ_２＝Ｃ（ＣＨ_３）ＣＯＯＣＨ_２ＣＨ_２ＯＣＯＣＨ_２ＣＯＣＨ_３ 〔６〕
【０１１１】
＜実施例３＞ポリマーポリオール組成物の製造−３
実施例１と同様の４口フラスコに、ＳＡＮ：１０部およびＧ５０：４４０部を投入し、窒素置換後、窒素雰囲気下（重合終了まで）で撹拌しながら１３０℃に昇温した。次いで、下記式〔７〕の開環ラクトン鎖を有する化合物（Ｍｎ＝３００、ＳＰ＝１０．４）：５０部とＡＮ：２００部、Ｓｔ：２５０部を予め混合した原料、並びに、予め、Ｇ５０：５０部およびＡＶＮ：１部を混合した原料を、各々同時に滴下ポンプを用いて１時間かけて連続的に滴下し、１３０℃で２時間重合させた。さらに未反応モノマーを減圧下ストリッピングして、ポリマー粒子含量５０％、粘度４２００ｍＰａ・ｓ（２５℃）のポリマーポリオール組成物（Ｆ−３）を得た。
ＣＨ_２＝ＣＨＣＯ〔Ｏ（ＣＨ_２）_５ＣＯ〕_２ＯＨ 〔７〕
【０１１２】
＜実施例４＞ポリマーポリオール組成物の製造−４
実施例１と同様の４口フラスコに、ＳＡＮ：１０部およびＧ５０：４４０部を投入し、窒素置換後、窒素雰囲気下（重合終了まで）で撹拌しながら１３０℃に昇温した。次いで、下記式〔８〕のコハク酸残基を有する化合物（Ｍｎ＝２３０、ＳＰ＝１１．２）：１８０部とＡＮ：１６０部、Ｓｔ：１６０部を予め混合した原料、並びに、予め、Ｇ５０：５０部およびＡＶＮ：１部を混合した原料を、各々同時に滴下ポンプを用いて１時間かけて連続的に滴下し、１３０℃で２時間重合させた。さらに未反応モノマーを減圧下ストリッピングして、ポリマー粒子含量５０％、粘度４９００ｍＰａ・ｓ（２５℃）のポリマーポリオール組成物（Ｆ−４）を得た。
ＣＨ_２＝Ｃ（ＣＨ_３）ＣＯＯＣＨ_２ＣＨ_２ＯＣＯＣＨ_２ＣＨ_２ＣＯＯＨ 〔８〕
【０１１３】
＜実施例５＞ポリマーポリオール組成物の製造−５
実施例１と同様の４口フラスコに、ＳＡＮ：１０部およびＧ５０：４４０部を投入し、窒素置換後、窒素雰囲気下（重合終了まで）で撹拌しながら１３０℃に昇温した。次いで、下記式〔９〕のフタル酸残基を有する化合物（Ｍｎ＝３３６、ＳＰ＝１２．０）：２５０部とＡＮ：１５０部、Ｓｔ：１００部を予め混合した原料、並びに、予め、Ｇ５０：５０部およびＡＶＮ：１部を混合した原料を、各々同時に滴下ポンプを用いて１時間かけて連続的に滴下し、１３０℃で２時間重合させた。さらに未反応モノマーを減圧下ストリッピングして、ポリマー粒子含量５０％、粘度５３００ｍＰａ・ｓ（２５℃）のポリマーポリオール組成物（Ｆ−５）を得た。
ＣＨ_２＝Ｃ（ＣＨ_３）ＣＯＯＣＨ_２ＣＨ_２ＯＣＯ（Ｐｈ）ＣＯＯＣＨ_２ＣＨ（ＯＨ）ＣＨ_３
〔ただし、（Ｐｈ）はオルトフェニレン基である〕 〔９〕
【０１１４】
＜実施例６＞ポリマーポリオール組成物の製造−６
分散剤のＳＡＮ：１０部を、反応性分散剤（Ｄ１−１）：１０部に代える以外は実施例１と同様にして、ポリマー粒子含量５０％、粘度３８００ｍＰａ・ｓ（２５℃）のポリマーポリオール組成物（Ｆ−６）を得た。
【０１１５】
＜実施例７＞ポリマーポリオール組成物の製造−７
分散剤のＳＡＮ：１０部を、反応性分散剤（Ｄ１−２）：１０部に代える以外は実施例１と同様にして、ポリマー粒子含量５０％、粘度３９００ｍＰａ・ｓ（２５℃）のポリマーポリオール組成物（Ｆ−７）を得た。
【０１１６】
＜実施例８＞ポリマーポリオール組成物の製造−８
実施例１と同様の４口フラスコに、反応性分散剤（Ｄ１−１）：１０部、Ｇ５０：４４０部およびキシレン８０部を投入し、窒素置換後、窒素雰囲気下（重合終了まで）で撹拌しながら１３０℃に昇温した。次いで、アリルアルコールプロピレンオキサイド２．２モル付加物（Ｍｎ＝１８６、ＳＰ＝１０．２）：２５０部とＡＮ：１５０部、Ｓｔ：１００部を予め混合した原料、並びに、予め、Ｇ５０：５０部およびＡＶＮ：１部を混合した原料を、各々同時に滴下ポンプを用いて１時間かけて連続的に滴下し、１３０℃で２時間重合させた。反応物に水：２０部を加えてから、１３０℃で３時間、１０ｍｍＨｇで減圧ストリッピングしてキシレンと未反応モノマーを除去し、ポリマー粒子含量５０％、粘度３１００ｍＰａ・ｓ（２５℃）のポリマーポリオール組成物（Ｆ−８）を得た。
【０１１７】
＜実施例９〜１３＞ポリマーポリオール組成物の製造−９〜１３
表３に記載の組成により、温度調節器、バキューム撹拌翼、滴下ポンプ、減圧装置、ジムロート冷却管、窒素流入および流出口を備えた１Ｌ容量の四つ口フラスコにポリオールの２５％相当量を入れ、撹拌下１２５℃に加熱し、次いで、滴下ポンプにより原料液（残りの原料配合液）を４時間かけて連続的に滴下し、さらに未反応モノマーを減圧下ストリッピングして、本発明のポリマーポリオール組成物（Ｆ−９）〜（Ｆ−１３）を合成した。これらの性状等を表３に示す。
【０１１８】
＜比較例１＞比較のポリマーポリオール組成物の製造−１
実施例１と同様の４口フラスコに、Ｇ５０：５０部を入れ、撹拌下で１２５℃に加熱した。次いで、予めＳｔ４５０部、ＡＣＮ３００部、ＧＭＡＰ２０部、Ｇ５０：６８０部、ＡＶＮ４部を混合した原料を滴下ポンプによりを４時間かけて連続的に滴下し、重合させた。さらに、未反応モノマーを減圧下ストリッピングした。ポリマー粒子含量５０％、粘度２０，０００ｍＰａ・ｓ（２５℃）の比較のポリマーポリオール組成物（Ｒ−１）を得た。
【０１１９】
＜比較例２＞比較のポリマーポリオール組成物の製造−２
比較例１と同様の装置および方法で、Ｇ５０：１５０部並びにＳｔ：２８０部、ＡＮ：１２０部、ＧＭＡＰ：８部、Ｇ５０：４４２部およびＡＶＮ：１．６部を使用して、ポリマー粒子含量４０％、粘度５５４０ｍＰａ・ｓ（２５℃）の比較ポリマーポリオール組成物（Ｒ−２）を得た。
【０１２０】
＜比較例３＞比較のポリマーポリオール組成物の製造−３
比較例１と同様の装置および方法で、Ｇ５０：１７５部並びにＳｔ：２１０部、ＡＮ：９０部、ＧＭＡＰ：６部、Ｇ５０：５１９部およびＡＶＮ：１．２部を使用して、ポリマー粒子含量３０％、粘度２０００ｍＰａ・ｓ（２５℃）の比較ポリマーポリオール組成物（Ｒ−３）を得た。
【０１２１】
＜比較例４〜５＞比較のポリマーポリオール組成物の製造−４〜５
表３に記載の組成により、温度調節器、バキューム撹拌翼、滴下ポンプ、減圧装置、ジムロート冷却管、窒素流入および流出口を備えた１Ｌ容量の四つ口フラスコにポリオールの２５％相当量を入れ、撹拌下１２５℃に加熱し、次いで、滴下ポンプにより原料液（残りの原料配合液）を４時間かけて連続的に滴下し、さらに未反応モノマーを減圧下ストリッピングして、比較のポリマーポリオール組成物（Ｒ−４）〜（Ｒ−５）を合成した。これらの性状等を表３に示す。
【０１２２】
＜実施例１〜８および比較例１〜３＞ポリウレタンフォームの製造
実施例１〜８および比較例１〜３から得られた、本発明のポリマーポリオール組成物（Ｆ−１〜Ｆ−８）および比較ポリマーポリオール組成物（Ｒ−１〜Ｒ−３）を使用し、表１および２に記載の配合比で、以下に示す発泡処方によりポリウレタンフォームを製造した。これらのフォーム物性評価結果を表１および２に示す。発泡処方は以下のとおりである。
▲１▼ポリマーポリオール組成物と有機ポリイソシアネートとをそれぞれ２５±２℃に温度調整する。
▲２▼ポリマーポリオール組成物、整泡剤、水、触媒の順で容量１リットルのステンレス性ビーカーに入れて、室温（２５±２℃）で撹拌混合し、直ちに有機ポリイソシアネートを加え、攪拌機〔ホモディスパー：特殊機化（株）製、攪拌条件：２０００ｒｐｍ×６秒）を用いて、攪拌して発泡を行った。
▲３▼攪拌停止後、２５×２５×１０ｃｍの木箱に内容物を投入して、ポリウレタンフォームを得た。
【０１２３】
＜実施例９〜１３および比較例４〜５＞ポリウレタンフォームの製造
表３記載の処方によって得た比較のポリマーポリオール組成物および本発明のポリマーポリオール組成物のいくつかのものを使用し、表３に記載の発泡処方により、各原料を２５±２℃で撹拌混合し、金型温度は６０℃、キュアー時間は６分にてポリウレタン樹脂を製造した。これらのフォーム物性評価結果を表４に示す。
【０１２４】
【表１】

【０１２５】
【表２】

【０１２６】
【表３】

【０１２７】
【表４】

【０１２８】
表１、２および４におけるフォーム物性の評価方法は以下の通りである。

なお、通常、ウレタンフォームの物性として、密度は、１５〜５０の範囲が好ましく、２５％ＩＬＤ、引張強度、引裂強度、切断伸度、反発弾性率および通気性は、数値が大きいほど好ましい。また、圧縮永久歪および湿熱圧縮永久歪は、数値が小さいほど好ましい。
【０１２９】
表１および２から明らかなように、実施例１〜８のポリマーポリオール組成物は、比較例１のポリマーポリオール組成物と比較して、粘度が低く、更にポリウレタンフォームとした場合のフォーム物性、特に、２５％ＩＬＤ（硬度）、通気性および圧縮永久歪が優れている。また、引裂強度、引張強度、切断伸度、反発弾性は、同等もしくはそれ以上であった。なお、比較例２および３のポリマーポリオール組成物は、ポリマー粒子の濃度が実施例１〜８のポリマーポリオール組成物および比較例１の比較ポリマーポリオール組成物よりも低いため、粘度は低いが、ポリウレタンフォームとした場合のフォーム物性、特に２５％ＩＬＤ（硬度）が著しく劣っている。なお、一般にポリマー粒子が高濃度になる程、引張強度、切断伸度、反発弾性、通気性は低下し、圧縮永久歪みは高くなる傾向にあるが、本発明のポリマーポリオール組成物を使用したポリウレタンフォーム（実施例１〜８）は、同じポリマー粒子濃度である比較例１と比較して同等もしくはそれ以上のフォーム物性を示している。
さらに、表４から明らかなように、実施例９〜１３のポリマーポリオール組成物は、比較例４〜５のポリマーポリオール組成物と比較して、粘度が低く、更にポリウレタンフォームとした場合のフォーム物性、特に湿熱圧縮永久歪が優れている。
【０１３０】
【発明の効果】
本発明のポリマーポリオール組成物およびその製造方法によれば、従来のポリマーポリオール組成物に比べてポリマー粒子の濃度を高くしても、低粘度かつ分散安定性が極めて良好なポリマーポリオール組成物を得ることができる。従って、ポリウレタン樹脂製造等において、作業効率を極め向上させることができる。また、本発明のポリマーポリオール組成物をポリオールの必須成分として用いて製造したポリウレタン樹脂は、とくにポリマーが（ｂ１）からなるモノマーの重合体であるとき、ポリマーポリオール組成物の粘度が同等のもので比較した場合、本発明のポリマーポリオール組成物を用いた場合の方が、従来のものを使用したのと比較して、２５％ＩＬＤ（硬度）が極めて良好である。また、同じポリマー粒子濃度の従来のポリマーポリオール組成物を使用した場合と比べて、本発明のポリマーポリオール組成物を使用した場合の方が、ウレタン樹脂の２５％ＩＬＤ、通気性および圧縮永久歪を大幅に向上させることができる。
また、本第２および第３発明のポリマーポリオール組成物は、ポリマーが通常用いられるモノマーのみからの重合体である場合でも、従来の技術のものに比べて分散安定性が極めて良好であり、従来の方法によるものに比べて、高硬度かつ湿熱圧縮永久歪に優れたポリウレタン樹脂を製造することができる。
上記効果を奏することから、本発明のポリマーポリオール組成物を用いて製造されたポリウレタン樹脂は、ポリウレタンフォームとして、自動車の内装部品や、家具などの室内調度等の用途に極めて好適である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a polymer polyol composition, a method for producing the same, and a method for producing a polyurethane resin using the obtained polymer polyol composition.
[0002]
[Prior art]
A polymer composition or mixture obtained by polymerizing an ethylenically unsaturated compound in a polyol is generally called a polymer polyol, and is widely used as a raw material for polyurethane resins such as polyurethane foams and polyurethane elastomers.
To further increase the polymer particle content in the polymer polyol for the purpose of producing a polymer polyol that provides a higher quality polyurethane having higher hardness and elastic modulus, as a means of obtaining such a polymer polyol, a part of the polyol is coupled. A vinyl monomer in the presence of a modified polyol having a high molecular weight by reacting it with an agent (silicon-containing compound, tetrakisalkoxyorthoformate, trialkoxyalkane, dialkoxyalkane, etc.) (for example, WO85 / 04891). And a method of polymerizing a vinyl monomer in the presence of a macromer containing a urethane bond (for example, JP-A-61-115919).
[0003]
[Problems to be solved by the invention]
However, there are problems such as poor dispersion stability of the obtained polymer polyol composition, and difficulty in handling due to poor mixing with the isocyanate at the time of polyurethane resin molding, and dispersion stability even when the polymer particle content is high. It was difficult to obtain a polymer polyol composition having good properties.
[0004]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in order to solve the above problems, and as a result, by using a specific terminal ethylenically unsaturated group-containing compound and / or a specific reactive dispersant, high-quality polyurethane. The present invention has been found to provide a polymer polyol composition having good dispersion stability and good dispersion stability.
[0005]
That is, the present invention is the following seven inventions.
[First invention] A dispersion medium comprising a polyol (A) or (A) and a diluent (C), and polymer particles (B) dispersed in the dispersion medium, wherein (B) is It is formed by polymerizing an ethylenically unsaturated compound (b) in the presence or absence of a dispersant (D), and at least 5% by mass of (b) has a number average molecular weight of 160 to 490 and a solubility of A polymer polyol composition comprising a terminal ethylenically unsaturated group-containing compound (b1) having a parameter SP of 9.5 to 13.
[Second invention] A dispersion medium comprising a polyol (A) or (A) and a diluent (C), and polymer particles (B) dispersed in the dispersion medium. A) A polymer polyol composition formed by polymerizing an ethylenically unsaturated compound (b) in the presence of 0.5 to 50 parts by mass of the following reactive dispersant (D1) based on 100 parts by mass.
Reactive dispersant (D1): A substantially saturated polyol (a) and a monofunctional active hydrogen compound (e) having at least one polymerizable unsaturated group are bound via a polyisocyanate (f). A dispersant comprising a nitrogen-containing bond-containing unsaturated polyol.
[Third invention] A dispersion medium comprising a polyol (A) or (A) and a diluent (C), and polymer particles (B) dispersed in the dispersion medium. A polymer polyol composition formed by polymerizing an ethylenically unsaturated compound (b) in the presence of a reactive dispersant (D11).
Reactive dispersant (D11): a substantially saturated polyol (a) and a monofunctional active hydrogen compound (e) having at least one polymerizable unsaturated group are bound via a polyisocyanate (f). (D11) a dispersant comprising a nitrogen-containing bond-containing unsaturated polyol having an average ratio of the number of unsaturated groups to the number of nitrogen-containing bonds derived from NCO groups in one molecule of 0.1 to 0.4. .
[0006]
[Fourth invention] Production of a polymer polyol composition in which an ethylenically unsaturated compound (b) is polymerized in a polyol (A) in the presence or absence of a dispersant (D) and / or a diluent (C). In the method, (b) containing 5% by mass or more of a terminal ethylenically unsaturated group-containing compound (b1) having a number average molecular weight of 160 to 490 and a solubility parameter SP of 9.5 to 13 is used. (1) A method comprising obtaining the polymer polyol composition of the present invention.
[Fifth invention] A polymer polyol composition for polymerizing an ethylenically unsaturated compound (b) in a polyol (A) in the presence of a dispersant (D), in the presence or absence of a diluent (C). In the production method, the following reactive dispersant (D1) is used as the dispersant (D) to obtain the polymer polyol composition of the second invention.
Reactive dispersant (D1): A substantially saturated polyol (a) and a monofunctional active hydrogen compound (e) having at least one polymerizable unsaturated group are bound via a polyisocyanate (f). A dispersant comprising a nitrogen-containing bond-containing unsaturated polyol.
[Sixth invention] A polymer polyol composition for polymerizing an ethylenically unsaturated compound (b) in a polyol (A) in the presence of a dispersant (D), in the presence or absence of a diluent (C). In the production method, the following reactive dispersant (D11) is used as the dispersant (D) to obtain the polymer polyol composition of the third invention.
Reactive dispersant (D11): a substantially saturated polyol (a) and a monofunctional active hydrogen compound (e) having at least one polymerizable unsaturated group are bound via a polyisocyanate (f). (D11) A dispersant comprising a nitrogen-containing bond-containing unsaturated polyol having an average ratio of the number of unsaturated groups to the number of nitrogen-containing bonds derived from NCO groups in one molecule of 0.1 to 0.4.
[0007]
[Seventh invention] In a method for producing a foamed or non-foamed polyurethane resin by reacting a polyol component and a polyisocyanate component in the presence or absence of a foaming agent, any one of the above-mentioned as at least a part of the polyol component A method for producing a polyurethane resin, comprising using a polymer polyol composition.
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
In the present invention, as the polyol (A), a known polyol generally used for producing a polymer polyol can be used. For example, a compound having a structure in which an alkylene oxide is added to a compound containing at least two (preferably 2 to 8) active hydrogens (polyhydric alcohol, polyhydric phenol, amines, polycarboxylic acid, phosphoric acid, etc.) ( A1) and mixtures thereof.
Of these, preferred are compounds having a structure in which an alkylene oxide is added to a polyhydric alcohol.
[0009]
Examples of the polyhydric alcohol include dihydric alcohols having 2 to 20 carbon atoms (eg, aliphatic diols such as ethylene glycol, propylene glycol, 1,3- and 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol). Alkylene glycols such as cycloaliphatic diols such as cyclohexanediol and cyclohexanedimethanol), and trihydric alcohols having 3 to 20 carbon atoms (aliphatic triols such as glycerin, trimethylolpropane, and trimethylol). Alkanetriols such as ethane and hexanetriol); polyhydric alcohols having 4 to 8 or more carbon atoms having 5 to 20 carbon atoms (aliphatic polyols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglyceride) Emissions, alkane polyols and their intramolecular or intermolecular dehydration products, such as dipentaerythritol; and sucrose, glucose, mannose, fructose, sugars and their derivatives such as methyl glucoside) and the like.
[0010]
Examples of the polyhydric phenol include monocyclic polyhydric phenols such as pyrogallol, hydroquinone, and phloroglucin; bisphenols such as bisphenol A, bisphenol F, and bisphenolsulfone; and condensates (novolak) of phenol and formaldehyde.
[0011]
Examples of the amines include ammonia; and examples of the aliphatic amines include alkanolamines having 2 to 20 carbon atoms (eg, monoethanolamine, diethanolamine, isopropanolamine, and aminoethylethanolamine), and alkylamines having 1 to 20 carbon atoms ( For example, n-butylamine and octylamine), alkylene diamine having 2 to 6 carbon atoms (eg, ethylene diamine, propylene diamine and hexamethylene diamine), polyalkylene polyamines (dialkylene triamine having 2 to 6 carbon atoms in the alkylene group) Hexaalkyleneheptamines, such as diethylenetriamine and triethylenetetramine).
An aromatic mono- or polyamine having 6 to 20 carbon atoms (for example, aniline, phenylenediamine, tolylenediamine, xylylenediamine, diethyltoluenediamine, methylenedianiline and diphenyletherdiamine); an alicyclic ring having 4 to 20 carbon atoms Formula amines (isophorone diamine, cyclohexylene diamine and dicyclohexyl methane diamine); heterocyclic amines having 4 to 20 carbon atoms (for example, aminoethylpiperazine) and the like.
[0012]
Examples of the polycarboxylic acid include aliphatic polycarboxylic acids having 4 to 18 carbon atoms (succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, etc.), and aromatic polycarboxylic acids having 8 to 18 carbon atoms (terephthalic acid, Isophthalic acid), and mixtures of two or more of these.
[0013]
The alkylene oxide to be added to the active hydrogen-containing compound is preferably one having 2 to 8 carbon atoms, such as ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), and 1,2-. , 1,3-, 1,4- and 2,3-butylene oxide (hereinafter abbreviated as BO), styrene oxide (hereinafter abbreviated as SO) and the like, and combinations of two or more of these (block and And / or random addition). Preferably, it is PO or a combination of PO and EO (EO content is 25% by mass or less).
[0014]
Specific examples of the above-mentioned polyol include those obtained by adding PO to the above-mentioned active hydrogen-containing compound, those obtained by adding PO and another alkylene oxide (hereinafter abbreviated as AO) in the following manner, or the addition of these. Esterified products of a compound and a polycarboxylic acid or phosphoric acid are exemplified.
(1) Blocks added in PO-AO order (tiped)
(2) PO-AO-PO-AO blocks added in order (balanced)
(3) Blocks added in the order of AO-PO-AO
{Circle around (4)} Blocks added in the order of PO-AO-PO (active secondary)
{Circle around (5)} Random admixture of PO and AO mixed and added
(6) Random or block added in the order described in US Pat. No. 4,226,756
Further, the hydroxyl equivalent of (A1) is preferably from 200 to 4,000, more preferably from 400 to 3,000. It is also preferred that two or more (A1) are used in combination and the hydroxyl equivalent is within this range.
[0015]
As the polyol (A), another polyol (A2) can be used in combination with the compound (A1) having a structure in which an alkylene oxide is added to the active hydrogen-containing compound. In this case, the use ratio (mass ratio) of (A1) / (A2) is preferably 100/0 to 80/20.
Examples of the other polyol (A2) include polymer polyols such as polyester polyols and diene-based polyols, and mixtures thereof.
[0016]
Examples of the polyester polyol include the above-mentioned polyhydric alcohols and / or polyether polyols [ethylene glycol, diethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and the like. Polyhydric alcohols or mixtures of these with trihydric or higher polyhydric alcohols such as glycerin and trimethylolpropane, and adducts of these polyhydric alcohols with low moles (1 to 10 moles) of alkylene oxides] Or an anhydride thereof, an ester-forming derivative such as a lower alkyl (alkyl group having 1 to 4 carbon atoms) ester (eg, adipic acid, sebacic acid, maleic anhydride, phthalic anhydride, dimethyl terephthalate, etc.); Carboxylic anhydride Reaction product of alkylene oxide (EO, PO, etc.) with a polylactone polyol, for example, ring-opening polymerization of a lactone (ε-caprolactone, etc.) using the above polyhydric alcohol as an initiator. And polycarbonate polyols, for example, a reaction product of the polyhydric alcohol and a carbonic acid diester of a lower alcohol (such as methanol).
[0017]
Further examples include diene-based polyols such as polybutadiene polyols and hydrogenated products thereof; hydroxyl-containing vinyl polymers such as acrylic polyols; natural oil-based polyols such as castor oil; and modified products of natural oil-based polyols.
These polyols (A2) usually have 2 to 8, preferably 3 to 8 hydroxyl groups, and usually have a hydroxyl equivalent of 200 to 4,000, preferably 400 to 3,000.
[0018]
The number average molecular weight of the polyol (A) [the same applies to the following number average molecular weight measured by gel permeation chromatography (GPC)] is usually 500 or more, preferably 500 to 20,000, particularly preferably 1,200 to 15: 2,000, most preferably from 2,000 to 9,000. A number average molecular weight of 500 or more is preferable in terms of foaming properties of the polyurethane foam, and a number average molecular weight of 10,000 or less is preferable in terms of low viscosity and handling properties of the polymer polyol. The hydroxyl equivalent of (A) is preferably from 200 to 4,000, and more preferably from 400 to 3,000.
[0019]
In the second, third, fifth and sixth aspects of the present invention using the specific reactive dispersant (D1) or (D11), the number average usually used as described below, particularly as the ethylenically unsaturated compound (b), is used. When only the ethylenically unsaturated compound (b2) having a molecular weight of less than 500 is used, (A1) is more preferable and (A1) is more preferable among these (A) from the viewpoint of good physical properties of the obtained polyurethane. , (A11), or (A11) and (A12).
Polyol (A11): The average number of functional groups is 2.5 to 4, the hydroxyl value is 20 to 40 (mgKOH / g), and the content of oxyethylene units (hereinafter abbreviated as EO content) is 10 to 30% by mass. A polyoxyethylene polyoxypropylene polyol having a terminal EO content of 10 to 25% by mass (therefore, an internal EO content of 0 to 5% by mass)
Polyol (A12): a polyoxyethylene polyoxypropylene polyol having an average number of functional groups of 2 to 6, a hydroxyl value of 15 to 130 (mgKOH / g), and an EO content of 50 to 80% by mass.
[0020]
The hydroxyl value of the above (A11) is from 20 to 40 (mgKOH / g), preferably from 24 to 38. When the hydroxyl value is within this range, the viscosity of the polymer polyol composition becomes low, and the obtained polyurethane has good elongation.
(A11) can be obtained by adding EO and PO to the active hydrogen-containing compound (particularly polyhydric alcohol). The method of adding EO and PO may be block addition or random addition, but is preferably a block addition method, in which EO is added at the end and, if necessary, inside. The EO content of (A11) is from 10 to 30% by mass, preferably from 11 to 25% by mass, and more preferably from 12 to 20% by mass. Among them, the terminal EO content is 10 to 25% by mass, and preferably 11 to 20% by mass. The internal EO content is 0-5% by weight. When the EO content is within the above range, the curing property at the time of producing the polyurethane is good.
[0021]
The hydroxyl value of (A12) is 15 to 130 (mgKOH / g), preferably 18 to 120 (mgKOH / g), and more preferably 20 to 115 (mgKOH / g). When the hydroxyl value is within this range, the viscosity of the polymer polyol composition becomes low, and the resulting polyurethane has good wet heat permanent set.
(A12) can be obtained by adding EO and PO to the active hydrogen-containing compound (particularly polyhydric alcohol). As a method for adding EO and PO, block addition or random addition may be used, but random addition is preferred, and the EO content is 50 to 80% by mass, preferably 60 to 80% by mass. And more preferably 65 to 75% by mass. If the EO content is within the above range, the polyurethane foam has good air permeability.
[0022]
The mass ratio between the polyols (A11) and (A12) in (A) is preferably from 100: 0 to 50:50, particularly preferably 99.9: 0.1 to 70:30. Within this range, a low-viscosity polymer polyol composition can be obtained.
[0023]
In the polymer polyol compositions of the first and fourth inventions, the ethylenically unsaturated compound (b) has a terminal ethylenic compound having a number average molecular weight of 160 to 490 and a solubility parameter SP of 9.5 to 13. It contains the unsaturated group-containing compound (b1) as an essential component in an amount of 5% by mass or more. The number average molecular weight of (b1) is preferably from 170 to 480, more preferably from 180 to 450, particularly preferably from 182 to 420, and most preferably from 185 to 400. When the number average molecular weight is 160 or more, the viscosity of the polymer polyol composition is low, which is preferable in terms of handleability, and the foamed foam has good hardness. When the number average molecular weight of (b1) is 490 or less, the hardness of the polyurethane foam obtained by using the same is good.
[0024]
The number of ethylenically unsaturated groups in (b1) may be one or more on average. The number is preferably from 1 to 10, more preferably from 1 to 2, and particularly preferably 1. When the number of ethylenically unsaturated groups is less than one on average, not only the amount of the soluble component of the polyol increases, the viscosity of the obtained polymer polyol increases, but also the physical properties of the polyurethane resin produced by using these are remarkably inferior. . In addition, as long as the ethylenically unsaturated group of (b1) has at least one (average) terminal at the terminal, the remaining unsaturated group may be present at a terminal or at a position other than the terminal even if it exists at the terminal. Is also good.
Specific examples of the above ethylenically unsaturated groups include (meth) acryloyl groups and α-alkenyl groups such as allyl groups.
[0025]
The molecular weight (X) per single double bond of (b1) is preferably 490 or less, more preferably 160 to 480, particularly preferably 180 to 450, and most preferably 185 to 400. If it is 490 or less, the effect of reducing the amount of the polyol-soluble oligomer in the polymer polyol produced by using them is large. Here, the molecular weight (X) per one double bond in (b1) is defined by the following formula.
X = 1000 / N
N: the degree of unsaturation of (b1) measured by the measurement method specified in JIS K-1557
[0026]
Further, the solubility parameter SP of (b1) is usually 9.5 to 13, preferably 9.8 to 12.5, and more preferably 10.0 to 12.2. When the SP of (b1) is less than 9.5, the viscosity of the polymer polyol produced by using them becomes high. On the other hand, when the SP exceeds 13, there are disadvantages such as a decrease in hardness of the foam obtained by using the polymer polyol.
[0027]
In the first and fourth inventions, the solubility parameter SP is represented by the square root of the ratio between the cohesive energy density and the molecular volume as shown below.
[Solubility parameter] = (ΔE / V)^1/2
Here, ΔE represents the cohesive energy density. V represents molecular volume, and the value is represented by Robert F. Calculations by Robert F. Fedors et al. Are described in, for example, Polymer Engineering and Science, Vol. 14, pp. 147-154. As an example of the solubility parameter of a typical resin, as the value of the vinyl polymer, polystyrene = 10.6, polyacrylonitrile = 14.4, polymethyl methacrylate = 9.9; 9.4, polypropylene glycol = 8.7; Polyolefin values for polyethylene = 8.6, polypropylene = 8.0; Polyester values for polyethylene terephthalate = 12.4, polybutylene terephthalate = 11.7; for polyamide The values are described as 6-nylon 11.9 and 6,6-nylon = 11.9. Other resins can be calculated by combining the values for each chemical bond described in the table. For example, the value of polyimide is 19.6 when calculated from pyromellitic acid and 1,4-diaminobenzene, and the value of polyurethane is 12.3 when calculated from 1,4-butanediol and diphenylmethane diisocyanate. However, these values may slightly deviate due to a minute difference in the structure or the structure of the terminal of the resin.
[0028]
As specific examples of (b1), the following (b11) to (b15) are preferable, since the viscosity of the polymer polyol decreases and the hardness of the obtained polyurethane foam increases, when used. You may.
(B11): (poly) oxyalkylene (alkylene group having 2 to 8 carbon atoms) ether of terminally unsaturated alcohol (having 3 to 24 carbon atoms)
(B12): a compound represented by the following general formula [1]
(B13): a compound represented by the following general formula [2]
(B14): a compound represented by the following general formula [3]
(B15): a compound represented by the following general formula [4]
CH₂= CRCOO (AO) kCOCH₂COCH₃                    [1]
CH₂= CRCOO (AO) k [CO (CH₂) SO] m (AO) nH [2]
CH₂= CRCO [O (CH₂) SCO] mO (AO) nH [3]
CH₂= CRCOO (AO) k [QO (AO) p] r (QO) tH [4]
[Wherein R is a hydrogen atom or a methyl group; A is an alkylene group having 2 to 8 carbon atoms; Q is a residue obtained by removing two OH from dicarboxylic acid; k is a number average molecular weight not exceeding 490 An integer of 1 or more, n and p are 0 or an integer of 1 or more whose number average molecular weight does not exceed 490, s is an integer of 3 to 7, m and r are an integer of 1 or more whose number average molecular weight does not exceed 490, t Is 0 or 1]
Here, the number average molecular weight of "the number average molecular weight does not exceed 490" indicates the number average molecular weight of the compound.
[0029]
Examples of the terminal unsaturated alcohol having 3 to 24 carbon atoms in the above (b11) include allyl alcohol and 1-hexen-3-ol. The number of oxyalkylene units of (b11) is usually 1 to 9, preferably 1 to 5, and more preferably 1 to 3.
In the above general formulas [1] to [4], A is an alkylene group having 2 to 8 carbon atoms, and the AO unit is usually formed by addition of an alkylene oxide having 2 to 8 carbon atoms, and k, n and p Each corresponds to the number of moles of alkylene oxide added. The (poly) oxyalkylene unit having 2 to 8 carbon atoms of the alkylene group (b11) is usually formed by addition of an alkylene oxide having 2 to 8 carbon atoms.
Examples of the alkylene oxide include the same alkylene oxides as those exemplified as the alkylene oxide to be added to the active hydrogen-containing compound in the above section of the polyol (A). Preferably, it is PO and / or EO.
k is preferably 1 to 7, more preferably 1 to 5, and particularly preferably 1. n is preferably 0 or 1 to 7, more preferably 0 or 1 to 5, and particularly preferably 0. p is preferably 0 or 1 to 6.
[0030]
Examples of Q include a residue obtained by removing two OH from a dicarboxylic acid. As the dicarboxylic acid, those having 4 to 10 carbon atoms are preferable, and specific examples include phthalic acid (including isophthalic acid and terephthalic acid), maleic acid, fumaric acid, and succinic acid. Preferred are phthalic acid and succinic acid.
[CO (CH₂) SO] and [O (CH₂) SCO] units are usually formed by the addition of lactones. s is preferably 4 to 6, and more preferably 5. m is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 2.
Further, r is preferably 1 to 5, more preferably 1 or 2, and particularly preferably 1.
Among these (b11) to (b15), more preferred are (b11) and (b12), and particularly preferred is (b11).
[0031]
As specific examples of (b11) to (b15), for example, (b11) includes 1 to 5 moles of PO and / or EO of allyl alcohol.
Examples of (b12) include acetoacetate of a compound obtained by adding 1 to 5 moles of PO and / or EO to 1 mole of (meth) acrylic acid.
As (b13), a compound obtained by adding 1 to 5 mol of ε-caprolactone to a compound obtained by adding 1 to 5 mol of PO and / or EO to 1 mol of (meth) acrylic acid; And compounds to which ５5 mol of PO and / or EO are added.
Examples of (b14) include a compound in which 1 to 5 mol of ε-caprolactone is added to 1 mol of (meth) acrylic acid, and a compound in which 1 to 5 mol of PO and / or EO is further added to 1 mol of this compound. Is mentioned.
(B15) includes a monoester of a compound obtained by adding 1 to 5 moles of PO and / or EO to 1 mole of (meth) acrylic acid and an equimolar amount of succinic acid, and 1 mole of (meth) acrylic acid contains PO and / or Or a monoester of maleic acid or fumaric acid in an equimolar amount with a compound obtained by adding 1 to 5 moles of EO, and an equimolar amount of a compound obtained by adding 1 to 5 moles of PO and / or EO to 1 mole of (meth) acrylic acid And 1 to 5 moles of EO and / or PO further added to 1 mole of the monoester with phthalic acid, and a monoester of this compound with an equimolar phthalic acid.
[0032]
In the polymer polyol composition of the present invention, as the ethylenically unsaturated compound (b), a commonly used ethylenically unsaturated compound (b2) other than (b1) having a number average molecular weight of less than 500 may be used. As (b2), aromatic hydrocarbon monomer (b2-1), unsaturated nitriles (b2-2) (meth) acrylates (b2-3), and other ethylenically unsaturated compounds (b2-4) ), And mixtures of two or more of these. In particular, when the reactive dispersant (D1) or (D11) of the second or third invention is used, only (b2) can be used.
[0033]
Examples of (b2-1) include styrene, α-methylstyrene, hydroxystyrene, chlorostyrene and the like.
Examples of (b2-2) include acrylonitrile and methacrylonitrile.
As (b2-3), methyl (meth) acrylate, butyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, (Meth) acrylic acid alkyl esters such as tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, eicosyl (meth) acrylate, docosyl (meth) acrylate, and the like. Hydroxypolyoxyalkylene (alkylene group having 2 to 8 carbon atoms) mono (meth) acrylates;
[0034]
(B2-4) includes (meth) acrylamide; vinyl group-containing carboxylic acids such as (meth) acrylic acid and derivatives thereof; aliphatic hydrocarbon monomers such as ethylene and propylene; perfluorooctylethyl methacrylate, perfluorooctyl Fluorine-containing vinyl monomers such as ethyl acrylate; nitrogen-containing vinyl monomers other than the above such as diaminoethyl methacrylate and morpholinoethyl methacrylate; vinyl-modified silicon; and cyclic olefin compounds such as norbornene, cyclopentadiene and norbornadiene.
Among these, (b2-1) and (b2-2) are preferable, and styrene and / or acrylonitrile are more preferable. The total content of the aromatic hydrocarbon monomer and the unsaturated nitriles in (b2) is preferably 50% by mass or more.
[0035]
In the second, third, fifth and sixth aspects of the present invention, (b2-1), (b2-2), (b2-3) and (b2-4) in (b) when only (b2) is used. The mass ratio can be changed according to the required physical properties of the polyurethane and the like, and is not particularly limited. An example is as follows.
(B2-1): Usually 0 to 100% by mass, preferably 20 to 80% by mass.
(B2-2): Usually 0 to 95% by mass, preferably 20 to 80% by mass.
(B2-3): Usually 0 to 50% by mass, preferably 0 to 20% by mass.
(B2-4): Usually 0 to 10% by mass, preferably 0 to 5% by mass.
[0036]
The mass ratio of (b2-1) to (b2-2) is preferably (5:95) to (100: 0), more preferably (20:80) to (100: 0), and particularly preferably. (25:75) to (80:20).
[0037]
In addition, as a part of (b) (preferably 0.05 to 1% by mass), a bifunctional or more (preferably 2 to 8 functional) polyfunctional vinyl group-containing monomer (b2 By using -5), the strength of the polymer can be further improved. Examples of polyfunctional vinyl group-containing monomers include divinylbenzene, ethylene di (meth) acrylate, polyalkylene (having 2 to 8 carbon atoms in the alkylene group) glycol di (meth) acrylate, pentaerythritol triallyl ether, and trimethylolpropane tri (meth). Acrylate and the like.
[0038]
Further, as (b), an ethylenically unsaturated compound (b3) having the following number average molecular weight of 500 or more may be used.
Among (b3), those having one double bond in the molecule include unsaturated alcohols of aliphatic alcohol (C1-24) (poly) oxyalkylene (C2-8 alkylene) ether Dicarboxylic acid (C4-24) diester, for example, maleic acid diester of polyoxypropylene (degree of polymerization: n = 4-30) monomethyl ether [where the degree of polymerization n indicates the degree of polymerization of the polyoxypropylene segment I have. Hereinafter, unless otherwise specified, the degree of polymerization of the (poly) oxyalkylene segment is shown. ), Fumaric acid diester of polyoxypropylene (n = 3-30) monobutyl ether and itaconic acid diester of butanol polyoxybutylene (n = 2-20) polyoxyethylene (n = 2-10) random adduct; fat Group alcohol (C1-24) polyoxyalkylene (C2-8 alkylene group) ether (meth) acrylate, for example, polyoxypropylene [n = 8 (7) -30] monomethyl ether (meth) acrylate However, the numerical value in parentheses of n is the case of methacrylate. The same applies to the following), polyoxybutylene [n = 6 (5) to 20] monobutyl ether (meth) acrylate, and polyoxypropylene (n = 5 to 30) monolauryl ether (meth) acrylate; unsaturated alcohol (3 carbon atoms) To 24) polyoxyalkylene (alkylene group having 2 to 8 carbon atoms) ethers, for example, polyoxypropylene (n = 4 to 30) monooleyl ether, polyoxypropylene (n = 8 to 30) monoallyl ether; Saturated aliphatic monocarboxylic acid (C3-24) polyoxyalkylene (C2-8 alkylene group) ester, for example, propylene oleate (n = 2-30) -ethylene having a number average molecular weight of 500 or more Oxide (n = 2 to 10) random adduct; and the like.
[0039]
Examples of (b3) having two double bonds in the molecule include polyalkylene (C2 to C8 alkylene group) glycol di (meth) acrylate, for example, polypropylene glycol [n = 7 (6) to 30] di (meth) acrylate and polybutylene glycol [n = 6 (5) to 20] di (meth) acrylate; aliphatic carboxylic acid of unsaturated alcohol (3 to 24 carbon atoms) (2 to 24 carbon atoms) Diester, for example, succinic diester of polyoxypropylene (n = 3 to 30) monoallyl ether, adipic acid diester of polyoxypropylene (n = 3 to 30) monoallyl ether, polyoxypropylene (n = 3 to 30) Succinic diester of monopropenyl ether; and the like.
[0040]
Among (b3), those having three double bonds in the molecule include unsaturated fatty acid (3 to 24 carbon) triesters of a trihydric alcohol having 3 to 12 carbon atoms, for example, glycerin polyoxypropylene [n = 5 (4) -30] ether tri (meth) acrylate, trimethylolpropanepolyoxypropylene [n = 4 (3) -30] ether tri (meth) acrylate, pentaerythritol polyoxypropylene [n = 4 ( 3) to 30] ether tri (meth) acrylate, diglycerin polyoxypropylene (n = 3 to 30) ether tri (meth) acrylate, and sorbitan polyoxybutylene [n = 3 (2) to 20] tri ( (Meth) acrylate; aliphatic carboxylic acid (3 to 24 carbon atoms) of unsaturated alcohol (3 to 24 carbon atoms) Ster, for example, hexanetricarboxylic acid triester of allyl alcohol (poly) oxypropylene (n = 1 to 30) ether; unsaturated alkyl group-containing ether compound, for example, glycerin polyoxypropylene (n = 5 to 30) ether triester Allyl ether; and the like.
[0041]
Examples of (b3) having four or more double bonds in the molecule include unsaturated fatty acid (3 to 24 carbon atoms) polyesters of polyvalent (4 to 8 or more) alcohols, for example, Polyglycerin having an average molecular weight of 500 or more (degree of polymerization of glycerin: n = 3 to 4) poly (meth) acrylate (hereinafter, for a polyglycerin group, n indicates the degree of polymerization of glycerin), and a number average molecular weight of 500 or more (N = 2-4) polyolate, dipentaerythritol poly (meth) acrylate having a number average molecular weight of 500 or more, polyglycerin (n = 2-4) (poly) oxypropylene having a number average molecular weight of 500 or more (N = 1-30) Poly (meth) acrylate, pentaerythritol polyoxypropylene [n = 3 (2) -30] ether tetra (Meth) acrylate, tetra (meth) acrylate of sorbitan polyoxybutylene (n = 2 to 20) ether, polyvinyl alcohol (degree of saponification 70 to 100, number average molecular weight 1,000 to 10,000) (meth) acrylate; Polycarboxylic acid esters (number average molecular weight: 1,000 to 10,000) of saturated alcohols (3 to 24 carbon atoms), for example, hexane tetracarboxylic acid esters of allyl alcohol (poly) oxypropylene (n = 1 to 30) ether Polyester of (meth) acrylic acid polymer and allyl alcohol (number average molecular weight 1,000 to 10,000), polyester of maleic acid polymer and allyl alcohol (number average molecular weight 1,000 to 10,000); unsaturated alkyl group Containing ether compound, for example, number average molecular weight 5 0 or more tetraglycerin polyallyl ether, polyallyl ether of polyglycerin (n = 2-4) (poly) oxypropylene (n = 1-30) ether having a number average molecular weight of 500 or more; unsaturated carboxylic acid (4 carbon atoms) To 22) and glycols (number average molecular weight of 500 to 10,000), for example, polyester of maleic acid and ethylene glycol (number average molecular weight of 500 to 10,000), polyester of maleic acid and diethylene glycol (number average) Polyester of maleic acid and propylene glycol (number average molecular weight of 500 to 10,000), polyester of maleic acid and 1,3- or 1,4-butanediol (number average molecular weight of 500 to 10,000) 000), poly of itaconic acid and ethylene glycol Ester (number average molecular weight 500 to 10,000), polyester of itaconic acid and diethylene glycol (number average molecular weight 500 to 10,000), polyester of maleic acid and polyoxypropylene glycol (n = 1 to 30) (number average molecular weight) 500-10,000), polyester (number average molecular weight 500-10,000) of itaconic acid and polyoxypropylene glycol (n = 1-30), and fumaric acid and polyoxybutylene glycol (n = 1-20). (Number average molecular weight of 500 to 10,000); and the like.
[0042]
Of these (b3), an ester compound comprising an unsaturated carboxylic acid (p) and a glycol (q) and / or an ester compound comprising an unsaturated alcohol (r) and a carboxylic acid (s) are preferable. A radical polymerizable compound comprising a saturated carboxylic acid (p) and a glycol (q) is particularly preferred.
The unsaturated carboxylic acid (p) is a carboxylic acid having a double bond (a non-conjugated double bond in the case of two or more) or a derivative thereof in the molecule, and examples thereof include acrylic acid, methacrylic acid, maleic acid, and fumaric acid. C3 to C24 carboxylic acids such as acid, itaconic acid, citraconic acid and oleic acid; and acid anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride. Preferably, it is at least one carboxylic acid selected from maleic acid, fumaric acid and itaconic acid, or a derivative thereof.
If necessary, other carboxylic acids can be used in combination. Other carboxylic acids include, for example, aliphatic carboxylic acids having 2 to 24 carbon atoms such as acetic acid, propionic acid, hexanoic acid, stearic acid, oxalic acid, malonic acid, succinic acid, glutamic acid, adipic acid and sebacic acid; C7 to C18 aromatic carboxylic acids such as acids and terephthalic acids; C6 to C20 alicyclic carboxylic acids such as 1,4-cyclohexanedicarboxylic acid and tetrahydrophthalic acid.
[0043]
As the glycols (q), among the active hydrogen-containing compounds described in the description of the polyol (A), polyhydric alcohols and polyphenols, and the alkylene oxides having 2 to 8 carbon atoms can be used. Preferably, alkylene glycols such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polyoxypropylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and EO, PO , BO, SO and the like, and more preferably, ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, EO and PO.
[0044]
The content of (b1) in (b) is preferably 2% by mass or more, more preferably 5 to 80% by mass, and particularly preferably 7 to 50% by mass.
When the amount of (b1) is 2% by mass or more, the viscosity of the obtained polymer polyol becomes low. (B1) is preferably at least 5% by mass (the present inventions 1 and 4), but when the reactive dispersant (D1) (including (D11)) described below is used, it may be less than 5% by mass. No problem. The component in (b) used in combination with (b1) is preferably (b2).
[0045]
Examples of the polymerization method (b) include radical polymerization, coordination anion polymerization, metathesis polymerization, Diels-Alder polymerization, and the like. Radical polymerization is preferred.
[0046]
The radical polymerization can be performed in the same manner as the polymerization in the conventional polymer polyol. For example, a method of polymerizing an ethylenically unsaturated compound (b) in the presence of a polymerization initiator in a polyol (A) containing a dispersant (D) (a method described in US Pat. No. 3,383,351) is known. No.
The polymerization can be carried out in a batch system or a continuous system, and can be carried out under normal pressure, under pressure or under reduced pressure. If necessary, a diluent (C), a chain transfer agent and the like can be used.
Hereinafter, each component used for radical polymerization will be described sequentially.
[0047]
The dispersant (D) is not particularly limited, and the following general dispersants used in polymer polyols can be used.
For example, (1) a macromer-type dispersant obtained by reacting a polyol such as an ethylenically unsaturated group-containing modified polyether polyol (for example, JP-A-08-333508) with an ethylenically unsaturated compound; Two or more polyol affinity segments having a solubility parameter difference of 1.0 or less as side chains, and a polymer affinity segment having a solubility parameter difference of 2.0 or less from a polymer derived from a vinyl monomer as a main chain. A graft-type dispersant in which a polyol and an oligomer such as a graft-type polymer (for example, JP-A-05-051134) are combined; and (3) methylene dihalide and / or ethylene dihalide Modified polyols having a high molecular weight by reacting with a halide (see, for example, JP-A-07-196749) (4) a vinyl oligomer having a weight-average molecular weight of 1,000 to 30,000, at least a part of which is soluble in a polyol, and the oligomer and the ethylenically unsaturated compound of the above (1) Oligomer-type dispersants such as a dispersant which uses a group-containing modified polyether polyol in combination (for example, JP-A-09-77968); and the like.
Of these, the types (1) and (4) are preferred. In each case, the number average molecular weight is preferably 1,000 to 10,000.
In addition, when these ordinary dispersants are used as (D), the amount used is preferably 15% by mass or less, more preferably 10% by mass or less, particularly preferably 0.1 to 10% by mass, based on the mass of (b). 8% by mass.
[0048]
As (D), in addition to these ordinary dispersants, the following reactive dispersants (D1) (including (D11)) of the present second, third, fifth and sixth inventions are used. Is particularly preferred.
The reactive dispersant (D1) is obtained by bonding a monofunctional active hydrogen compound (e) having at least one polymerizable unsaturated group to a substantially saturated polyol (a) via a polyisocyanate (f). This is a dispersant comprising the obtained nitrogen-containing bond-containing unsaturated polyol.
[0049]
As (a) constituting the reactive dispersant (D1), the same ones as those exemplified as the above (A) can be used. (A) and (A) may be the same or different.
The number of hydroxyl groups in one molecule of (a) is at least 2, preferably 2 to 8, more preferably 3 to 4, and the hydroxyl equivalent of (a) is preferably 1,000 to 3, 000, more preferably 1,500 to 2,500.
[0050]
(E) used to obtain (D1) is a compound having one active hydrogen-containing group and at least one polymerizable unsaturated group. Examples of the active hydrogen-containing group include a hydroxyl group, an amino group, an imino group, a carboxyl group, and an SH group, and a hydroxyl group is particularly preferable.
The polymerizable unsaturated group of (e) is preferably a polymerizable double bond, and the number of polymerizable unsaturated groups in one molecule is preferably from 1 to 3, particularly preferably 1. That is, an unsaturated monohydroxy compound having one polymerizable double bond is preferable as (e).
Examples of the unsaturated monohydroxy compound include monohydroxy-substituted unsaturated hydrocarbons, monoesters of unsaturated monocarboxylic acids and dihydric alcohols, monoesters of unsaturated dihydric alcohols and monocarboxylic acids, and alkenyl side chains. Phenol having a group, unsaturated polyether monol, and the like.
[0051]
Examples of the monohydroxy-substituted unsaturated hydrocarbon include alkenols having 3 to 6 carbon atoms, such as (meth) allyl alcohol, 2-buten-1-ol, 3-buten-2-ol, and 3-buten-1-ol; Alkynol, for example, propargyl alcohol and the like.
Examples of the monoester of an unsaturated monocarboxylic acid and a dihydric alcohol include, for example, an unsaturated monocarboxylic acid having 3 to 8 carbon atoms such as acrylic acid, methacrylic acid, crotonic acid, and itaconic acid; And monohydric alcohols having 2 to 12 carbon atoms, such as glycol, propylene glycol, and butylene glycol. Specific examples thereof include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl acrylate. , 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, and the like.
[0052]
Examples of the monoester of an unsaturated dihydric alcohol and a monocarboxylic acid include monoesters of an unsaturated dihydric alcohol having 3 to 8 carbon atoms and a monocarboxylic acid having 2 to 12 carbon atoms, such as acetic acid monoester of butenediol. Is mentioned.
Examples of the phenol having an alkenyl side chain group include a phenol having an alkenyl side chain group having 2 to 8 carbon atoms of an alkenyl group such as oxystyrene and hydroxy α-methylstyrene.
Examples of the unsaturated polyether monool include 1 to 50 moles of the above-mentioned monohydroxy-substituted unsaturated hydrocarbon or alkylene oxide (2 to 8 carbon atoms) of phenol having an alkenyl side chain group [for example, polyoxyethylene (polymerization degree 2 to 10) monoallyl ether].
[0053]
Examples of (e) other than the unsaturated monohydroxy compound include the following.
Examples of (e) having an amino group or an imino group include mono- and di- (meth) allylamine, aminoalkyl (2-4 carbon atoms) (meth) acrylate (such as aminoethyl (meth) acrylate), monoalkyl (carbon (Equation 1 to 12) aminoalkyl (C2 to C4) (meth) acrylate [such as monomethylaminoethyl-methacrylate]; (e) having a carboxyl group includes the unsaturated monocarboxylic acid described above; )) Includes compounds corresponding to the unsaturated monohydroxy compounds (OH is replaced by SH).
Examples of (e) having two or more polymerizable double bonds include poly (meth) allyl ether of the above-mentioned trivalent, 4- to 8-valent or more polyhydric alcohol or polyester with the above unsaturated carboxylic acid. [For example, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, glycerin di (meth) acrylate, etc.].
[0054]
Among these compounds, preferred are alkenol having 3 to 6 carbon atoms, monoester of an unsaturated monocarboxylic acid having 3 to 8 carbon atoms and a dihydric alcohol having 2 to 12 carbon atoms, and phenol having an alkenyl side chain group. And more preferably a monoester of (meth) acrylic acid with ethylene glycol, propylene glycol or butylene glycol; allyl alcohol; and hydroxy α-methylstyrene, and particularly preferably 2-hydroxyethyl (meth) acrylate.
The molecular weight of (e) is not particularly limited, but is preferably 1,000 or less, particularly preferably 500 or less.
[0055]
The polyisocyanate (f) is a compound having at least two isocyanate groups, and is an aromatic polyisocyanate, an aliphatic polyisocyanate, an alicyclic polyisocyanate, an araliphatic polyisocyanate, or a modified product of these polyisocyanates (urethane Group, carbodiimide group, allophanate group, urea group, buret group, isocyanurate group or oxazolidone group-containing modified product), isocyanate group-terminated prepolymer, and a mixture of two or more of these.
[0056]
Examples of the aromatic polyisocyanate include aromatic diisocyanates having 6 to 16 carbon atoms (excluding carbon in the NCO group; the same applies to the following polyisocyanates), aromatic triisocyanates having 6 to 20 carbon atoms, and crude products of these isocyanates And the like. Specific examples include 1,3- and 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- and / or 4,4 ' Diphenylmethane diisocyanate (MDI), crude MDI [condensation product of crude diaminodiphenylmethane @ formaldehyde and an aromatic amine (aniline) or a mixture thereof: Phosgenated product of the mixture {: polyallyl polyisocyanate (PAPI), etc.], naphthylene-1,5-diisocyanate, triphenylmethane-4,4 ′, 4 ″ -triisocyanate and the like.
Examples of the aliphatic polyisocyanate include an aliphatic diisocyanate having 2 to 18 carbon atoms. Specific examples include 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and the like.
[0057]
Examples of the alicyclic polyisocyanate include an alicyclic diisocyanate having 4 to 16 carbon atoms. Specific examples include isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, norbornane diisocyanate, and the like.
Examples of the araliphatic isocyanates include araliphatic diisocyanates having 8 to 15 carbon atoms. Specific examples include xylylene diisocyanate and α, α, α ′, α′-tetramethylxylylene diisocyanate.
Specific examples of the modified polyisocyanate include urethane-modified MDI, carbodiimide-modified MDI, sucrose-modified TDI, and castor oil-modified MDI.
Of these, aromatic diisocyanates are preferred, and 2,4- and / or 2,6-TDI are more preferred.
[0058]
The nitrogen-containing bond of the reactive dispersant (D1) is generated by a reaction between an isocyanate group and an active hydrogen-containing group. When the active hydrogen-containing group is a hydroxyl group, a urethane bond is mainly generated and an amino group is formed. In some cases, mainly urea bonds are formed. An amide bond is formed in the case of a carboxyl group, and a thiourethane bond is formed in the case of an SH group. In addition to these groups, other bonds such as a burette bond and an allophanate bond may be formed.
This nitrogen-containing bond is formed by the reaction between the hydroxyl group of the substantially saturated polyol (a) and the isocyanate group of the polyisocyanate (f), and the active hydrogen-containing group of the unsaturated monofunctional active hydrogen compound (e) ( Some are caused by the reaction of f) with isocyanate groups.
[0059]
In light of the dispersion stability of the polymer polyol, the average value of the number of hydroxyl groups in one molecule of (D1) is usually 2 or more, preferably 2.5 to 10, and more preferably 3 to 6. The average value of the number of unsaturated groups in one molecule of (D1) is preferably 0.8 to 2, and more preferably 0.9 to 1.2.
From the viewpoint of dispersion stability of the polymer polyol, the hydroxyl equivalent of (D1) is preferably from 500 to 10,000, more preferably from 1,000 to 7000, particularly preferably from 2,000 to 6,000.
The viscosity of (D1) is preferably 10,000 to 50,000 mPa · s / 25 ° C., and more preferably 15,000 to 35,000 mPa · s / 25 ° C. When the viscosity is within the above range, the dispersibility of the polymer is better, and the viscosity of the polymer polyol obtained by using (D1) is low and the handling is easy.
[0060]
The method for producing the reactive dispersant (D1) using these raw materials is not particularly limited.
As a preferred method, a method of adding a polyisocyanate (f) to a mixture of an unsaturated monofunctional active hydrogen compound (e) and a substantially saturated polyol (a) and reacting the mixture in the presence of a catalyst if necessary, (E) and (f) are optionally reacted in the presence of a catalyst to produce an unsaturated compound having an isocyanate group, and then reacted with (a). The latter method is the most preferred method because it is a method capable of obtaining a nitrogen-containing bond-containing unsaturated polyol with less generation of by-products such as a compound having no hydroxyl group.
Further, after reacting with (f) using the precursor instead of (e) or (a), the precursor portion may be modified to form (D1). [For example, an unsaturated monocarboxylic acid or an ester-forming derivative thereof is reacted after the reaction with an isocyanate to introduce an unsaturated group, and after the reaction with the isocyanate, jumping with an alkylene dihalide, a dicarboxylic acid, or the like to form (D1) Form〕
[0061]
Examples of the catalyst at the time of the above reaction include, for example, a commonly used urethane-forming catalyst, such as a tin-based catalyst (such as dibutyltin dilaurate and Starnas octoate), another metal catalyst (such as tetrabutyl titanate), and an amine-based catalyst ( Triethylenediamine and the like are used. Preferred among these is tetrabutyl titanate.
The amount of the catalyst is preferably 0.0001 to 5% by mass, more preferably 0.001 to 3% by mass, based on the mass of the reaction mixture.
[0062]
As for the reaction ratio of these three components, the equivalent ratio of the active hydrogen-containing group of (e) and (a) to the isocyanate group of (f) is preferably (1.2 to 4) based on the total amount used in the reaction. : 1, more preferably (1.5 to 3): 1.
The amount of (e) used in the reaction with respect to 100 parts by mass of (a) is preferably less than 2 parts by mass, more preferably 0.5 to 1.8 parts by mass.
[0063]
The reactive dispersant (D1) obtained by the above method may be a single compound, but in many cases, a mixture of various compounds represented by the following general formula [5].
[0064]
Embedded image

[0065]
[Wherein, Z is a residue of (f) having a valence of h (where h is an integer of 2 or more); T is a residue of (e) (provided that it has a polymerizable unsaturated group);₁  Is q₁  Residue of a polyvalent polyol [(a) or the OH prepolymer from (a) and (f)], A₂  Is q₂  Residue of a multivalent polyol [(a) or the OH prepolymer from (a) and (f)] (only

T 'is H or an alkyl group having 1 to 12 carbon atoms; g is an integer of 1 or more; j is an integer of 1 or more. Where q₁  −g ≧ 0 and h−j−1 ≧ 0. The total number of OH groups is 2 or more. ]
[0066]
That is, one (a) and one (e) are connected via one (f), and a plurality of (e) are each connected to one (a) via one (f). ), And a combination of a total of three or more of (a) and (e) via a plurality of (f). In addition, as other by-products, (a) one having a bond bonded through (f) (a nitrogen-containing bond-containing polyol having no unsaturated group), and (e) two bonds having a bond bonded via (f) (An unsaturated compound containing a nitrogen-containing bond having no hydroxyl group) may be formed, and may contain unreacted (a) or (e).
This mixture can be used as a dispersant as it is, but those containing a small amount of a nitrogen-containing bond-containing polyol having no unsaturated group or a nitrogen-containing bond-containing unsaturated compound having no hydroxyl group are preferable, and these impurities which can be further removed are preferable. Can also be applied after removal.
Further, since the unsaturated group in (D1) is located at or near the terminal of the molecular chain of the polyol, it is easy to copolymerize with the monomer.
[0067]
(D11) used in the third and sixth inventions is an average of the ratio of the number of unsaturated groups to the nitrogen-containing bond derived from the NCO group of (f) in one molecule, which is obtained by the following formula (4): (A), (e), and (f) are reacted at such a ratio that is 0.1 to 0.4.
K = [number of moles of (e) × number of unsaturated groups of (e)] / [number of moles of (f) × number of NCO groups of (f)] --- (4)
The value of K is more preferably from 0.1 to 0.3, and particularly preferably from 0.2 to 0.3. When the value of K is within the above range, the dispersion stability of the polymer polyol becomes particularly good.
[0068]
The constituent ratio of the polyol (A) and the reactive dispersant (D1) at the time of preparing the polymer polyol is preferably such that 0.5 to 50 parts by mass of (D1) is used with respect to 100 parts by mass of (A). 2nd and 5th inventions]. More preferably, (D1) is 0.8 to 15 parts, particularly preferably 1 to 10 parts, per 100 parts of (A). When (D1) is 50 parts by mass or less, the viscosity of the polymer polyol does not increase, and when it is 0.5 parts by mass or more, the dispersibility is good.
In the case of (D11), since the dispersion stability is excellent, the use ratio can be changed in a wide range (for example, 0.1 to 80 parts by mass with respect to 100 parts by mass of (A)), but the above range is preferable.
[0069]
The reactive dispersants (D1) and (D11) of the second, third, fifth, and sixth inventions have very good dispersion stability of the polymer polyol composition obtained by using them, and As the unsaturated compound, it can be used for producing a polymer polyol composition using only the conventional monomer (b2), but the specific ethylenically unsaturated group-containing compound (b1) of the first and fourth inventions is used. It is particularly suitably used for the production of a polymer polyol composition, and a polymer polyol composition having a lower viscosity can be obtained.
[0070]
Next, as the radical polymerization initiator used in the polymerization of (b), those which generate free radicals and initiate polymerization can be used. For example, 2,2′-azobisisobutyronitrile, 2,2 ′ -Azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2 , 4,4-trimethylpentane), dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis [2- (hydroxymethyl) propionitrile] and 1,1'-azobis ( Azo compounds such as 1-acetoxy-1-phenylethane); dibenzoyl peroxide, dicumyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate DOO, benzoyl peroxide, organic peroxides such as lauroyl peroxide and peracetic acid; inorganic peroxides such as persulfates and perborate salts. In addition, these can use 2 or more types together.
[0071]
The amount used when the radical polymerization initiator is used is usually 0.05 to 20% by mass, preferably 0.1 to 15% by mass, and particularly preferably 0.2 to 10% by mass, based on the amount of (b) used. %. When the amount of the polymerization initiator used is in the range of 0.05 to 20% by mass, the polymerization rate of (b) in the polymer polyol becomes sufficiently high and the molecular weight also becomes large, so that when the urethane foam is used, a sufficient foam is obtained. It is excellent in that compression hardness can be obtained.
[0072]
Examples of polymerization initiators in polymerization methods other than radical polymerization include, in coordination anion polymerization, organic alkyl compounds of various metals of Groups I, II, and III of the periodic table and metal salts of Groups IV to VII. An initiator consisting of a combination is mentioned. In the metathesis polymerization, WCl₆  And MoCl₅  And an initiator composed of a combination of benzene and an organoaluminum.
[0073]
Examples of the diluent (C) used in the radical polymerization include aromatic hydrocarbon solvents such as toluene and xylene; saturated aliphatic hydrocarbon solvents having 5 to 15 carbon atoms such as hexane and heptane; octene, nonene and decene. C5-30 unsaturated aliphatic hydrocarbon solvents; alcohol solvents such as methanol, isopropanol and n-butanol; ether solvents such as dioxane; ester solvents such as ethyl acetate; nitriles such as acetonitrile Amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide. Preferred as (C) is an aromatic hydrocarbon-based solvent, more preferably xylene, because the viscosity of the obtained polymer polyol composition becomes low.
The amount of the diluent used is preferably 0 to 50% by mass, more preferably 1 to 40% by mass, based on the amount of (b) used.
[0074]
The (C) used is preferably removed by stripping under reduced pressure or the like after the polymerization reaction, but if necessary, the (C) may be left in the polymer polyol composition (I) or newly added to the polymer polyol composition (I). ) Can be further reduced in viscosity. Examples of (C) contained in (I) include the above-mentioned unsaturated aliphatic hydrocarbon solvents; aromatic solvents; and low-viscosity (100 mPa · s / 25 ° C. or less) flame retardants, for example, tris (chloroethyl). Phosphate, tris (chloropropyl) phosphate; and the like.
The content of (C) in (I) is preferably 3% by mass or less, more preferably 2% by mass or less, and particularly preferably 1% by mass or less.
[0075]
Examples of the chain transfer agent include alkyl mercaptans such as dodecyl mercaptan and mercaptoethanol; alcohols such as isopropyl alcohol, methanol, 2-butanol and allyl alcohol; and halogenated carbons such as carbon tetrachloride, carbon tetrabromide and chloroform. Hydrogen and the like.
The amount of the chain transfer agent to be used is generally 0 to 2% by mass based on the amount of (b) used.
[0076]
The content of the polymer particles (B) dispersed in (A) in the polymer polyol composition of the first to third inventions is preferably 35 to 75 mass, particularly when (b) is composed of (b1). %, More preferably 45 to 75% by mass. When the content of (B) is 35% by mass or more, sufficient foam compression hardness is obtained, and when it is 75% by mass or less, aggregation and sedimentation of polymer particles can be prevented, and a polymer polyol having good handleability can be obtained. Is preferred.
[0077]
In the polymer polyol composition (I) of the first to third inventions obtained by the production method of the fourth to sixth inventions, the content of (B) is 35 to 75% by mass based on the mass of (I). In particular, when (b) comprises (b1), the amount of the soluble polymer (P) dissolved in (A) can be 5% by mass or less based on the mass of (A). The amount of (P) is preferably at most 3% by mass. When the amount of (P) is 5% by mass or less, the viscosity of the polymer polyol composition is low, the handling is easy, and the hardness of the foamed foam is high. In the case of the polymer polyol composition (I) obtained using the dispersant (D), the content of (P) is preferably 5% by mass or less, but may be 10% by mass or less.
Here, the soluble polymer (P) dissolved in the polyol (A) refers to the polymer particles (B) insoluble in (A) and the polymer particles (A) (a small amount of low molecular weight additive) from the polymer polyol composition (I). (Including living organisms) and is usually a compound having a higher molecular weight than the polyol (A).
[0078]
The content of the polymer particles (B) and the amount of the soluble polymer (P) are measured by the following methods.
20 g of methanol is added to 5 g of (I), and the mixture is placed in a 100 cc stainless steel tube and centrifuged at 20 ° C. at 18,000 rpm × 60 minutes to aggregate (B), thereby obtaining a clear supernatant solution. The ratio (%) of the obtained mass of (B) to (I) is defined as the content of (B). After methanol was removed from this solution by a reduced-pressure drier, the polyol (A) (including a small amount of low-molecular-weight by-product) and the polymer (P) soluble in (A) (weight average) were analyzed by preparative liquid chromatography. (A molecular weight of 4000 or more, usually a peak appears on the higher molecular weight side than the peak of (A) in chromatography). The weight average molecular weight (by GPC) of (P) is usually 6,000 to 30,000, but may further include those having a higher molecular weight.
In the case where the soluble polymer (P) cannot be separated from the polyol (A) by preparative liquid chromatography (when the molecular weights overlap), centrifugation is carried out in the same manner as described above to aggregate (B), and the supernatant clear solution is used. Get. After methanol is removed from this solution by a vacuum drier, diethyl ether is added, the precipitate is separated by filtration and dried, whereby the soluble polymer (P) can be separated from (A).
[0079]
The polymer polyol compositions (I) of the first to third inventions obtained by the production methods of the fourth to sixth inventions have a content of (B) of 35 to 75 based on the mass of (I). %, Particularly when (b) is composed of (b1), the viscosity V (mPa · s) of the (I) measured at 25 ° C. by a Brookfield viscometer is within the range of the following formula (1), preferably A polymer polyol composition having a range satisfying both of the following formulas (2) and (3) can be obtained.
V ≦ (Va−Va × C / 10) ＾ [e ＾ x] (1)
V ≦ (Va−Va × C / 10) ＾ [e ＾ y] (2)
V ≧ 0.5 × (Va−Va × C / 10) ＾ [e ＾ y] (3)
However, x = 0.0010354 × Bp ＾ 1.5
y = 0.0009514 × Bp ＾ 1.5
Va: viscosity of (A) at 25 ° C. by Brookfield viscometer (mP
a · s).
C: Content of (C) in (I) (% by mass)
Bp: Content of (B) in (I) (% by mass)
＾: Indicates a power.
e: base of natural logarithm.
[0080]
However, V and Va are measured under the following conditions.

Within the range of the above formula (1), the polymer polyol composition (I) has a better mixability with other raw materials, and the polymer polyol composition has good handleability.
[0081]
The method for producing a polyurethane resin of the seventh invention is a method for producing a polyurethane resin comprising using the polymer polyol composition (I) according to any one of the first to third inventions as at least a part of a polyol component. is there.
In a method of producing a polyurethane resin by reacting a polyol component and a polyisocyanate component, if necessary, in the presence of a foaming agent, a catalyst, a foam stabilizer, and other additives, a polyol component other than the polymer polyol composition of the present invention. If necessary, it can be used in combination with other known active hydrogen atom-containing compounds. As other active hydrogen atom-containing compounds, other high molecular weight polyols or monools (T) and low molecular weight active hydrogen atom-containing compounds (U) commonly used for producing polyurethane can be used.
[0082]
As other polymer polyols or monools (T), polyether polyols, polyester polyols, other various polyols or monols, and mixtures thereof can be used.
Examples of the polyether polyol include those similar to the polyether polyol exemplified in the section of the polyol (A1).
Examples of the polyester polyol include those exemplified as the polyester polyol (A2).
Other polyols or monools other than these include diene polyols such as polybutadiene polyols and hydrogenated products thereof; hydroxyl-containing vinyl polymers such as acrylic polyols; natural oil-based polyols such as castor oil; modification of natural oil-based polyols Compounds: Active hydrogen compounds having terminal-radical polymerizable functional groups described in WO 98/44016 (including monools); polymer polyols other than the present invention can also be used.
[0083]
These other high molecular polyols or monools (T) preferably have 2 to 8, more preferably 3 to 8 hydroxyl groups and usually 200 or more, preferably 300 to 4000, more preferably 400 to 3000 Has a hydroxyl equivalent.
Particularly preferred are polyether polyols.
[0084]
The low molecular weight active hydrogen atom-containing compound (U) has at least 2 (preferably 2 to 3, particularly preferably 2) active hydrogen atoms (hydroxyl group, amino group, mercapto group, etc., preferably hydroxyl group). Compounds having an equivalent per active hydrogen atom of less than 200 (preferably 30 to 180) are exemplified. The molecular weight of (U) is preferably 500 or less, more preferably 60 to 400.
Examples of (U) include low molecular polyols and amino alcohols.
[0085]
Examples of the low molecular polyol include dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, neopentyl glycol, and hexanediol; glycerin, trimethylolpropane, pentaerythritol, diglycerin, α Polyhydric alcohols having 3 to 8 or more valences such as methyl glucoside, sorbitol, xylitol, mannitol, dipentaerythritol, glucose, fructose, sucrose; low molecular weight (for example, 200 to 400) polyhydric alcohol alkylene oxide addition (Polyethylene glycol, polypropylene glycol, etc.); low molecular weight diols having a ring structure, for example, propylene oxide adduct of bisphenol A and the like. It is.
Amino alcohols include mono- or dialkanolamines (such as monoethanolamine, diethanolamine, monopropanolamine).
Preferred among these are low molecular weight polyols, especially diols, specifically ethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol and mixtures of two or more of these. is there.
[0086]
The amount of the polymer polyol composition (I) of the present invention in the polyol component (Z) [(I) and, if necessary, (T) and / or (U)] used for the production of the polyurethane resin is preferably 5% by mass or more. , More preferably at least 10% by mass, particularly preferably at least 20% by mass. When the content is 5% by mass or more, the compression hardness of the foam in the case of urethane foam is easily obtained.
The content of (B) in (Z) is preferably 5 to 75% by mass, more preferably 7 to 55% by mass. Within the above range, both foam hardness and liquid flowability are good.
[0087]
Further, the content of (T) is preferably 0 to 95% by mass, more preferably 0 to 80% by mass. When the (T) is 95% by mass or less, the foam has a high compression hardness.
The content of (U) is preferably 0 to 30% by mass, and more preferably 0 to 10% by mass. When (U) is 30% by mass or less, the exothermic temperature during the reaction does not become too high, and there is no possibility that scorch is generated.
[0088]
As the polyisocyanate component used for producing the polyurethane resin of the seventh invention, a known organic polyisocyanate conventionally used for producing a polyurethane resin can be used.
Examples of such a polyisocyanate include those described above as the polyisocyanate (f).
Preferred among these are 2,4- and 2,6-TDI, mixtures of these isomers, crude TDI; 4,4'- and 2,4'-MDI, mixtures of these isomers, crude MDI; and modified polyisocyanates containing urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, and isocyanurate groups derived from these polyisocyanates.
[0089]
The isocyanate index [equivalent ratio of (NCO group / active hydrogen atom-containing group) × 100] in the production of the polyurethane resin is usually 80 to 140, preferably 85 to 120, and particularly preferably 95 to 115. The polyisocyanurate group can also be introduced into the polyurethane by setting the isocyanate index significantly higher than the above range (for example, 300 to 1000).
[0090]
In producing the polyurethane resin, a catalyst generally used for a polyurethane reaction may be used to accelerate the reaction. For example, amine catalysts [tertiary amines such as triethylenediamine, N-ethylmorpholine, bis-2-dimethylaminoethyl ether; 1,8-diaza-bicyclo [5.4.0] undecene-7 (DBU, manufactured by San-Apro Co.) ); Etc.), tin-based catalysts (stannous octoate, dibutyltin dilaurate, etc.), other metal catalysts (lead octoate, etc.) and isocyanurate-forming catalysts described in US Pat. No. 4,299,924. No. Among them, amine catalysts and / or tin catalysts are preferred.
When a catalyst is used, the amount used is preferably 0.001 to 5% by mass, based on the mass of the reaction mixture.
[0091]
In the production method of the present invention, a polyurethane foam (preferably having an expansion ratio of 5 to 100 times) can be used, if necessary, by using a blowing agent usually used for a polyurethane reaction.
As the foaming agent, at least one selected from hydrogen atom-containing halogenated hydrocarbons, water, low-boiling hydrocarbons, liquefied carbon dioxide and the like is used.
Specific examples of the hydrogen atom-containing halogenated hydrocarbon,
HCFC (hydrochlorofluorocarbon) type (eg, HCFC-123, HCFC-141b, HCFC-22 and HCFC-142b)
HFC (hydrofluorocarbon) type (eg, HFC-134a, HFC-152a, HFC-356mff, HFC-236ea, HFC-245ca, HFC-245fa and HFC-365mfc)
And the like.
Among these, preferred are HCFC-141b, HFC-134a, HFC-356mff, HFC-236ea, HFC-245ca, HFC-245fa, HFC-365mfc, and a combination of two or more thereof.
The low-boiling hydrocarbon is a hydrocarbon having a boiling point of usually -5 to 70 ° C, and specific examples thereof include butane, pentane, cyclopentane, and a mixture thereof.
[0092]
When the halogenated hydrocarbon compound containing a hydrogen atom is used, the amount is usually not more than 50 parts by mass, preferably 5 to 45 parts by mass, per 100 parts by mass of the polyol component (Z).
When the low boiling point hydrocarbon is used, the amount used is usually not more than 45 parts by mass, preferably 5 to 40 parts by mass, per 100 parts by mass of (Z).
When liquefied carbon dioxide gas is used, the amount used is usually not more than 30 parts by mass, preferably 5 to 25 parts by mass, per 100 parts by mass of (Z).
When a hydrogen atom-containing halogenated hydrocarbon is used in combination with water, the amount of the hydrogen atom-containing halogenated hydrocarbon is usually not more than 45 parts by mass, preferably 5 to 40 parts by mass per 100 parts by mass of (Z). And the amount of water used is usually not more than 10 parts by mass, preferably 0.5 to 8 parts by mass, per 100 parts by mass of (Z).
When a low boiling point hydrocarbon and water are used in combination, the amount of the low boiling point hydrocarbon used is usually not more than 40 parts by mass, preferably 2 to 35 parts by mass, per 100 parts by mass of (Z). The amount used is usually not more than 10 parts by mass, preferably 0.5 to 8 parts by mass, per 100 parts by mass of (Z).
When liquefied carbon dioxide and water are used in combination, the amount of liquefied carbon dioxide used is usually not more than 25 parts by mass, preferably 0.1 to 20 parts by mass, per 100 parts by mass of (Z). The amount used is usually not more than 10 parts by mass, preferably 0.5 to 8 parts by mass, per 100 parts by mass of (Z).
When only water is used alone as the blowing agent, the amount of water to be used is generally 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, per 100 parts by mass of (Z).
[0093]
In the method for producing a polyurethane resin or a foam thereof of the present invention, if necessary, the reaction may be carried out in the presence of a foam stabilizer or other additives as described below.
As the foam stabilizer, any one used in the production of ordinary polyurethane foams can be used. Examples thereof include dimethylsiloxane-based foam stabilizers [for example, “SRX-253” manufactured by Toray Dow Corning Silicone Co., Ltd., Shin-Etsu Chemical Co., Ltd. "F-122" manufactured by Kogyo Co., Ltd.], a polyether-modified dimethylsiloxane-based foam stabilizer [for example, "L-5309", "L-3601", "SZ-1311" manufactured by Nippon Unicar Co., Ltd.] And the like, and "F-242T" manufactured by Shin-Etsu Chemical Co., Ltd. and the like].
In addition, colorants (dyes, pigments, carbon black, etc.), plasticizers (phthalates, adipates, etc.), organic fillers (synthetic short fibers, hollow microspheres made of thermoplastic or thermosetting resin, etc.), Inorganic fillers (inorganic salts (calcium carbonate, barium sulfate, etc.), inorganic fibers (glass fibers, carbon fibers, etc.), whiskers (potassium titanate whiskers, etc.), flame retardants (phosphate esters, halogenated phosphate esters) , Melamines, phosphazene derivatives, etc.), antioxidants (triazoles, benzophenones, etc.), antioxidants (hindered phenols, hindered amines, etc.), adhesives (modified polycaprolactone polyol, etc.), internal mold release The reaction can be carried out in the presence of a known additive such as an agent or a bactericide.
[0094]
With respect to the amount of these additives to be used with respect to 100 parts by mass of the polyol component (Z), the foam stabilizer is preferably 10 parts by mass or less, more preferably 0.2 to 5 parts by mass. The colorant is preferably at most 1 part by mass. The amount of the plasticizer is preferably 10 parts by mass or less, more preferably 5 parts by mass or less. The amount of the organic filler is preferably 50 parts by mass or less, more preferably 30 parts by mass or less. The amount of the inorganic filler is preferably 50 parts by mass or less, more preferably 30 parts by mass or less. The amount of the flame retardant is preferably 20 parts by mass or less, more preferably 5 to 15 parts by mass. The antioxidant is preferably 1 part by mass or less, more preferably 0.01 to 0.5 part by mass. The amount of the antioxidant is preferably 1 part by mass or less, more preferably 0.01 to 0.5 part by mass. The above-mentioned additives other than these are preferably 1 part by mass or less.
[0095]
The polyurethane resin can be produced by a usual method, and can be produced by a known method such as a one-shot method, a semi-prepolymer method, a prepolymer method, or the like.
For the production of the polyurethane resin, a commonly used production apparatus can be used. In the case of no solvent, for example, a device such as a kneader or an extruder can be used. For example, various non-foamed or foamed polyurethane resins can be manufactured in a closed mold or an open mold. The pack ratio [(density at the time of mold foaming / density at the time of free foaming) × 100] in the case of producing a foamed polyurethane resin using a closed mold is preferably 110 to 200%.
The production of a polyurethane resin is usually carried out by mixing and reacting raw materials using a low-pressure or high-pressure mechanical device. Further, before and after the mixing of the raw materials (particularly before the mixing of the raw materials), a polyurethane resin can be produced by removing a gas such as dissolved air in the raw materials or air mixed during the mixing by a vacuum method.
[0096]
The polymer polyol obtained by the production method of the present invention is useful for producing a polyurethane foam, particularly a flexible mold foam and a slab foam. Further, the present invention can be applied to molding by RIM (reaction injection molding).
The polyurethane resin produced using the polymer polyol composition of the present invention is used, for example, as a polyurethane foam for interior preparation of automobile interior parts, furniture, and the like. It is also used as a material for sealants and synthetic leather.
[0097]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto. In the following, parts,%, and ratio indicate parts by mass, mass%, and mass ratio, respectively.
[0098]
The compositions and symbols of the raw materials used in the following production examples are as follows.
(1) Unsaturated monofunctional active hydrogen compound (e)
HEMA: 2-hydroxyethyl methacrylate
HEA: 2-hydroxyethyl acrylate
(2) Catalyst for producing reactive dispersant
TBT: Tetrabutyl titanate [manufactured by Nakarai Tesque Co., Ltd.]
(3) Polyisocyanate for production of reactive dispersant (f)
TDI: Coronate T-80 [manufactured by Nippon Polyurethane Co., Ltd.]
(4) Polyol (a)
Polyol (a-1): a polyol having an EO content of 12% and a hydroxyl value of 32 obtained by adding 104 mol of PO on average to pentaerythritol and then adding 19 mol of EO on average.
[0099]
<Production Example 1> Production of reactive dispersant (D1) -1
In a 500 mL four-necked flask equipped with a temperature controller, a stirring blade, and a dropping funnel, 28 parts (0.16 mol) of TDI and 0.01 part of TBT are placed, cooled to 30 ° C., and then 9 parts of HEMA is added. (0.07 mol) was added dropwise over 2 hours. Meanwhile, the reaction temperature was maintained at 40 to 50 ° C. The reaction solution was put into 963 parts (0.14 mol) of polyol (a-1) previously placed in a 1 L four-necked flask equipped with a temperature controller, a stirring blade, and a dropping funnel. Stirred at ~ 90 ° C for 4 hours. After confirming that there was no unreacted isocyanate group in the infrared absorption spectrum, a reactive dispersant (D1-1) was obtained.
The hydroxyl value of (D1-1) was 20, the viscosity was 20,000 mPa · s / 25 ° C., and the ratio of the number of unsaturated groups / the number of nitrogen-containing bonds was 0.22.
[0100]
<Production Example 2> Production of reactive dispersant (D1) -2
Reactive dispersant (D1-2) was prepared in the same manner as in Production Example 1 except that 9 parts of HEMA was replaced with 8 parts (0.07 mol) of HEA and 963 parts of polyol (a-1) was replaced with 964 parts (0.14 mol). ) Got.
The hydroxyl value of (D1-2) was 20, the viscosity was 19,500 mPa · s / 25 ° C., and the ratio of the number of unsaturated groups / the number of nitrogen-containing bonds was 0.22.
[0101]
The compositions, symbols, etc. of the raw materials used in the following Examples and Comparative Examples are as follows.
(5) Polyol (A)
G50: a polyol having a number average molecular weight (hereinafter referred to as Mn) of 3,000 and a hydroxyl value of 56, obtained by adding 50 mol of PO to glycerin, and a viscosity of 500 mPa · s (25 ° C.).
Polyol A11-1: a polyol having an EO content of 15% and a hydroxyl value of 37.5, obtained by adding 64 moles of PO on average to glycerin and then adding 15 moles of EO on average.
Polyol A11-2: A polyol having an EO content of 12% and a hydroxyl value of 32 obtained by adding 104 mol of PO on average to pentaerythritol and then adding 19 mol of EO on average.
Polyol A11-3: A polyol having an EO content of 14% and a hydroxyl value of 28 obtained by adding 118 mol of PO on average to pentaerythritol and then adding 25 mol of EO on average.
Polyol A11-4: a polyol having an EO content of 18% and a hydroxyl value of 37.5 obtained by adding 83 mol of PO on average to pentaerythritol and then adding 24 mol of EO on average.
[0102]
Polyol A12-1: a polyol having an EO content of 70% and a hydroxyl value of 24, obtained by randomly adding 35 mol of PO and 111 mol of EO to glycerin on average.
Polyol A12-2: A polyol having an EO content of 70% and a hydroxyl value of 112 obtained by randomly adding 6 mol of PO and 24 mol of EO to glycerin on average.
(6) Ethylenically unsaturated compound (b2)
AN: Acrylonitrile
St: Styrene
[0103]
(7) Dispersant (D)
SAN: acrylonitrile / styrene = 80/20 mass% copolymer (Mn = 5,000)
GMAP: Equimolar glycidyl methacrylate adduct of polypropylene glycol (Mn = 3,000)
Reactive dispersant (D1-1): Prepared in Production Example 1
Reactive dispersant (D1-2): prepared in Production Example 2
(8) Polymerization initiator
AVN: 2,2'-azobis (2,4-dimethylvaleronitrile)
(9) Organic polyisocyanate
TDI-80: Coronate T-80 [manufactured by Nippon Polyurethane Industry Co., Ltd.]
TM-20: CE-729 [TDI / polymeric MDI = 80/20% by mass; manufactured by Nippon Polyurethane Co., Ltd.]
(10) Catalyst
Catalyst A: Neostan U-28 (stannous octoate) [Nitto Kasei Co., Ltd.]
Catalyst B: DABCO (triethylenediamine) [Nippon Emulsifier Co., Ltd.]
Catalyst C: TEDAL-33 [triethylene diamine / dipropylene glycol = 33/67% by mass solution; manufactured by Tosoh Corporation]
Catalyst D: TOYOCAT ET [bis-2-dimethylaminoethyl ether / dipropylene glycol = 33/67% by mass solution: manufactured by Tosoh Corporation]
(11) Foam stabilizer
F-242T: polyether siloxane polymer [Shin-Etsu Chemical Co., Ltd.]
SZ-1311: polyether siloxane polymer [manufactured by Nippon Unicar Co., Ltd.]
L-5309: polyether siloxane polymer [manufactured by Nippon Unicar Co., Ltd.]
[0104]
The number average molecular weight, degree of unsaturation, viscosity, polyol-soluble polymer, dispersion stability, and polymer particle size were measured as follows.

[0105]
<Unsaturation>
Measured according to the measurement method specified in JIS K-1557.
<Viscosity>
Model: BL viscometer (manufactured by TOKIMEC)
Measurement temperature: 25 ° C
Rotor No: No3 or No4
Number of rotations: Based on the measured viscosity, the viscosity V (mPa · s) is based on the number of rotations described in the description of the equation (1).
[0106]
<Polyol-soluble polymer>
According to the method described above. However, the following preparative liquid chromatograph was used.

[0107]
<Dispersion stability (1)>
The polymer polyol composition placed in a 140 ml glass sealed container (sample bottle) is left in a thermostat at 50 ° C. for 30 days. After standing, the dispersion stability was visually checked.
Evaluation criteria
○ There was no sediment and it was in a uniformly dispersed state.
△ There was a sediment, and after the sample bottle was turned down 5 times, it was uniformly redispersed.
X: There was a precipitate, and the sample bottle was not redispersed after turning over five times.
<Dispersion stability (2)>
The polymer polyol composition contained in a 140 ml glass sealed container (sample bottle) is left in a thermostat at 70 ° C. for 30 days. After standing, the dispersion stability was visually checked.
Evaluation criteria
◎ There was no sediment, and it was in a uniformly dispersed state.
○ There was a sediment, and after the sample bottle was turned down 5 times, it was uniformly redispersed.
X: There was a precipitate, and the sample bottle was not redispersed after turning over five times.
[0108]
<Polymer particle size>
The polymer polyol is diluted with the polyol A11 used so that the transmittance of the laser light is 70 to 90%, and the particle size distribution measuring device (laser diffraction / scattering type particle size distribution measuring device LA-700; manufactured by Horiba, Ltd.) Was measured. The particle diameter corresponding to 50% of the volume-based particle size distribution was defined as the polymer particle diameter (μm).
[0109]
<Example 1> Production of polymer polyol composition-1
SAN: 10 parts and G50: 440 parts were charged into a four-necked flask equipped with a temperature controller, a vacuum stirring blade, a dropping pump, a pressure reducing device, a Dimroth condenser, a nitrogen inlet and an outlet, and after nitrogen replacement, nitrogen was replaced. The temperature was raised to 130 ° C. with stirring under an atmosphere (until the polymerization was completed). Next, a raw material in which 250 parts of an allyl alcohol propylene oxide adduct (Mn = 186, SP = 10.2): 250 parts, AN: 150 parts, St: 100 parts, and G50: 50 parts And AVN: the raw materials obtained by mixing 1 part were continuously dropped simultaneously over 1 hour using a dropping pump, respectively, and polymerized at 130 ° C. for 2 hours. The unreacted monomer was further stripped under reduced pressure to obtain a polymer polyol composition (F-1) having a polymer particle content of 50% and a viscosity of 4000 mPa · s (25 ° C.).
[0110]
<Example 2> Production of polymer polyol composition-2
The same four-necked flask as in Example 1 was charged with 10 parts of SAN and 440 parts of G50. After the replacement with nitrogen, the temperature was raised to 130 ° C. while stirring under a nitrogen atmosphere (until the polymerization was completed). Next, a raw material in which a compound having an acetoacetyl group of the following formula [6] (Mn = 215, SP = 11.5): 200 parts, AN: 150 parts, St: 150 parts was previously mixed, and G50: Raw materials obtained by mixing 50 parts and AVN: 1 part were respectively continuously dropped over 1 hour simultaneously using a dropping pump, and polymerized at 130 ° C. for 2 hours. The unreacted monomer was further stripped under reduced pressure to obtain a polymer polyol composition (F-2) having a polymer particle content of 50% and a viscosity of 4000 mPa · s (25 ° C).
CH₂= C (CH₃) COOCH₂CH₂OCOCH₂COCH₃          [6]
[0111]
<Example 3> Production of polymer polyol composition-3
The same four-necked flask as in Example 1 was charged with 10 parts of SAN and 440 parts of G50. After the replacement with nitrogen, the temperature was raised to 130 ° C. while stirring under a nitrogen atmosphere (until the polymerization was completed). Next, a raw material obtained by previously mixing 50 parts of a compound having a ring-opened lactone chain represented by the following formula [7] (Mn = 300, SP = 10.4), 200 parts of AN, and 250 parts of St: : 50 parts and AVN: 1 part were mixed at the same time and continuously dropped over 1 hour using a dropping pump, and polymerized at 130 ° C for 2 hours. The unreacted monomer was further stripped under reduced pressure to obtain a polymer polyol composition (F-3) having a polymer particle content of 50% and a viscosity of 4,200 mPa · s (25 ° C.).
CH₂= CHCO [O (CH₂)₅CO]₂OH [7]
[0112]
Example 4 Production of Polymer Polyol Composition-4
The same four-necked flask as in Example 1 was charged with 10 parts of SAN and 440 parts of G50. After the replacement with nitrogen, the temperature was raised to 130 ° C. while stirring under a nitrogen atmosphere (until the polymerization was completed). Next, a raw material in which a compound having a succinic acid residue of the following formula [8] (Mn = 230, SP = 11.2): 180 parts and AN: 160 parts, St: 160 parts was previously mixed, and G50 was previously prepared. : 50 parts and AVN: 1 part were mixed at the same time and continuously dropped over 1 hour using a dropping pump, and polymerized at 130 ° C for 2 hours. The unreacted monomer was further stripped under reduced pressure to obtain a polymer polyol composition (F-4) having a polymer particle content of 50% and a viscosity of 4900 mPa · s (25 ° C.).
CH₂= C (CH₃) COOCH₂CH₂OCOCH₂CH₂COOH [8]
[0113]
<Example 5> Production of polymer polyol composition-5
The same four-necked flask as in Example 1 was charged with 10 parts of SAN and 440 parts of G50. After the replacement with nitrogen, the temperature was raised to 130 ° C. while stirring under a nitrogen atmosphere (until the polymerization was completed). Next, a raw material obtained by previously mixing a compound having a phthalic acid residue of the following formula [9] (Mn = 336, SP = 12.0): 250 parts, AN: 150 parts, St: 100 parts, and G50 : 50 parts and AVN: 1 part were mixed at the same time and continuously dropped over 1 hour using a dropping pump, and polymerized at 130 ° C for 2 hours. The unreacted monomer was further stripped under reduced pressure to obtain a polymer polyol composition (F-5) having a polymer particle content of 50% and a viscosity of 5300 mPa · s (25 ° C.).
CH₂= C (CH₃) COOCH₂CH₂OCO (Ph) COOCH₂CH (OH) CH₃
[However, (Ph) is an orthophenylene group] [9]
[0114]
<Example 6> Production of polymer polyol composition-6
Polymer polyol having a polymer particle content of 50% and a viscosity of 3800 mPa · s (25 ° C.) in the same manner as in Example 1 except that 10 parts of SAN of the dispersant is replaced with 10 parts of reactive dispersant (D1-1). A composition (F-6) was obtained.
[0115]
<Example 7> Production of polymer polyol composition-7
Polymer polyol having a polymer particle content of 50% and a viscosity of 3900 mPa · s (25 ° C.) in the same manner as in Example 1 except that SAN: 10 parts of the dispersant is replaced by 10 parts of the reactive dispersant (D1-2). A composition (F-7) was obtained.
[0116]
Example 8 Production of Polymer Polyol Composition-8
Into the same four-neck flask as in Example 1, 10 parts of the reactive dispersant (D1-1), 440 parts of G50 and 80 parts of xylene were charged, and after purging with nitrogen, the mixture was stirred under a nitrogen atmosphere (until the polymerization was completed). While heating, the temperature was raised to 130 ° C. Next, a raw material in which 250 parts of an allyl alcohol propylene oxide adduct (Mn = 186, SP = 10.2): 250 parts, AN: 150 parts, St: 100 parts, and G50: 50 parts And AVN: the raw materials obtained by mixing 1 part were continuously dropped simultaneously over 1 hour using a dropping pump, respectively, and polymerized at 130 ° C. for 2 hours. Water: 20 parts was added to the reaction product, and xylene and unreacted monomers were removed by stripping under reduced pressure at 10 mmHg at 130 ° C. for 3 hours to obtain a polymer having a polymer particle content of 50% and a viscosity of 3100 mPa · s (25 ° C.). A polyol composition (F-8) was obtained.
[0117]
<Examples 9 to 13> Production of polymer polyol composition-9 to 13
According to the composition shown in Table 3, 25% equivalent of polyol was put into a 1 L four-necked flask equipped with a temperature controller, a vacuum stirring blade, a dropping pump, a decompression device, a Dimroth condenser, a nitrogen inlet and an outlet. Then, the mixture was heated to 125 ° C. with stirring, and then the raw material liquid (remaining raw material blended liquid) was continuously dropped by a dropping pump over 4 hours, and the unreacted monomer was stripped under reduced pressure to obtain the polymer of the present invention. Polyol compositions (F-9) to (F-13) were synthesized. Table 3 shows their properties and the like.
[0118]
Comparative Example 1 Production of Comparative Polymer Polyol Composition-1
50:50 parts of G was placed in the same four-necked flask as in Example 1, and heated to 125 ° C. with stirring. Next, a raw material in which 450 parts of St, 300 parts of ACN, 20 parts of GMAP, 680 parts of G50 and 4 parts of AVN were previously mixed was continuously dropped by a dropping pump over 4 hours to polymerize. Further, unreacted monomers were stripped under reduced pressure. A comparative polymer polyol composition (R-1) having a polymer particle content of 50% and a viscosity of 20,000 mPa · s (25 ° C.) was obtained.
[0119]
Comparative Example 2 Production of Comparative Polymer Polyol Composition-2
Using the same apparatus and method as in Comparative Example 1, polymer particle content using 150 parts of G50 and 280 parts of St, 120 parts of AN, 8 parts of GMAP, 442 parts of G50 and 1.6 parts of AVN A comparative polymer polyol composition (R-2) having a viscosity of 40% and a viscosity of 5540 mPa · s (25 ° C.) was obtained.
[0120]
Comparative Example 3 Production of Comparative Polymer Polyol Composition-3
Polymer particle content using the same apparatus and method as in Comparative Example 1, using 175 parts of G50 and 210 parts of St, 90 parts of AN, 6 parts of GMAP, 519 parts of G50 and 1.2 parts of AVN. A comparative polymer polyol composition (R-3) having 30% and a viscosity of 2000 mPa · s (25 ° C.) was obtained.
[0121]
<Comparative Examples 4 to 5> Production of Comparative Polymer Polyol Compositions-4 to 5
According to the composition shown in Table 3, 25% equivalent of polyol was put into a 1 L four-necked flask equipped with a temperature controller, a vacuum stirring blade, a dropping pump, a decompression device, a Dimroth condenser, a nitrogen inlet and an outlet. Then, the mixture was heated to 125 ° C. with stirring, and then the raw material liquid (remaining raw material blended liquid) was continuously dropped by a dropping pump over 4 hours, and the unreacted monomer was further stripped under reduced pressure to obtain a comparative polymer polyol. Compositions (R-4) to (R-5) were synthesized. Table 3 shows their properties and the like.
[0122]
<Examples 1 to 8 and Comparative Examples 1 to 3> Production of polyurethane foam
Using the polymer polyol compositions (F-1 to F-8) and the comparative polymer polyol compositions (R-1 to R-3) of the present invention obtained from Examples 1 to 8 and Comparative Examples 1 to 3. Polyurethane foams were produced at the compounding ratios shown in Tables 1 and 2 by the following foaming formulation. Tables 1 and 2 show the evaluation results of these foam properties. The foaming formulation is as follows.
{Circle around (1)} The temperature of each of the polymer polyol composition and the organic polyisocyanate is adjusted to 25 ± 2 ° C.
{Circle around (2)} A polymer polyol composition, a foam stabilizer, water, and a catalyst are placed in a stainless beaker having a capacity of 1 liter in this order, and stirred and mixed at room temperature (25 ± 2 ° C.). Using a homodisper (manufactured by Tokushu Kika Co., Ltd., stirring condition: 2000 rpm × 6 seconds), the mixture was stirred and foamed.
{Circle around (3)} After the stirring was stopped, the contents were put into a wooden box of 25 × 25 × 10 cm to obtain a polyurethane foam.
[0123]
<Examples 9 to 13 and Comparative Examples 4 to 5> Production of polyurethane foam
Using the comparative polymer polyol composition obtained by the formulation shown in Table 3 and some of the polymer polyol compositions of the present invention, each raw material was stirred and mixed at 25 ± 2 ° C. by the foaming formulation shown in Table 3. A polyurethane resin was manufactured at a mold temperature of 60 ° C. and a curing time of 6 minutes. Table 4 shows the evaluation results of these foam properties.
[0124]
[Table 1]

[0125]
[Table 2]

[0126]
[Table 3]

[0127]
[Table 4]

[0128]
The methods for evaluating foam properties in Tables 1, 2 and 4 are as follows.

Usually, as the physical properties of the urethane foam, the density is preferably in the range of 15 to 50, and the larger the numerical value, the better the 25% ILD, tensile strength, tear strength, cut elongation, rebound resilience, and air permeability. Further, the compression set and wet heat compression set are preferably as small as possible.
[0129]
As is clear from Tables 1 and 2, the polymer polyol compositions of Examples 1 to 8 have a lower viscosity than the polymer polyol composition of Comparative Example 1, and furthermore have a foam property in the case of a polyurethane foam, particularly , 25% ILD (hardness), air permeability and compression set. Further, the tear strength, tensile strength, cut elongation, and rebound resilience were equal or higher. In addition, since the polymer polyol compositions of Comparative Examples 2 and 3 have lower concentrations of polymer particles than the polymer polyol compositions of Examples 1 to 8 and the comparative polymer polyol composition of Comparative Example 1, the viscosity is low. In the case of a foam, the properties of the foam, particularly the 25% ILD (hardness), are remarkably inferior. In general, the higher the concentration of polymer particles, the lower the tensile strength, the elongation at break, the rebound resilience and the air permeability, and the compression set tends to be higher, but the polyurethane using the polymer polyol composition of the present invention tends to be higher. The foams (Examples 1 to 8) show the same or higher foam physical properties as compared to Comparative Example 1 having the same polymer particle concentration.
Furthermore, as is clear from Table 4, the polymer polyol compositions of Examples 9 to 13 have lower viscosities than the polymer polyol compositions of Comparative Examples 4 to 5, and furthermore have foam properties in the case of a polyurethane foam. In particular, the wet heat compression set is excellent.
[0130]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to the polymer polyol composition of this invention and its manufacturing method, even if the density | concentration of a polymer particle is made high compared with the conventional polymer polyol composition, the low viscosity and dispersion stability are obtained very favorable polymer polyol composition. be able to. Therefore, in the production of a polyurethane resin or the like, the working efficiency can be extremely improved. In addition, the polyurethane resin produced by using the polymer polyol composition of the present invention as an essential component of the polyol has the same viscosity as the polymer polyol composition, particularly when the polymer is a polymer of a monomer composed of (b1). In comparison, the case of using the polymer polyol composition of the present invention has a much better 25% ILD (hardness) than the case of using the conventional one. In addition, when the polymer polyol composition of the present invention is used, the 25% ILD of the urethane resin, the air permeability, and the compression set are lower than when the conventional polymer polyol composition having the same polymer particle concentration is used. It can be greatly improved.
In addition, the polymer polyol compositions of the second and third inventions have extremely good dispersion stability as compared with those of the prior art, even when the polymer is a polymer composed of only monomers that are usually used. Polyurethane resin having high hardness and excellent wet heat compression set as compared with the method according to the above method can be produced.
Because of the above-mentioned effects, the polyurethane resin produced by using the polymer polyol composition of the present invention is extremely suitable as a polyurethane foam for uses such as interior parts of automobiles and indoor furniture such as furniture.

Claims (7)

A dispersion medium comprising a polyol (A) or (A) and a diluent (C), and polymer particles (B) dispersed in the dispersion medium, wherein (B) is a dispersion medium and a dispersant (D). Is formed by polymerizing the ethylenically unsaturated compound (b) in the presence or absence of (b), at least 5% by mass of (b) has a number average molecular weight of 160 to 490 and a solubility parameter SP of 9. A polymer polyol composition comprising a terminal ethylenically unsaturated group-containing compound (b1) having 5 to 13. A dispersion medium comprising a polyol (A) or (A) and a diluent (C); and polymer particles (B) dispersed in the dispersion medium, wherein (B) is a dispersion medium and a dispersant (D). Is formed by polymerizing the ethylenically unsaturated compound (b) in the presence or absence of at least 5% by mass of (b) having a number average molecular weight of 160 to 490 and a solubility parameter SP of 9. A polymer polyol composition comprising a terminal ethylenically unsaturated group-containing compound (b1) of 5 to 13, wherein (b1) is at least one member selected from the following (b11) to (b15).
(B11): (poly) oxyalkylene (C2 to C8 alkylene group) ether of terminally unsaturated alcohol (C3 to C24) (b12): Compound (b13) represented by the following general formula [1]: Compound (b14) represented by the following general formula [2]: Compound (b15) represented by the following general formula [3]: Compound represented by the following general formula [4] CH ₂ = CRCOO (AO) kCOCH ₂ COCH ₃ [ 1]
CH ₂ = CRCOO (AO) k [CO (CH ₂ ) sO] m (AO) nH [2]
CH ₂ = CRCO [O (CH ₂ ) sCO] mO (AO) nH [3]
CH ₂ = CRCOO (AO) k [QO (AO) p] r (QO) tH [4]
[Wherein R is a hydrogen atom or a methyl group; A is an alkylene group having 2 to 8 carbon atoms; Q is a residue obtained by removing two OH from dicarboxylic acid; k is a number average molecular weight not exceeding 490 An integer of 1 or more, n and p are 0 or an integer of 1 or more whose number average molecular weight does not exceed 490, s is an integer of 3 to 7, m and r are an integer of 1 or more whose number average molecular weight does not exceed 490, t Is 0 or 1] The content of (B) is 35 to 75% by mass based on the mass of the polymer polyol composition, and the amount of the soluble polymer (P) dissolved in (A) is 5% by mass based on the mass of (A). % Or less. The content of (B) is 35 to 75% by mass based on the mass of the polymer polyol composition, and the viscosity V (mPa · s) measured at 25 ° C. by a Brookfield viscometer is within the range of the following formula (1). The polymer polyol composition according to claim 1, wherein
V ≦ (Va−Va × C / 10) ＾ [e ＾ x] (1)
However, x = 0.0010354 × Bp ＾ 1.5

In the method for producing a polymer polyol composition in which an ethylenically unsaturated compound (b) is polymerized in the polyol (A) in the presence or absence of a dispersant (D) and / or a diluent (C), a number average 2. The polymer polyol according to claim 1, wherein (b) containing 5% by mass or more of the terminal ethylenically unsaturated group-containing compound (b1) having a molecular weight of 160 to 490 and a solubility parameter SP of 9.5 to 13 is used. A method comprising obtaining a composition. The method according to claim 5, wherein the diluent (C) is composed of an aromatic hydrocarbon solvent. The method for producing a foamed or non-foamed polyurethane resin by reacting a polyol component and a polyisocyanate component in the presence or absence of a foaming agent, wherein at least a part of the polyol component according to any one of claims 1 to 4. A method for producing a polyurethane resin, comprising using a polymer polyol composition.