JPWO2017200052A1 - 樹脂組成物、フィルム及び合わせガラス用中間膜 - Google Patents
樹脂組成物、フィルム及び合わせガラス用中間膜 Download PDFInfo
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- JPWO2017200052A1 JPWO2017200052A1 JP2018518360A JP2018518360A JPWO2017200052A1 JP WO2017200052 A1 JPWO2017200052 A1 JP WO2017200052A1 JP 2018518360 A JP2018518360 A JP 2018518360A JP 2018518360 A JP2018518360 A JP 2018518360A JP WO2017200052 A1 JPWO2017200052 A1 JP WO2017200052A1
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- Prior art keywords
- resin
- film
- polyvinyl acetal
- thermoplastic polyolefin
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10605—Type of plasticiser
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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Abstract
Description
比が1/99〜99/1となるように、熱可塑性ポリオレフィン系樹脂(B)に、該樹脂組成物を添加することを特徴とする、ポリビニルアセタール系樹脂組成物の製造方法;を提供することにより達成される。
アルデヒド、ヒドロシンナムアルデヒド、1−ベンズアルデヒド−2−スルホン酸、4−クロロベンズアルデヒド、4−t−ブチルフェニルアセトアルデヒド、2−フェニルプロピオンアルデヒド及びその誘導体等の芳香族アルデヒドと他のアルデヒドを共アセタール化する方法が挙げられる。芳香族アルデヒドと共アセタール化する他のアルデヒドとしては、ホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、n−ブチルアルデヒド、イソブチルアルデヒド、バレルアルデヒド、イソバレルアルデヒド、n−ヘキシルアルデヒド、2−エチルブチルアルデヒド、n−ヘプチルアルデヒド、n−オクチルアルデヒド、2−エチルヘキシルアルデヒド、n−ノニルアルデヒド、n−デシルアルデヒドが挙げられる。全アルデヒドに対する芳香族アルデヒドによる変性量は、0.1モル%以上であることが好ましく、0.5モル%以上であることがより好ましく、1モル%以上であることがさらに好ましい。また、全アルデヒドに対する芳香族アルデヒドによる変性量は、80モル%以下であることが好ましく、40モル%以下であることがより好ましく、20モル%以下であることがさらに好ましい。芳香族アルデヒドによる変性量が0.1モル%以上であると、得られるフィルムの透明性が十分向上し、芳香族アルデヒドによる変性量が80モル%以下であると、製造時におけるポリビニルアセタール樹脂(A’)の水溶性が担保でき、均一なアセタール化物を製造することができる。
単位の割合は、芳香族ビニル重合体ブロック中の全単量体単位に対して、80質量%以上であることが好ましく、95質量%以上であることがより好ましく、98質量%以上であることがさらに好ましい。
する単量体とを共重合させたものであってもよい。該α−オレフィンとしては、エチレン、1−ブテン、1−ペンテン、1−ヘキセン、1−オクテン、4−メチル−1−ペンテン、シクロヘキセンなどが挙げられる。該α−オレフィンは、公知の方法で、前記官能基を有する単量体とを共重合することができ、ランダム共重合、ブロック共重合またはグラフト共重合などの方法が挙げられる。これらプロピレン以外のα−オレフィンを由来とする構造単位の全構造単位に対する割合は、0モル%以上であることが好ましく、45モル%以下であることが好ましく、35モル%以下であることがより好ましく、25モル%以下であることがさらに好ましい。
(B)よりも低い屈折率の化合物(b)) 本発明の樹脂組成物には、熱可塑性ポリオレフィン系樹脂(B)よりも屈折率が低いポリビニルアセタール樹脂(A)以外の化合物(b)を含有することが、透明性に優れるフィルムを得ることができる点で好ましい。化合物(b)は、熱可塑性ポリオレフィン系樹脂(B)への相溶性が、ポリビニルアセタール樹脂(A)への相溶性に比べて高い化合物であることが好ましい。透明性に優れるフィルムを得ることができる点で、化合物(b)は、熱可塑性ポリオレフィン系樹脂(B)への相溶性がポリビニルアセタール樹脂(A)への相溶性に比べて高い化合物であることが好ましい。化合物(b)の熱可塑性ポリオレフィン系樹脂(B)への相溶性がより高いと、ポリビニルアセタール樹脂(A)の連続相中に熱可塑性ポリオレフィン系樹脂(B)の相が島成分として分散している場合に、熱可塑性ポリオレフィン系樹脂(B)相に化合物(b)を含有する割合が大きくなり、結果としてポリビニルアセタール樹脂(A)の相と熱可塑性ポリオレフィン系樹脂(B)の相との屈折率の差が小さくなり、結果として透明性が向上する。透明性が向上する化合物(b)としては、例えば、シリコーンオイルが挙げられる。シリコーンオイルの中でも、ポリシロキサンの側鎖の一部がフェニル基で置換された、メチルフェニルシリコーンオイルが好ましい。メチルフェニルシリコーンオイルとしては、例えば、信越化学工業株式会社製のKF−50−100cs(25℃での屈折率:1.425)、KF−50−300cs(25℃での屈折率:1.425)、KF−50−1,000cs(25℃での屈折率:1.425)、KF−50−3,000cs(25℃での屈折率:1.425)、KF−53(25℃での屈折率:1.485)等が挙げられる。
リセリントリ(リシノール酸)エステル、L−酒石酸ジ(1−(2−エチルヘキシル))、ひまし油の他、ヒドロキシカルボン酸の多価アルコールエステルのk個のヒドロキシカルボン酸由来の基を、水酸基を含まないカルボン酸由来の基または水素原子に置き換えた化合物も使用可能であり、これらヒドロキシカルボン酸エステルは従来公知の方法で得られるものを使用することができる。
pm以上であることが好ましく、100ppm以上であることがより好ましい。また、紫外線吸収剤の添加量は、ポリビニルアセタール樹脂(A)に対して質量基準で50,000ppm以下であることが好ましく、10,000ppm以下であることがより好ましい。紫外線吸収剤の添加量が10ppmより少ないと充分な効果が発揮されにくくなることがあり、また、紫外線吸収剤の添加量を50,000ppmより多くしても格段の効果は望めない。これら紫外線吸収剤は2種以上を組み合わせて用いることもできる。
中間膜は、自動車用フロントガラス、自動車用サイドガラス、自動車用サンルーフ、ヘッドアップディスプレイ用ガラスなどに好適に用いることができる。本発明の積層体の構成を内部に有する合わせガラスが、ヘッドアップディスプレイ用ガラスに適用される場合、用いられる該積層体の断面形状は、一方の端面側が厚く、他方の端面側が薄い形状であることが好ましい。その場合、断面形状は、一方の端面側から他方の端面側に漸次的に薄くなるような、全体が楔形である形状であってもよいし、一方の端面から該端面と他方の端面の間の任意の位置までは同一の厚さで、該任意の位置から他方の端面まで漸次的に薄くなるような、断面の一部が楔形のものであってもよい。
)〜(III)、末端水酸基変性エラストマー(IV)からなる単層シート(厚さ0.76mm)をそれぞれ円板形状の試験シートとして用い、上記試験シートで2枚の平板間の隙間を完全に充填した。なお、試験シートには、温度20℃、湿度60%RHで24時間以上保管したものを用いた。歪み量1.0%で、上記試験シートに1Hzの周波数で振動を与え、測定温度を−40〜100℃まで1℃/minの定速で昇温した。せん断損失弾性率及びせん断貯蔵弾性率の測定値に変化がなくなるまで、上記試験シートと円板の温度を保持した。このようにして、各エラストマーについて、tanδのピーク高さおよびピーク温度を測定した。
表4に示すように可塑剤を使用した以外は、実施例1と同様にして、フィルムを成形した。用いたポリビニルブチラール樹脂組成物の組成と、得られたフィルムの物性評価の結果を表4に示す。
Claims (27)
- ポリビニルアセタール樹脂(A)100質量部に対して熱可塑性ポリオレフィン系樹脂(B)0.5〜100質量部を含み、厚さ0.76±0.03mmのフィルムに成形して厚さ3mmのフロートガラス2枚の間に積層したときのヘイズが5%未満である樹脂組成物。
- 前記ポリビニルアセタール樹脂(A)の連続相中に、前記熱可塑性ポリオレフィン系樹脂(B)の相が島成分として分散している、請求項1に記載の樹脂組成物。
- 前記ポリビニルアセタール樹脂(A)のビニルアルコール単位の含有量が15〜50モル%である、請求項1または2に記載の樹脂組成物。
- 前記ポリビニルアセタール樹脂(A)のビニルアルコール単位の含有量が30〜50モル%である、請求項3に記載の樹脂組成物。
- 前記ポリビニルアセタール樹脂(A)よりも高い屈折率を有する前記熱可塑性ポリオレフィン系樹脂(B)以外の化合物(a)を含む、請求項1〜4のいずれかに記載の樹脂組成物。
- 前記化合物(a)が水酸基を有する、請求項5に記載の樹脂組成物。
- 前記熱可塑性ポリオレフィン系樹脂(B)よりも低い屈折率を有する前記ポリビニルアセタール樹脂(A)以外の化合物(b)を含む、請求項1〜6のいずれかに記載の樹脂組成物。
- 前記ポリビニルアセタール樹脂(A)が、芳香族基を有するポリビニルアセタール樹脂(A’)である、請求項1〜7のいずれかに記載の樹脂組成物。
- 前記熱可塑性ポリオレフィン系樹脂(B)が、芳香族ビニル単量体と、前記芳香族ビニル単量体とは異なるビニル単量体もしくは共役ジエン単量体との共重合体又は該共重合体の水添物である、請求項1〜8のいずれかに記載の樹脂組成物。
- 前記熱可塑性ポリオレフィン系樹脂(B)がブロック共重合体である、請求項9に記載の樹脂組成物。
- 前記熱可塑性ポリオレフィン系樹脂(B)の芳香族ビニル単量体単位の含有量が25質量%以下である、請求項9または10に記載の樹脂組成物。
- 前記熱可塑性ポリオレフィン系樹脂(B)が、カルボキシル基、ボロン酸基、シラノール基、エポキシ基及びイソシアネート基のいずれの官能基も有さない熱可塑性ポリオレフィン系樹脂(B1)である、請求項1〜11のいずれかに記載の樹脂組成物。
- 前記熱可塑性ポリオレフィン系樹脂(B)が、カルボキシル基、ボロン酸基、シラノール基、エポキシ基及びイソシアネート基のいずれの官能基も有さない熱可塑性ポリオレフィン系樹脂(B1)とカルボキシル基、ボロン酸基、シラノール基、エポキシ基及びイソシアネート基からなる群から選ばれる少なくとも一種の官能基を含有する官能基含有ポリオレフィン系重合体(B2)とからなる、請求項1〜11のいずれかに記載の樹脂組成物。
- 前記熱可塑性ポリオレフィン系樹脂(B1)と、前記官能基含有ポリオレフィン系重合体(B2)との含有量の質量比B1/B2が、1/99〜99.9/0.1である、請求項13に記載の樹脂組成物。
- さらに、ポリビニルアセタール樹脂(A)100質量部に対して1〜100質量部の可塑剤を含有する、請求項1〜14のいずれかに記載の樹脂組成物。
- 前記可塑剤の10〜100質量%が水酸基を有する化合物である、請求項15に記載の樹脂組成物。
- 請求項1〜16のいずれかに記載の樹脂組成物を含むフィルム。
- 請求項17に記載のフィルムからなる層を含む合わせガラス用中間膜。
- 前記フィルムからなる層を少なくとも2層含み、さらに前記熱可塑性ポリオレフィン系樹脂(B)を含む樹脂層を含み、該樹脂層の第一の表面に前記フィルムからなる層の一層が配置され、かつ該樹脂層の第二の表面に前記フィルムからなる層の他の一層が配置されてなる、請求項18に記載の合わせガラス用中間膜。
- JIS K 6728に従って測定したビニルアルコール単位の含有量が30〜50モル%であるポリビニルアセタール樹脂(A)を含有する組成物AからなるA層と、熱可塑性ポリオレフィン系樹脂(B)を含有する組成物BからなるB層とを含む合わせガラス用中間膜であって、該合わせガラス用中間膜を溶融混練した後に、厚さ0.76±0.03mmのフィルムに成形して厚さ3mmのフロートガラス2枚の間に積層したときのヘイズが5%未満である、合わせガラス用中間膜。
- ポリビニルアセタール樹脂(A)及びポリビニルアセタール樹脂(A)よりも高い屈折率を有する熱可塑性ポリオレフィン系樹脂(B)以外の化合物(a)を含有する組成物AからなるA層と、熱可塑性ポリオレフィン系樹脂(B)を含有する組成物BからなるB層とを含む合わせガラス用中間膜であって、該合わせガラス用中間膜を溶融混練した後に、厚さ0.76±0.03mmのフィルムに成形して厚さ3mmのフロートガラス2枚の間に積層したときのヘイズが5%未満である、合わせガラス用中間膜。
- ポリビニルアセタール樹脂(A)を含有する組成物AからなるA層と、熱可塑性ポリオレフィン系樹脂(B)及び前記熱可塑性ポリオレフィン系樹脂(B)よりも低い屈折率を有する前記ポリビニルアセタール樹脂(A)以外の化合物(b)を含有する組成物BからなるB層とを含む合わせガラス用中間膜であって、該合わせガラス用中間膜を溶融混練をした後に、厚さ0.76±0.03mmのフィルムに成形して厚さ3mmのフロートガラス2枚の間に積層したときのヘイズが5%未満である、合わせガラス用中間膜。
- 芳香族基で変性されたポリビニルアセタール樹脂(A’)を含むA層と、熱可塑性ポリオレフィン系樹脂(B)を含有するB層とを含む合わせガラス用中間膜であって、該合わせガラス用中間膜を溶融混練した後に、厚さ0.76±0.03mmのフィルムに成形して厚さ3mmのフロートガラス2枚の間に積層したときのヘイズが5%未満である、合わせガラス用中間膜。
- 熱可塑性ポリオレフィン系樹脂(B)がカルボキシル基、ボロン酸基、シラノール基、エポキシ基及びイソシアネート基のいずれの官能基も有さない熱可塑性ポリオレフィン系樹脂(B1)とカルボキシル基、ボロン酸基、シラノール基、エポキシ基及びイソシアネート基からなる群から選ばれる少なくとも一種の官能基を有する熱可塑性ポリオレフィン系樹脂(B2)とからなる、請求項21〜24のいずれかに記載の合わせガラス用中間膜。
- ガラス2枚の間に、請求項18〜24のいずれかに記載の合わせガラス用中間膜が配置されてなる合わせガラス。
- ポリビニルアセタール樹脂(A)と、請求項1〜17のいずれかに記載の樹脂組成物との質量比が1/99〜99/1となるように、ポリビニルアセタール樹脂(A)に、該樹脂組成物を添加することを特徴とする、ポリビニルアセタール系樹脂組成物の製造方法。
- 熱可塑性ポリオレフィン系樹脂(B)と、請求項1〜17のいずれかに記載の樹脂組成物との質量比が1/99〜99/1となるように、熱可塑性ポリオレフィン系樹脂(B)に、該樹脂組成物を添加することを特徴とする、ポリビニルアセタール系樹脂組成物の製造方法。
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MX2020007936A (es) * | 2018-02-02 | 2020-09-03 | Sekisui Chemical Co Ltd | Pelicula intermedia para vidrio laminado y vidrio laminado. |
US20210394491A1 (en) * | 2018-11-30 | 2021-12-23 | Showa Denko Materials Co., Ltd. | Laminated glass for vehicle |
WO2021117835A1 (ja) * | 2019-12-11 | 2021-06-17 | 積水化学工業株式会社 | 樹脂組成物、該樹脂組成物からなる樹脂フィルム、該樹脂フィルムを備えるガラス積層体 |
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