JP3897519B2 - Laminated glass interlayer film and laminated glass - Google Patents

Description

【００８５】
【実施例】
本発明をさらに詳しく説明するため以下に実施例を挙げるが、本発明はこれら実施例のみに限定されるものではない。
なお、実施例において、ＩＴＯとは錫ドープ酸化インジウムを表し、３ＧＯとはトリエチレングリコールジ２−エチルヘキサノエートを表す。
【００８６】
実施例は以下の方法で評価した。
（１）溶液中のＩＴＯ粒度分布
日機装株式会社製マイクロトラックＵＰＡ粒度分析計にて３ＧＯ溶液中におけるＩＴＯ粒子の粒度分布測定を行った。
【００８７】
（２）ＩＴＯ微粒子の膜中分布状態
中間膜の超薄片作製後、以下の透過型電子顕微鏡（ＴＥＭ）を使用して、以下の測定条件でＩＴＯ微粒子の分散状態を撮影、観察した。尚、撮影は３μｍ×４μｍの範囲を×２０，０００倍で撮影し、写真の焼き付けで３倍に引き伸ばした。
ＩＴＯ微粒子の粒径は、上記撮影により得られた写真中のＩＴＯ微粒子の最も長い径とした。また、上記撮影範囲３μｍ×４μｍ中の全ＩＴＯ微粒子の粒子径を測定し、体積換算平均により、平均粒子径を求めた。更に上記撮影範囲中に存在する粒子径１００ｎｍ以上の微粒子数を求め、撮影面積１２μｍ^２で除することにより、１μｍ^２当たりの個数を算出した。
〔装置、測定条件〕
透過型電子顕微鏡
観察装置：透過型電子顕微鏡 日立製作所株式会社製 H-7100FA型
加速電圧：１００ｋＶ
切片作製装置：ウルトラミクロトーム ライカ株式会社製 EM-ULTRACUT・S
：FC−S型 凍結切削システムライカ株式会社製
REICHERT−NISSEI-FCS
ナイフ ：DIATOME株式会社製 DIATOME ULTRA CRYO DRY
【００８８】
（３）合わせガラス特性
（ａ）光学特性
自記分光光度計（商品名「Ｕ４０００」、日立製作所株式会社製）を使用して合わせガラスの３００〜２５００ｎｍの透過率を測定し、ＪＩＳ Ｚ ８７２２およびＪＩＳ Ｒ ３１０６（１９９８）によって３８０〜７８０ｎｍの可視光透過率Ｔｖ、３００〜２５００ｎｍの日射透過率Ｔｓを求めた。
（ｂ）ヘイズ（Ｈ）
ＪＩＳ Ｋ ６７１４に準拠して測定した。
（ｃ）電磁波透過性
ＫＥＣ法測定（電磁波シールド効果試験）によって、１０〜２０００ＭＨｚの範囲の反射損失値（ｄＢ）を通常の板厚２．５ｍｍのフロートガラス単板と比較し、上記周波数での差の最大値（ΔｄＢｍａｘ）をΔｄＢとして記載した。
【００８９】
（ｄ）パンメル値
中間膜のガラスに対する接着性はパンメル値で評価する。その試験方法の詳細は次の通りである。パンメル値が大きいほどガラスとの接着力も大きく、小さいと接着力は小さい。
合わせガラスを−１８±０．６℃の温度に１６時間放置して調整し、これを頭部が０．４５ｋｇのハンマーで打ってガラスの粒径が６ｍｍ以下になるまで粉砕した。ガラスが部分剥離した後の膜の露出度をあらかじめグレード付けした限度見本で判定し、その結果を表２に従いパンメル値として表した。
【表２】

【００９０】
〔実施例１〕
（１）ポリビニルブチラールの合成
純水２８９０gに、平均重合度１７００、鹸化度９９．２モル％のポリビニルアルコール２７５ｇを加えて加熱溶解した。反応系を１５℃に温度調節し、３５重量％の塩酸２０１ｇとｎ−ブチルアルデヒド１５７ｇを加え、この温度を保持して反応物を析出させた。その後、反応系を６０℃で３時間保持して反応を完了させ、過剰の水で洗浄して未反応のｎ−ブチルアルデヒドを洗い流し、塩酸触媒を汎用な中和剤である水酸化ナトリウム水溶液で中和し、さらに、過剰の水で２時間水洗および乾燥を経て、白色粉末状のポリビニルブチラール樹脂を得た。この樹脂の平均ブチラール化度は６８．５モル％であった。
【００９１】
（２）ＩＴＯ分散可塑剤の作製
３ＧＯ４０重量部に対し、ＩＴＯ粉末０．３重量部仕込み、分散剤としてポリリン酸エステル塩を用い、水平型のマイクロビーズミルにて、３ＧＯ中にＩＴＯ微粒子を分散させた。その後、当該溶液にアセチルアセトン０．１重量部を撹拌下で添加し、ＩＴＯ分散可塑剤を作製した。溶液中のＩＴＯ微粒子の平均粒径は３５ｎｍであった。
【００９２】
（３）合わせガラス用中間膜の製造
上記で得られたポリビニルブチラール樹脂１００重量部に対し、上記ＩＴＯ分散可塑剤を４０重量部、さらに全系に対してマグネシウム含有量が６０ｐｐｍとなるよう２−エチル酪酸マグネシウムを適量添加し、ミキシングロールで十分に溶融混練した後、プレス成形機を用いて１５０℃で３０分間プレス成形し、平均膜厚０．７６ｍｍの中間膜を得た。膜中のＩＴＯ微粒子の平均粒径は５６ｎｍであり、粒径が１００ｎｍ以上の粒子は観察されなかった。
【００９３】
（４）合わせガラスの製造
上記で得られた合わせガラス用中間膜を、その両端から透明なフロートガラス（縦３０ｃｍ×横３０ｃｍ×厚さ２．５ｍｍ）で挟み込み、これをゴムバック内に入れ、２．７ｋＰａ（２０ｔｏｒｒ）の真空度で２０分間脱気した後、脱気したままオーブンに移し、さらに９０℃で３０分間保持しつつ真空プレスした。このようにして予備圧着された合わせガラスをオートクレーブ中で１３５℃、圧力１．２ＭＰａ（１２ｋｇ／ｃｍ^２）の条件で２０分間圧着を行い、合わせガラスを得た。得られた合わせガラスを前述の方法で評価した結果、可視光透過率（Ｔｖ）８７．３％、日射透過率（Ｔｓ）６３．２％、ヘイズ（Ｈ）０．５％、電磁波透過性（ΔｄＢ）３、パンメル（Ｐ）５であった。
また可視光透過率８５％、日射透過率７０％、９００〜１３００ｎｍ域での最低分光透過率が５２％である厚さ２．５ｍｍのグリーンガラスを使用して、上記同様合わせガラスを作製し、評価した結果、可視光透過率（Ｔｖ）７６．７％、日射透過率（Ｔｓ）４３．６％、ヘイズ（Ｈ）０．５％であった。
【００９４】
〔実施例２〜１０〕
アセチルアセトンの代わりに，表３〜８に示した化合物を添加しＩＴＯ分散可塑剤を作製したこと以外は実施例１と同様の方法で製膜、評価を行った。実施例７〜１０においては、キレート試薬とカルボン酸化合物を各０．１重量部ずつ添加した。
【００９５】
〔実施例１１〕
合わせガラス用中間膜の製造において、２軸同方向の押し出しのプラストミルにて製膜したこと以外は、実施例８と同様の方法で製膜、評価を行った。
【００９６】
〔実施例１２〜１４〕
合わせガラス用中間膜の製造において、２−エチル酪酸マグネシウムの代わりに、表に示した金属塩を用いたこと以外は実施例８と同様の方法で製膜、評価を行った。
【００９７】
〔実施例１５〜１８〕
キレート試薬および／またはカルボン酸化合物を、樹脂との混練り前のＩＴＯ微粒子を分散させた可塑剤中に添加する代わりに、ミキシングロールに可塑剤、樹脂を投入する際に、同時に化合物単独で添加すること以外は、それぞれ実施例１，４，５，９と同様の方法で製膜、評価を行った。
【００９８】
〔実施例１９〕
可塑剤中でのＩＴＯ微粒子が凝集しており、分散が十分でないＩＴＯ分散可塑剤を用いたこと以外は、実施例１８と同様の方法で製膜、評価を行った。
【００９９】
〔実施例２０〜２３〕
ＩＴＯ粉末を可塑剤に分散させるのに、分散剤としてポリリン酸エステル塩の代わりに、硫酸エステル塩、ポリカルボン酸塩、有機スルホン酸塩、ポリオールエステルを用いたこと以外は、実施例９と同様の方法で行った。
【０１００】
〔実施例２４〜４３〕
ＩＴＯ部数を１．０重量部にしたこと以外は、実施例１〜１９と同様の方法で製膜、評価を行った。実施例４２、４３はともに実施例１９と同様に行った。
【０１０１】
〔実施例４４〕
中間膜製造におけるプレス成形の調製により平均膜厚０．４ｍｍの中間膜を得たこと以外は、実施例３２と同様の方法で製膜、評価を行った。
【０１０２】
〔実施例４５〜４８〕
ＩＴＯ部数を２．０重量部にしたこと以外は、実施例７〜１０と同様の方法で製膜、評価を行った。
【０１０３】
〔比較例１〕
ＩＴＯおよびアセチルアセトンを添加しないこと以外は、実施例１と同様の方法で製膜、評価を行った。
【０１０４】
〔比較例２〕
ＩＴＯ部数を０．０５重量部にしたこと以外は、実施例８と同様の方法で製膜、評価を行った。
【０１０５】
〔比較例３〜５〕
ＩＴＯ部数を５重量部にしたこと以外は、実施例４〜６と同様の方法で製膜、評価を行った。
【０１０６】
〔比較例６〕
アセチルアセトンを添加しないこと以外は、実施例１と同様の方法で製膜、評価を行った。
【０１０７】
〔比較例７〕
アセチルアセトンを添加する代わりに、カルボキシ変性シリコンを添加したこと以外は、実施例１と同様の方法で製膜、評価を行った。
【０１０８】
〔比較例８〕
ＩＴＯ微粒子を可塑剤中により細かく分散させたＩＴＯ分散可塑剤を用いたこと以外は、比較例６と同様の方法で製膜、評価を行った。
【０１０９】
〔比較例９〕
アセチルアセトンを添加しないこと以外は、実施例２４と同様の方法で製膜、評価を行った。
【０１１０】
〔比較例１０〕
ＩＴＯ微粒子を可塑剤中により細かく分散させたＩＴＯ分散可塑剤を用いたこと意外は、比較例９と同様の方法で製膜、評価を行った。
【０１１１】
〔比較例１１〕
アセチルアセトンを添加しないこと以外は、実施例４５と同様の方法で製膜、評価を行った。
【０１１２】
〔比較例１２〕
ＩＴＯを添加しない通常の中間膜（平均厚さ０．７６ｍｍ）を用い合わせガラスを作製する際用いるフロートガラスの１枚を熱線反射ガラスとし、合わせガラスを作製後、評価を行った。
【０１１３】
〔比較例１３〕
ＩＴＯを添加しない通常の中間膜（平均厚さ０．３８ｍｍ）２枚で熱線反射ＰＥＴ（熱線反射コーティングされたポリエチレンテレフタラート）を挟み込み、さらに両端から透明フロートガラスで挟み合わせガラスを作成後、評価を行った。
【０１１４】
【表３】

【０１１５】
【表４】

【０１１６】
【表５】

【０１１７】
【表６】

【０１１８】
【表７】

【０１１９】
【表８】

【０１２０】
〔実施例４９〕
（ポリビニルブチラール樹脂の合成）
純水２８９０ｇに、平均重合度１７００、鹸化度９９．２モル％のポリビニルアルコール２７５ｇを加えて加熱溶解した。反応系を１５℃に温度調節し、３５重量％の塩酸２０１ｇとｎ−ブチルアルデヒド１５７ｇとを加え、この温度を保持して反応物を析出させた。
その後、反応系を６０℃で３時間保持して反応を完了させ、過剰の水で洗浄して未反応のｎ−ブチルアルデヒドを洗い流し、塩酸触媒を汎用な中和剤である水酸化ナトリウム水溶液で中和し、更に、過剰の水で２時間水洗および乾燥を経て、白色粉末状のポリビニルブチラール樹脂を得た。この樹脂の平均ブチラール化度は６８．５モル％であった。
【０１２１】
（分散液の調製）
分散剤として、市販のリン酸エステル塩を可塑剤溶液中で０．５重量％となるよう用いた、ＩＴＯ粒子５重量％を含有する３ＧＯ溶液に、２−エチルヘキサン酸をＩＴＯ１００重量部に対して１０重量部加え、よく撹拌した。得られた３ＧＯ溶液中のＩＴＯ粒子の加熱安定性評価を下記（１）の方法で評価し、結果を表９に示した。
【０１２２】
（合わせガラス用中間膜および合わせガラスの作製）
上記で得られたポリビニルブチラール樹脂１００重量部に、得られた３ＧＯ溶液４１重量部を加えミキシングロールに供給し、混練して得られた混練物をプレス成形機にて１５０℃で３０分間プレス成形し、厚さ０．８ｍｍの中間膜を得た。この中間膜を、２．４ｍｍ厚のフロート板ガラス２枚の間に挟み込み、ロール法で予備接着した。ついで１４０℃のオートクレーブで１．２ＭＰａの圧力で圧着し合わせガラスを得た。得られた合わせガラスの性能を下記（２）、（３）の方法で評価し、結果を表９に示した。
【０１２３】
（１）粒度分布測定
日機装株式会社製マイクロトラックＵＰＡ粒度分析計にて、３ＧＯ溶液中におけるＩＴＯ粒子の粒度分布測定を行った。まず常温で測定し、次に３ＧＯ溶液を２００℃まで加熱した後、常温まで戻して測定を行った。
（２）光学特性
前記と同一の方法で、３８０〜７８０ｎｍの可視光透過率（Ｔｖ）、３００〜２５００ｎｍの日射透過率（Ｔｓ）を評価した。
（３）ヘイズ（Ｈ）
ＪＩＳ Ｋ ６７１４に準拠して測定した。
【０１２４】
〔比較例１４〕
２−エチルヘキサン酸を用いなかったこと以外は、実施例４９と同様の方法で製膜、評価を行った。結果を表９に示した。
【０１２５】
【表９】

【０１２６】
〔実施例５０〕
（１）ポリビニルアセタール樹脂の合成
攪拌装置を備えた反応器に、イオン交換水２８９０ｇ、平均重合度１７００、鹸化度９９．２モル％のポリビニルアルコール２７５ｇを投入し、攪拌しながら加熱溶解した。次に、この溶液を１５℃に温度調節した後、触媒として３５重量％の塩酸２０１ｇおよびアルデヒドとしてｎ−ブチルアルデヒド１５７ｇを加え、この温度を保持した状態で反応物を析出させた。
次いで、反応系の液温を６０℃に昇温し、３時間保持して反応を完了させた。その後、過剰の水で洗浄して未反応のｎ−ブチルアルデヒドを洗い流し、中和剤として水酸化ナトリウム水溶液を加えて塩酸触媒を中和し、さらに、過剰の水で２時間水洗した後、乾燥を行って、白色粉末状のポリビニルブチラール樹脂を得た。得られたポリビニルブチラール樹脂の平均ブチラール化度は６８．５モル％であった。
【０１２７】
（２）錫ドープ酸化インジウム（ＩＴＯ）の可塑剤分散液の作製
可塑剤としてトリエチレングリコールジ２−エチルヘキサノエート（３ＧＯ）を用い、この３ＧＯに対し添加量が１．４重量％となるようにＩＴＯの粉末を添加し、アトライターにて１０時間ＩＴＯを分散させて、ＩＴＯの３ＧＯ分散液を作製した。得られた分散液中のＩＴＯの粒子径は最小粒子径１１ｎｍであり、最大粒子径６０ｎｍであり、重量換算平均粒子径は２０ｎｍであった。
なお、ＩＴＯの粒子径は、光散乱測定装置（商品名「ＤＬＳ−６０００ＡＬ」、大塚電子株式会社製）を使用し、Ａｒレーザーを光源として、動的光散乱法により測定した。
【０１２８】
（３）合わせガラス用中間膜の製造
（１）で得られたポリビニルブチラール樹脂１００重量部に対し、（２）で得られたＩＴＯの３ＧＯ分散液４０重量部を添加混合し、ミキシングロールで十分に溶融混練した後、プレス成形機を用いて１５０℃で３０分間プレス成形を行って、平均膜厚０．７６ｍｍの合わせガラス用中間膜を製造した。
【０１２９】
（４）合わせガラスの製造
（３）で得られた中間膜を３００ｍｍ×３００ｍｍに裁断して、２枚のフロート板ガラス（縦３００ｍｍ×横３００ｍｍ×厚み３ｍｍ）間に挟着し、この挟着物を真空バッグ（ゴムバッグ）に入れて真空度２．７ｋＰａ（２０Ｔｏｒｒ）で２０分間保持して脱気した後、真空にしたままの状態で９０℃のオーブン内に入れ、３０分間保持して予備接着を行った。次いで、予備接着された挟着物を真空バッグから取り出し、オートクレーブ中で温度１５０℃、圧力１．３ＭＰａ（１３ｋｇ／ｃｍ^２）の条件で本接着を行って、合わせガラスを製造した。
【０１３０】
〔実施例５１〕
ＩＴＯの可塑剤分散液の作製において、ＩＴＯの粒子径を最小粒子径１５ｎｍ、最大粒子径８０ｎｍおよび重量換算平均粒子径３０ｎｍとしたこと以外は実施例５０の場合と同様にして、合わせガラス用中間膜および合わせガラスを製造した。
【０１３１】
〔実施例５２〕
ＩＴＯの可塑剤分散液の作製において、最小粒子径１３ｎｍ、最大粒子径７５ｎｍおよび重量換算平均粒子径２５ｎｍのＩＴＯを３ＧＯ（可塑剤）に対し添加量が２．５重量％となるように添加したこと以外は実施例５０の場合と同様にして、合わせガラス用中間膜および合わせガラスを製造した。
【０１３２】
〔実施例５３〕
ＩＴＯの可塑剤分散液の作製において、ＩＴＯのアトライターによる分散時間を５時間として、ＩＴＯの粒子径を最小粒子径３０ｎｍ、最大粒子径１００ｎｍおよび重量換算平均粒子径５０ｎｍとしたこと以外は実施例５０の場合と同様にして、合わせガラス用中間膜および合わせガラスを製造した。
【０１３３】
〔比較例１５〕
合わせガラス用中間膜の製造において、予めＩＴＯの可塑剤分散液を作製することなく、中間膜中のＩＴＯの添加量が０．４重量％となるようにポリビニルブチラール樹脂に対しＩＴＯを直接添加し分散させたこと以外は実施例５０の場合と同様にして、合わせガラス用中間膜および合わせガラスを製造した。得られた中間膜中のＩＴＯの粒子径を透過式電子顕微鏡により直接観察したところ、最小粒子径１０ｎｍ、最大粒子径３０ｎｍおよび個数平均粒子径１５ｎｍであった。
【０１３４】
実施例５０〜実施例５３、および、比較例１５で得られた５種類の合わせガラスの性能｛▲１▼波長３８０〜７８０ｎｍの光線に対する可視光透過率（Ｔｖ）、▲２▼波長３００〜２５００ｎｍの光線に対する日射透過率（Ｔｓ）、▲３▼波長３４０〜１８００ｎｍの光線に対するヘイズ（Ｈ）〔曇価〕、▲４▼周波数１０〜２０００ＭＨｚの電磁波に対する電磁波シールド性（ΔｄＢ）｝を前記測定方法により測定した。その結果は表１０に示すとおりであった。
【０１３５】
【表１０】

【０１３６】
〔実施例５４〕
（１）ポリビニルブチラール樹脂の合成
純水２８９０ｇに、平均重合度１７００、鹸化度９９．２モル％のポリビニルアセタール２７５ｇを加えて加熱溶解した。次に、この溶液反応系を１５℃に温度調節し、３５重量％の塩酸２０１ｇとｎ−ブチルアルデヒド１５７ｇとを加え、この温度を保持した状態で反応物を析出させた。その後、反応系の液温を６０℃で３時間保持して反応を完了させ、過剰の水で洗浄して未反応のｎ−ブチルアルデヒドを洗い流し、塩酸触媒を水酸化ナトリウム水溶液で中和し、さらに、過剰の水で２時間水洗した後、乾燥を行って、白色粉末状のポリビニルブチラール樹脂を得た。得られたポリビニルブチラール樹脂のブチラール化度は６８．５モル％であった。
【０１３７】
（２）添加剤分散液の調製
３ＧＯに１０重量％となるように錫ドープ酸化インジウム粉末を仕込み、同時に分散剤として、平均重合度１７００、鹸化度９９．２モル％のポリビニルアセタールから合成されたブチラール化度６５．３モル％のポリビニルブチラール樹脂粉末を、錫ドープ酸化インジウム１００重量部に対し、５０重量部となるようアトライターに仕込み、１０時間分散させて添加剤分散液を調製した。
【０１３８】
（３）中間膜の製造
上記で得られたポリビニルブチラール樹脂１００重量部に対し、錫ドープ酸化インジウム１．０重量部を分散させた３ＧＯを３９重量部、酢酸マグネシウム２０ｐｐｍおよび２−エチル酪酸マグネシウム４０ｐｐｍを添加し、ミキシングロールで十分に溶融混練した後、プレス成形機を用いて１５０℃で３０分間プレス成形し、膜厚０．７６ｍｍの中間膜を得た。
【０１３９】
（４）合わせガラスの製造
上記で得られた中間膜を、その両側から透明なフロートガラス（縦３０ｃｍ×横３０ｃｍ×厚さ３ｍｍ）で挟み込み、これをゴムバック内に入れ、２．７ｋＰａの真空度で２０分間脱気した後、脱気したままの状態でオーブンに移し、さらに９０℃で３０分間保持して真空プレスした。このようにして予備圧着された合わせガラスを、オートクレーブ内で１３５℃、圧力１．２ＭＰａの条件で２０分間加熱加圧して本接着を行い、合わせガラスを得た。
【０１４０】
（５）評価
（４）で得られた合わせガラスの性能のうち、光学特性、ヘイズ、電磁波透過性、パンメル値については前記記載の方法で評価した。その結果は表１１に示すとおりであった。
【０１４１】
〔耐湿試験後剥離〕
合わせガラスを８０℃、相対湿度９５％の雰囲気下に２週間放置した後、取り出して直ちに、合わせガラス端部の剥離状態を観察した。その結果は表１１に示すとおりであった。
【０１４２】
〔実施例５５〕
中間膜の製造において、錫ドープ酸化インジウム１．０重量部の代わりに、アンチモンドープ酸化錫１．０重量部を用いたこと以外は実施例５４と同様にして合わせガラスを得た。
【０１４３】
〔実施例５６〕
中間膜の製造において、錫ドープ酸化インジウムの添加量を１．６重量部としたこと以外は実施例５４と同様にして合わせガラスを得た。
【０１４４】
〔実施例５７〕
中間膜の製造において、錫ドープ酸化インジウムの添加量を２．８重量部としたこと以外は実施例５４と同様にして合わせガラスを得た。
【０１４５】
〔実施例５８〕
添加剤分散液の調製において、錫ドープ酸化インジウム１００重量部に対し、分散剤として、ポリビニルブチラール樹脂粉末５０重量部の代わりに、カルボキシ変性シリコーンオイル１０重量部を用いたこと以外は実施例５４と同様にして合わせガラスを得た。
【０１４６】
〔比較例１６〕
中間膜の製造において、錫ドープ酸化インジウムを添加しないこと以外は、実施例５４と同様にして合わせガラスを得た。
【０１４７】
〔比較例１７〕
実施例５４において、錫ドープ酸化インジウムを添加せずに中間膜を製造し、透明なフロートガラスの代わりに、錫ドープ酸化インジウムを蒸着したガラスを用いて合わせガラスを得た。
【０１４８】
〔比較例１８〕
実施例５４において、錫ドープ酸化インジウムを添加せずに膜厚０．３８ｍｍの中間膜を製造し、この中間膜２枚の間に錫ドープ酸化インジウムを蒸着した膜厚５０μｍのポリエステルフィルムを挟着したものを用いて合わせガラスを得た。
【０１４９】
〔比較例１９〕
中間膜の製造において、錫ドープ酸化インジウムの添加量を０．０３重量部としたこと以外は実施例５４と同様にして合わせガラスを得た。
【０１５０】
〔比較例２０〕
中間膜の製造において、錫ドープ酸化インジウムの添加量を３．６重量部としたこと以外は実施例５４と同様にして合わせガラスを得た。
【０１５１】
実施例５４〜５８、および、比較例１６〜２０で得られた合わせガラスの性能を実施例５４の場合と同様にして評価した。その結果は表１１に示すとおりであった。
【０１５２】
【表１１】

【０１５３】
【発明の効果】
本発明は、優れた赤外線（熱線）カット機能を有する錫ドープ酸化インジウムまたはアンチモンドープ酸化錫を含むので、優れた遮熱性を有する中間膜を提供できる。
また、錫ドープ酸化インジウムまたはアンチモンドープ酸化錫の平均粒子径が特定の範囲の粒子を添加分散させることによって、優れた遮熱性と透明性を発現する合わせガラスを得るに適する中間膜を提供できる。
さらに、ガラスと中間膜との適正な接着力、耐貫通性、衝撃吸収性、耐候性等の合わせガラスとして必要な基本性能にも優れる合わせガラスを得るに適する中間膜を提供できる。
【０１５４】
本発明の中間膜は、複雑な多層コーティングや保護膜を要さないので、電磁波透過性と透明性に優れる合わせガラスを得るに適すると共に、安価でもある。
【０１５５】
本発明の合わせガラスは、上記本発明の中間膜を用いて作製されるので、優れた遮熱性と電磁波透過性を発現し、且つ、透明性、ガラスと中間膜との適正な接着力、耐貫通性、衝撃吸収性、耐候性等の合わせガラスとして必要な基本性能にも優れる。また、さらに、吸湿による白化が起こりにくい。
【０１５６】
特に、波長３８０〜７８０ｎｍの光線に対する可視光透過率（Ｔｖ）を特定値以上とし、波長３００〜２５００ｎｍの光線に対する日射透過率（Ｔｓ）とヘイズ（Ｈ）および周波数１０〜２０００ＭＨｚの電磁波に対する電磁波シールド性（ΔｄＢ）を特定値以下とすることにより、上記遮熱性、透明性および電磁波透過性は著しく優れたものとなる。
【０１５７】
したがって、本発明の合わせガラスは、自動車のフロントガラス用やサイドガラス用あるいは建築物の窓ガラス用等として好適に用いられる。[0001]
[Technical field to which the invention belongs]
The present invention relates to an interlayer film for laminated glass that is excellent in transparency, heat shielding properties, weather resistance and electromagnetic wave permeability, has excellent adhesion to glass, and does not cause whitening due to moisture absorption, and a laminated glass using the same.
[0002]
[Prior art]
Conventionally, laminated glass has been widely used for windshields and side glasses of automobiles, window glass of buildings, and the like. As a typical example of the laminated glass, an interlayer film for laminated glass composed of a plasticized polyvinyl acetal resin film such as polyvinyl butyral resin plasticized with a plasticizer is interposed between at least two transparent glasses, The one manufactured by integrating is mentioned.
[0003]
In such a laminated glass, when an impact is applied to the glass, the glass is broken, but the intermediate film interposed between the glasses is not easily broken, and the glass remains adhered to the intermediate film even after the breakage. Therefore, the broken pieces are less likely to be scattered, and therefore, a person inside the automobile or the building has a function of preventing injury from the broken pieces of glass.
[0004]
Laminated glass has such an excellent function, but generally has a problem of poor heat shielding properties.
Among light rays, infrared light having a wavelength of 780 nm or more has a small energy amount of about 10% compared to ultraviolet light, but has a large thermal effect and is released as heat when absorbed by a substance, resulting in an increase in temperature. Therefore, it is called hot wire.
Therefore, by blocking the infrared rays (heat rays) entering from the windshield and side glass of the automobile and the infrared rays (heat rays) entering from the window glass of the building, that is, by increasing the heat shielding property of the windshield, side glass or window glass, the automobile. The temperature rise inside and inside the building can be suppressed. As such a heat shielding glass, for example, a heat ray cut glass is commercially available.
[0005]
The heat ray-cut glass has a metal / metal oxide multi-layer coating provided on the surface of a glass plate by metal deposition, sputtering or the like for the purpose of blocking direct sunlight. However, since this multilayer coating is weak against external scratches and inferior in chemical resistance, for example, an interlayer film made of plasticized polyvinyl butyral resin or the like needs to be laminated to form a laminated glass.
[0006]
However, the heat ray-cut glass on which the intermediate film made of the plasticized polyvinyl butyral resin or the like is laminated is (a) expensive, (b) because the multilayer coating is thick, transparency (visible light transmittance) is reduced, (C) The adhesion between the multilayer coating and the intermediate film is reduced, and the intermediate film is peeled off or whitened. (D) Transmission of electromagnetic waves is inhibited, and communication functions such as a mobile phone, a car navigation system, a garage opener, and automatic cash collection. There were problems such as causing trouble.
[0007]
As a solution to such a problem, for example, Japanese Patent Publication No. Sho 61-52093, Japanese Patent Laid-Open Publication No. 64-36442, etc., laminated a metal-deposited polyester film between plasticized polyvinyl butyral resin sheets. Laminated glass has been proposed.
However, this laminated glass has a problem in adhesiveness between the plasticized polyvinyl butyral resin sheet and the polyester film, and not only does the peeling occur at the interface with time, but also the electromagnetic wave transmission is insufficient. was there.
[0008]
Further, for the purpose of imparting heat insulation performance to the intermediate film itself, a laminated glass in which fine particles of a heat insulating inorganic substance are dispersed in the intermediate film layer has also been proposed (for example, JP-A-8-259279). By blocking the infrared rays with these functional fine particles and suppressing the temperature rise of vehicles and buildings, it can be expected to improve the heat insulation.
[0009]
When functional fine particles such as metals and metal oxides are kneaded into the intermediate film, the problem is haze deterioration when laminated glass is used. This deterioration in haze is largely governed by the particle size of the metal and metal oxide in the film. If the particle size is large, the haze also increases. Since the same problem occurs when the functional fine particles are kneaded, a technique for defining the primary particle size has been introduced so far (Japanese Patent No. 2715859).
[0010]
However, in the intermediate film, no matter how much the particle size of the primary particles or the particle size in the dispersion is controlled, the particles are re-aggregated between the particles because they are heated and kneaded with the adhesive resin during film formation. A diameter will become large and will become larger than the particle size of a primary particle or the particle size in a dispersion liquid. That is, in the intermediate film, it is desirable not only to define the primary particles and the particle diameter in the solution, but also to define the particle diameter of the functional fine particles in the film.
[0011]
In addition, since laminated glass typified by laminated glass for automobiles also requires penetration resistance, it is not sufficient as laminated glass even if only haze is sufficient, and it is necessary to appropriately adjust the adhesive strength with glass. It is said. In order to uniformly disperse fine particles such as metals and metal oxides in the intermediate film, a dispersant is required. However, since this dispersant affects the adhesive force, the necessary adhesive force can be obtained. There may not be. That is, the dispersant used when dispersing the fine particles in the plasticizer affects the adhesion between the glass and the interlayer film, resulting in the occurrence of delamination and penetration resistance, and the dispersion of the dispersant. -There was a problem that the adhesive force changed over time due to the -d.
[0012]
[Problems to be solved by the invention]
In view of the above-mentioned conventional problems, the object of the present invention is to exhibit excellent heat shielding properties and electromagnetic wave permeability, transparency, particularly good haze, and appropriate adhesion between glass and interlayer film, resistance to resistance. An object of the present invention is to provide an interlayer film for laminated glass suitable for obtaining a laminated glass excellent in basic performance required as a laminated glass such as penetrability, impact absorbability and weather resistance, and a laminated glass using the interlayer film.
[0013]
Another object of the present invention is to provide an interlayer film for laminated glass that is inexpensive and capable of adjusting the adhesive force, and a laminated glass using the same.
[0014]
  That is, the present invention
(1) tin-doped indium oxide and / or antimony-doped tin oxide having an average particle size exceeding 0 and not exceeding 80 nm is dispersed1 μm of tin-doped indium oxide or antimony-doped tin oxide particles having a particle size of 100 nm or more ² 1 or less per 100 parts by weight of the adhesive resin, and 0.1 to 3.0 parts by weight of tin-doped indium oxide and / or antimony-doped tin oxide is contained, and tin-doped indium oxide and / or antimony It contains one or more dispersants selected from the following group together with doped tin oxideInterlayer film for laminated glass,
(A) β diketones
(B) C2-C18 carboxylic acid
(C) Hydroxycarboxylic acid having 2 to 18 carbon atoms
(2) Plasticizer is contained in adhesive resin(1) characterized in thatAn interlayer film for laminated glass as described in
(3) Adhesive resin is polyvinyl acetal resin(1) or (2) characterized in thatAn interlayer film for laminated glass as described in
(4) Β-diketone is acetylacetone,1) Interlayer film for laminated glass according to
(5) C2-C18carboxylic acidIs 2-ethylbutyric acid or 2-ethylhexanoic acid,1) Interlayer film for laminated glass according to
(6) Dispersion liquid in which tin-doped indium oxide and / or antimony-doped tin oxide is dispersed in an organic solvent with a dispersant.The above (1), characterized in that it is obtained by adding a resin to an adhesive resin containing a plasticizer, melt-kneading and then forming a film.An interlayer film for laminated glass as described in
(7The organic solvent is a plasticizer of the same type as the plasticizer added to the adhesive resin.6) Interlayer film for laminated glass according to
(8)Same as two axesFilm formation by extrusion using a direction extruder(6) or (7), characterized in thatAn interlayer film for laminated glass as described in
(9)DispersionThe average particle diameter of tin-doped indium oxide and / or antimony-doped tin oxide is 10 to 80 nm at room temperature, and 10 to 80 nm even after the dispersion is heated to 200 ° C.As described in said (6) or (7)Interlayer film for laminated glass,
(10) Between at least a pair of glasses,Any of (9)A laminated glass characterized in that the interlayer film for laminated glass described in 1 is interposed and integrated.and
(11) Electromagnetic wave shielding performance ΔdB at 10 to 2000 MHz is 10 dB or less,10)Laminated glass as described in
About.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
The adhesive resin constituting the interlayer film for laminated glass (hereinafter simply referred to as the interlayer film) according to the present invention has its own adhesive property with glass under an appropriate temperature and pressure without applying an adhesive to the surface. Any resin may be used as long as it is a resin, and any known resin used as a base material for an interlayer film for laminated glass is not particularly limited.
Specifically, for example, polyvinyl acetal resin, polyurethane resin, ethylene-vinyl acetate resin, acrylic copolymer resin having acrylic acid or methacrylic acid or a derivative thereof as a structural unit, vinyl chloride-ethylene-glycidyl methacrylate copolymer Resin etc. are mentioned.
These resins can be easily produced by known methods or similar methods.
[0017]
As the adhesive resin used in the present invention, a polyvinyl acetal resin is preferable.
The method for producing the polyvinyl acetal resin is not particularly limited. For example, polyvinyl alcohol is dissolved in warm water, and the obtained aqueous solution is maintained at, for example, about 0 to 95 ° C., and an acid catalyst and an aldehyde are added. There is a method in which the acetalization reaction is completed with stirring, followed by neutralization, washing with water and drying to obtain a polyvinyl acetal resin powder.
Further, in the acetalization reaction, the reaction may be completed by advancing the acetal reaction while stirring and then raising the reaction temperature and aging.
[0018]
In the method for synthesizing the polyvinyl acetal resin, the polyvinyl alcohol preferably has an average degree of polymerization of about 500 to 5000, more preferably about 800 to 3000, and an average degree of polymerization of about 1000 to 2500. Are more preferred.
If the average degree of polymerization of polyvinyl alcohol is less than about 500, the strength of the resin film becomes too weak, and the penetration resistance of the resulting laminated glass may be reduced. Conversely, the average degree of polymerization of polyvinyl alcohol is about If it exceeds about 5000, it may be difficult to mold the resin film, and the strength of the resin film may be too strong, and the impact absorption of the resulting laminated glass may be reduced, and the penetrability may be reduced. Sometimes.
[0019]
Further, the vinyl acetal component of the polyvinyl acetal resin obtained as described above is preferably set to about 30 mol% or less. For this purpose, a polyvinyl alcohol having a saponification degree of about 70 mol% or more is preferably used. When the degree of saponification of polyvinyl alcohol is less than about 70 mol%, the transparency and heat resistance of the polyvinyl acetal resin may be lowered, and the reactivity may also be lowered.
The average degree of polymerization and the degree of saponification of polyvinyl alcohol can be measured, for example, according to JIS K6726 “Testing methods for polyvinyl alcohol”.
[0020]
In the present invention, the aldehyde used for the synthesis of the polyvinyl acetal resin is not particularly limited. For example, an aldehyde having about 3 to 10 carbon atoms, preferably about 4 to 8 carbon atoms is suitably used.
If the carbon number of the aldehyde is less than 3, the moldability of the resin film may be insufficient. Conversely, if the carbon number of the aldehyde exceeds 10, the reactivity during the acetalization reaction decreases, Resin blocks are likely to occur during the reaction, and it may be difficult to synthesize the resin.
[0021]
Specific examples of such aldehydes include, for example, propionaldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, n-hexylaldehyde, 2-ethylbutyraldehyde, n-heptylaldehyde, n-octylaldehyde, n-nonyl. Aliphatic, aromatic, and alicyclic aldehydes such as aldehyde, n-decylaldehyde, benzaldehyde, cinnamaldehyde and the like can be mentioned, and these are preferably used.
These aldehydes may be used alone or in combination of two or more.
[0022]
Among the aldehydes having about 3 to 10 carbon atoms, for example, n-butyraldehyde, n-hexylaldehyde, 2-ethylbutyraldehyde, n-octylaldehyde, etc. having about 4 to 8 carbon atoms are more preferably used. It is done.
[0023]
Among the polyvinyl acetal resins obtained by acetalizing polyvinyl alcohol with an aldehyde having about 4 to 8 carbon atoms, polyvinyl butyral resin obtained by acetalizing polyvinyl alcohol with n-butyraldehyde having 4 carbon atoms is particularly preferable. .
By using the polyvinyl butyral resin, the adhesion of the resin film to the glass is increased, so that the resin film has a more appropriate adhesive force to the glass, and is excellent in transparency, weather resistance, and the like. Butyral resin itself is easy to manufacture.
[0024]
The polyvinyl butyral resin thus obtained is composed of a vinyl butyral component, a vinyl alcohol component, and a vinyl acetate component.
The amount of each component can be measured in accordance with, for example, JIS K-6728 “Testing method for polyvinyl butyral” and infrared absorption spectrum (IR).
In the case of a polyvinyl acetal resin other than the polyvinyl butyral resin, the amount of vinyl alcohol component and the amount of vinyl acetate component are measured, and the remaining amount of vinyl acetal component can be calculated by subtracting the above two component amounts from 100. .
[0025]
The average degree of butyralization of the polyvinyl butyral resin is not particularly limited, but is preferably about 60 to 75 mol%, and more preferably about 62 to 72 mol%.
If the average degree of butyralization of the polyvinyl butyral resin is less than about 60 mol%, the compatibility with the plasticizer described later may be reduced, making it difficult to mix the plasticizer in an amount necessary to ensure penetration resistance. On the other hand, if the average butyralization degree of the polyvinyl butyral resin exceeds about 75 mol%, mechanical properties necessary for ensuring penetration resistance may not be ensured.
[0026]
In the interlayer film according to the present invention, it is necessary that the adhesive resin contains tin-doped indium oxide and / or antimony-doped tin oxide as a material for imparting heat shielding properties.
That is, since tin-doped indium oxide and / or antimony-doped tin oxide has an excellent infrared (heat ray) cutting function, if the substance is added and dispersed in the adhesive resin film, the resulting intermediate film and laminated glass are excellent. The heat shielding property can be expressed.
[0027]
  The amount of the tin-doped indium oxide and / or antimony-doped tin oxide is about 0.1 to 3.0 parts by weight with respect to 100 parts by weight of the adhesive resin described above.Is. Of these, about 0.13 to 3.0 parts by weight is preferable. If the addition amount is less than about 0.1 parts by weight, the effect of infrared shielding is not sufficiently exhibited, so that the heat shielding property of the obtained intermediate film or laminated glass may not be sufficiently improved. If it exceeds the part, the visible light transmittance of the interlayer film or laminated glass obtained may be lowered.
[0028]
  The tin-doped indium oxideOrAntimony-doped tin oxide has an average particle size exceeding 0About 80nmIt is as follows. More preferably, the average particle size is about 10 to 80 nm.
  Especially, the case where a particle diameter exists in the range of about 10-80 nm is more preferable. In other words, the tin-doped indium oxide or antimony-doped tin oxide preferably has a minimum particle size of about 10 nm or more and a maximum particle size of about 80 nm or less.
[0029]
When the average particle diameter of the tin-doped indium oxide or antimony-doped tin oxide exceeds about 200 nm, the visible light scattering by the particles becomes significant, and the transparency of the resulting intermediate film may be impaired. As a result, the haze (cloudiness value) deteriorates when the laminated glass is formed, and it becomes impossible to satisfy the high degree of transparency required for, for example, an automobile windshield.
The particle diameter of the tin-doped indium oxide or antimony-doped tin oxide is determined by dynamic light scattering using a light scattering measurement device (trade name “DLS-6000AL”, manufactured by Otsuka Electronics Co., Ltd.) and using Ar laser as a light source. Measure by the method.
[0030]
  In the present invention, the average particle diameter exceeds 0.About 80nm or lessThe tin-doped indium oxide and / or antimony-doped tin oxide is uniformly finely dispersed in the intermediate film.Yes.By finely dispersing, when laminated glass, it has low haze and excellent transparency, heat insulation is high throughout the interlayer film, and furthermore, the adhesive force between the glass and interlayer film can be adjusted. The penetration resistance is also excellent.
[0031]
  Intermediate film of the present inventionIs a tin-doped indium oxide and / or antimony-doped tin oxide having a particle size of 100 μm or more.²1 or less perTheThat is, when the intermediate film is photographed and observed with a transmission electron microscope, the above particles having a particle diameter of 100 μm or more are not observed, or 1 μm when observed.²When a particle having a particle diameter of 100 μm or more is placed in the center of the frame, the particle size is 1 μm.²In other words, no other particles having a particle diameter of 100 μm or more are observed in the frame.
  In addition, observation with a transmission electron microscope is performed about what was image | photographed with the acceleration voltage of 100 kv using Hitachi Ltd. H-7100FA type | mold transmission electron microscope.
[0032]
Further, as a preferred embodiment of the interlayer film according to the present invention, the average particle diameter of tin-doped indium oxide particles and / or antimony-doped tin oxide particles in the dispersion is 10 to 80 nm at room temperature, and the dispersion Is an interlayer film for laminated glass having a thickness of 10 to 80 nm even after being heated to 200 ° C.
When an interlayer film for laminated glass is formed using such a dispersion, the resulting interlayer film for laminated glass is transparent with low haze, in which tin-doped indium oxide particles and / or antimony-doped tin oxide particles are finely dispersed in the film. Excellent in properties.
Although the dispersion is described in detail later, a suspension or solution in which tin-doped indium oxide particles and / or antimony-doped tin oxide particles are dispersed using an organic solvent or a plasticizer, preferably using a dispersant. Say.
[0033]
  In the present invention, as described above, the tin-doped indium oxide particles and / or antimony-doped tin oxide particles are used in order to produce an intermediate film excellent in transparency, light shielding properties, adhesion to glass, and the like. Evenly finely dispersed in the membraneCageUse a dispersant for thatTheDispersion in the present inventionThe agent (a)β diketones, (B)C2-C18 carboxylic acid, (C)It is a C2-C18 hydroxycarboxylic acid.
[0034]
  In the present invention, it is used as a dispersant.β diketonesIs considered to improve the haze in order to prevent aggregation of tin-doped indium oxide and / or antimony-doped tin oxide particles by coordinating with tin-doped indium oxide and / or antimony-doped tin oxide.
  Theβ diketones areThose with good compatibility with plasticizers or adhesive resins are preferred.ItOf these, acetylacetone is preferably used. In addition to acetylacetone, trifluoroacetylacetone, benzoyltrifluoroacetone, dipivaloylmethane, or the like may be used.
[0035]
  Theβ diketonesIt is preferable to add about 0.001 to 2 parts by weight with respect to 100 parts by weight of the adhesive resin. More preferably, it is about 0.01 to 1 part by weight. If the amount added exceeds about 2 parts by weight, foaming may occur during film formation or foaming may occur during the production of laminated glass. On the other hand, if it is about 0.001 part by weight or less, the effect cannot be expected.
[0036]
  In the present invention, it is used as a dispersant.C2-C18 carboxylic acid or C2-C18 hydroxycarboxylic acidHas a high dispersibility, so that tin-doped indium oxide particles and / or antimony-doped tin oxide particles can be uniformly dispersed in the resin.
  Also, aboveC2-C18 carboxylic acid or C2-C18 hydroxycarboxylic acidBy using this, the dispersibility of tin-doped indium oxide particles and / or antimony-doped tin oxide particles becomes stable even at high temperatures, and even if the intermediate film is heated during molding, tin-doped indium oxide particles and / or antimony-doped tin oxide particles Aggregation or sedimentation of particles does not occur and a good dispersion state is maintained. Therefore, the obtained interlayer film for laminated glass has low haze and excellent transparency.
[0037]
  carboxylic acidExamples thereof include aliphatic carboxylic acids, aliphatic dicarboxylic acids, aromatic carboxylic acids, and aromatic dicarboxylic acids. Specific examples include benzoic acid, phthalic acid, salicylic acid, ricinoleic acid, stearic acid, 2-ethylhexanoic acid, 2-ethylbutyric acid, castor oil fatty acid, or hydrogenated ricinol. These may be used alone or in combination of two or more. Especially, a C2-C18 aliphatic carboxylic acid is preferable and a C2-C10 aliphatic carboxylic acid is more preferable. Specific examples include acetic acid, propionic acid, n-butyric acid, 2-ethylbutyric acid, n-hexanoic acid, 2-ethylhexanoic acid and n-octanoic acid.
[0038]
  the aboveC2-C18 carboxylic acid or C2-C18 hydroxycarboxylic acidAlthough it does not specifically limit as content of, It is preferable to add about 0.001-2 weight part with respect to 100 weight part of adhesive resin. More preferably, it is about 0.01 to 1 part by weight. If the amount added exceeds about 2 parts by weight, the film may be yellowed, and the adhesive force between the glass and the film may be impaired. On the other hand, if it is about 0.001 part by weight or less, the effect cannot be expected.
[0039]
  In addition, as the dispersantC2-C18 carboxylic acid or C2-C18 hydroxycarboxylic acidThe content of is preferably about 0.1 to 300 parts by weight with respect to 100 parts by weight of tin-doped indium oxide particles and / or antimony-doped tin oxide particles.
  If the content is less than about 0.1 parts by weight, tin-doped indium oxide particles and / or antimony-doped tin oxide particles may not be well dispersed in the plasticizer. If it exceeds about 300 parts by weight, the film may turn yellow, or the resulting adhesive strength between the laminated glass interlayer film and the glass may be too low or too high. More preferably, it is about 0.5 to 150 parts by weight.
[0040]
  Also, aboveC2-C18 carboxylic acid or C2-C18 hydroxycarboxylic acidIn addition to being used at the time of dispersion, it may be added after being dispersed with another dispersant, and in any case, dispersion stability at high temperatures can be imparted.
  Moreover, even if it adds at the time of shaping | molding of an intermediate film, the intermediate film for laminated glasses in which the tin dope indium oxide particle and / or the antimony dope tin oxide particle were finely disperse | distributed favorably can be obtained.
[0043]
  As the dispersant in the present invention, the above (a)β diketones,(B)C2-C18 carboxylic acidOr (c)Hydroxycarboxylic acid having 2 to 18 carbon atomsAnd other dispersants can be used in combination. Examples of the other dispersants include, for example, phosphate ester compounds such as phosphate ester salts or polyphosphate ester salts, sulfate ester compounds such as organic sulfonates, polycarboxylates, and polyhydric alcohols such as polyol esters. And dispersants generally used as dispersants for inorganic fine particles, such as type surfactants.
[0044]
In the present invention, it is one of preferred embodiments that the adhesive resin is plasticized with a plasticizer.
The plasticizer used in the present invention may be a plasticizer known per se that is generally used as a plasticizer for an interlayer film, and is not particularly limited, and examples thereof include monobasic acid esters and polybasic acids. Examples thereof include organic plasticizers such as esters, and phosphoric acid plasticizers such as organic phosphoric acid and organic phosphorous acid. These are preferably used.
These plasticizers may be used alone or in combination of two or more.
[0045]
The monobasic acid ester is not particularly limited. For example, triethylene glycol and butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptanoic acid, n-octylic acid, 2-ethylhexylic acid or pelargonic acid (N-nonyl acid), glycol esters obtained by reaction with organic acids such as decyl acid, glycol esters obtained by reaction of tetraethylene glycol or tripropylene glycol with the above organic acids, etc. These are preferably used.
These monobasic esters may be used alone or in combination of two or more.
[0046]
Although it does not specifically limit as polybasic acid ester, For example, by reaction with organic acids, such as adipic acid, sebacic acid, or azelaic acid, and C4-C8 linear or branched alcohol Examples are esters that can be obtained, and these are preferably used.
These polybasic acid esters may be used alone or in combination of two or more.
[0047]
Although it does not specifically limit as an organic phosphoric acid type plasticizer, For example, a tributoxy ethyl phosphate, an isodecyl phenyl phosphate, or a triisopropyl phosphite etc. are mentioned, These are used suitably.
These organophosphate plasticizers may be used alone or in combination of two or more.
[0048]
Among the above various plasticizers, for example, triethylene glycol di-2-ethylhexanoate (3GO), oligoethylene glycol di-2-ethylhexanoate (NGO), tetraethylene glycol di-n-heptanoate (4G7), triethylene glycol, Ethylene glycol di-2-ethylbutyrate (3GH), triethylene glycol di n-heptanoate (3G7) and the like are particularly preferably used.
These plasticizers may be used alone or in combination of two or more.
[0049]
The plasticizer can be easily produced by a method known per se. For example, the plasticizer is produced as follows.
The 3GO can be obtained by reacting triethylene glycol with 2-ethylhexylic acid of about twice the equivalent or more under a catalyst.
NGO can be obtained by reacting oligoethylene glycol with 2-ethylhexylic acid at least twice as much in the presence of a catalyst. Oligoethylene glycol contains about 90% by weight or more of those having 3 to 9 ethylene glycol units, and is commercially available from, for example, Mitsui Toatsu Chemicals, Mitsubishi Chemical, Nisso Chemical Co., Ltd. Yes.
4G7 can be obtained by reacting tetraethylene glycol and n-heptanoic acid at least about twice as much in the presence of a catalyst.
Further, 3GH can be obtained by reacting triethylene glycol and 2-ethylbutyric acid of about 2 equivalents or more under a catalyst.
[0050]
The amount of the plasticizer added to the adhesive resin is not particularly limited, but it is preferably about 20 to 60 parts by weight, more preferably about 100 parts by weight of the adhesive resin. About 30 to 50 parts by weight.
[0051]
If the amount of the plasticizer added relative to 100 parts by weight of the adhesive resin is less than about 20 parts by weight, the impact absorption of the resulting interlayer film or laminated glass may be insufficient, and conversely 100 parts by weight of the adhesive resin. When the added amount of the plasticizer exceeds about 60 parts by weight, the plasticizer bleeds out, the optical distortion of the resulting intermediate film or laminated glass increases, transparency, adhesion between the glass and the intermediate film, etc. May be damaged.
[0052]
The interlayer film for laminated glass of the present invention may contain an adhesive strength adjusting agent as desired.
For example, an alkali metal salt or an alkaline earth metal salt of an organic acid or an inorganic acid is preferably used as the adhesive strength adjusting agent.
It does not specifically limit as said alkali metal salt and alkaline-earth metal salt, For example, salts, such as potassium, sodium, or magnesium, are mentioned. The organic acid is not particularly limited, and examples thereof include carboxylic acids such as octylic acid, hexyl acid, butyric acid, acetic acid, and formic acid. The inorganic acid is not particularly limited, and examples thereof include hydrochloric acid and nitric acid.
These adhesive strength modifiers may be used alone or in combination of two or more.
[0053]
Among the alkali metal salts or alkaline earth metal salts of organic acids or inorganic acids, alkali metal salts or alkaline earth metal salts of organic acids having about 2 to 16 carbon atoms are preferred. More preferably, it is a magnesium salt or potassium salt of a carboxylic acid having 2 to 16 carbon atoms.
The magnesium salt or potassium salt of the carboxylic acid having 2 to 16 carbon atoms is not particularly limited. For example, magnesium acetate, potassium acetate, magnesium propionate, potassium propionate, magnesium 2-ethylbutanoate, potassium 2-ethylbutanoate, Examples include magnesium 2-ethylhexanoate or potassium 2-ethylhexanoate. These may be used alone or in combination of two or more.
[0054]
As the adhesive strength modifier, magnesium salts and potassium salts of carboxylic acids having about 2 to 10 carbon atoms are also preferred.
The magnesium salt of the carboxylic acid having about 2 to 10 carbon atoms is not particularly limited. For example, magnesium acetate, magnesium propanoate, magnesium butanoate, magnesium pentanoate, magnesium hexanoate, magnesium 2-ethylbutyrate, magnesium heptanoate , Magnesium octoate or magnesium 2-ethylhexanoate.
The potassium salt of the carboxylic acid having 2 to 10 carbon atoms is not particularly limited. For example, potassium acetate, potassium propanoate, potassium butanoate, potassium pentanoate, potassium hexanoate, potassium 2-ethylbutyrate, potassium heptanoate, Examples include potassium octoate and potassium 2-ethylhexanoate.
These may be used alone or in combination of two or more, but preferably in combination of two or more. By using two or more of the above-mentioned salts together, the adhesive strength can be adjusted with a small amount.
[0055]
The content of the adhesive strength adjusting agent is preferably about 0.001 to 0.5 parts by weight with respect to 100 parts by weight of the adhesive resin. If it is less than about 0.001 part by weight, the adhesive strength of the peripheral part of the interlayer film for laminated glass may decrease in a high humidity atmosphere. If it exceeds about 0.5 parts by weight, the adhesive strength of the resulting interlayer film for laminated glass becomes too low, and the transparency of the film may be lost. In addition, the moisture resistance of the resulting interlayer film may be reduced.
More preferably, it is about 0.01 to 0.2 parts by weight with respect to 100 parts by weight of the adhesive resin, and the content of magnesium or / and potassium in the intermediate film is about 10 to 150 ppm. If the magnesium or / and potassium content is less than about 10 ppm, the adhesive strength of the peripheral part of the interlayer film for laminated glass may be lowered in a high humidity atmosphere. On the other hand, if it exceeds about 150 ppm, the adhesive strength of the resulting interlayer film for laminated glass becomes too low, and the transparency of the film may be lost. In addition, the moisture resistance of the resulting interlayer film may be reduced.
[0056]
Moreover, you may use together the modified silicone oil currently disclosed by Japanese Patent Publication No.55-29950 as an adhesive force regulator.
However, when a modified silicone oil is used as a dispersant, it is not necessary to add a modified silicone oil as an adhesive strength modifier. When another dispersant is used, the modified silicone oil is used as an adhesive strength modifier. Also good.
The modified silicone oil is generally a viscous liquid obtained by reacting a compound to be modified with polysiloxane. The modified silicone oil is not particularly limited, and examples thereof include carboxyl-modified silicone oil, ether-modified silicone oil, epoxy-modified silicone oil, ester-modified silicone oil, and amine-modified silicone oil. These may be used alone or in combination of two or more.
[0057]
The content of the modified silicone oil is preferably about 0.005 to 0.5 parts by weight with respect to 100 parts by weight of the adhesive resin. If it exceeds about 0.5 parts by weight, the adhesive force between the obtained interlayer film for laminated glass and the glass becomes too low, and peeling, foaming and the like occur. More preferably, it is about 0.02 to 0.2 parts by weight.
[0058]
The method for producing the interlayer film according to the present invention is not particularly limited, and can be performed using a method known per se. For example, if desired, a dispersant, a plasticizer or an adhesion regulator is added to the adhesive resin to disperse tin-doped indium oxide and / or antimony-doped tin oxide, and a resin composition is produced. What is necessary is just to melt-knead and film-form.
As a manufacturing method, the following methods etc. are mentioned, for example.
(Method A) Method of forming a film after melt-kneading a resin composition to which an adhesive resin, tin-doped indium oxide and / or antimony-doped tin oxide, and optionally a dispersant, a plasticizer, or an adhesion regulator are individually added .
(Method B) Adhesive resin and tin-doped indium oxide and / or antimony-doped tin oxide are mixed in advance using a dispersant as desired, and a resin composition to which a plasticizer or adhesion modifier is added is melted as desired. A method of forming a film after kneading.
(Method C) A dispersion in which tin-doped indium oxide and / or antimony-doped tin oxide is dispersed in an organic solvent with a dispersant is added to an adhesive resin containing a plasticizer as required, and melt-kneaded, and then manufactured. How to membrane.
[0059]
Mixing or melt-kneading in the above method can be carried out by an apparatus such as a sand mill, a ball mill, a homogenizer, an attritor, a high-speed rotary stirrer, or an ultrasonic disperser, which is generally used for dispersion and blending of paint.
After melt-kneading, for example, the film may be formed into a sheet by an extrusion method, a calendering method, a pressing method, a casting method, an inflation method, or the like, and this may be used as an intermediate film. Especially, it is preferable to form into a film by the extrusion method using the extruder of a 2 axis same direction.
[0060]
As the method for producing an intermediate film according to the present invention, the C method capable of more uniformly dispersing tin-doped indium oxide and / or antimony-doped tin oxide particles in the resin film is preferable.
In the A method and the B method, tin-doped indium oxide particles and / or antimony-doped tin oxide particles cause reaggregation at the time of melt kneading of the resin composition, and the haze (cloudiness value) of the obtained interlayer film and laminated glass is deteriorated. Sometimes.
[0061]
In the method C, an organic solvent is preferable as a medium in which the tin-doped indium oxide particles and / or antimony-doped tin oxide is dispersed, and an organic solvent that is compatible with the adhesive resin or the dispersant is particularly preferable. In particular, a plasticizer used for the interlayer film according to the present invention or a plasticizer of the same kind is more preferable.
[0062]
As a method for adding and dispersing tin-doped indium oxide and / or antimony-doped tin oxide particles in a dispersion medium, a predetermined amount of tin-doped indium oxide and / or antimony-doped tin oxide particles is used with respect to a predetermined amount of the organic solvent. A method may be employed in which a total amount of the above is added and dispersed, and a predetermined amount of the total amount of tin-doped indium oxide and / or antimony-doped tin oxide is added to and dispersed in a part of the predetermined amount of the organic solvent. First, a dispersion medium master batch of tin-doped indium oxide and / or antimony-doped tin oxide may be prepared, and this may be mixed uniformly with a predetermined amount of the remaining amount of the organic solvent.
[0063]
In addition, as a method for causing the average particle diameter of tin-doped indium oxide and / or antimony-doped tin oxide to exceed 0 and not more than about 80 nm, tin-doped indium oxide having an average particle diameter in the above range and / or A method of adding and dispersing antimony-doped tin oxide in the organic solvent may be adopted, or first, tin-doped indium oxide and / or antimony-doped tin oxide is added and dispersed in the organic solvent. Alternatively, a method of setting the particle diameter of tin-doped indium oxide and / or antimony-doped tin oxide within the above range by using a pulverizing mixer such as an agglomeration machine or the like may be adopted.
[0064]
In addition, the intermediate film according to the present invention may include an ultraviolet absorber, a light stabilizer, an antioxidant, for example, a surfactant such as sodium lauryl sulfate or sodium alkylbenzene sulfonate, as desired, as long as the object of the present invention is not impaired. 1 type, or 2 or more types of various additives generally used for the interlayer film for laminated glasses, such as a coloring agent, may be contained.
What is necessary is just to add in any process of the manufacturing process of the said intermediate film, when mix | blending these additives.
[0065]
Although it does not specifically limit as an ultraviolet absorber, For example, the thing of a benzotriazole type | system | group is preferable, for example, the brand name "Tinubin P", "Tinubin 320" by Ciba Special Chemicals Co., Ltd. , “Tinuvin 326”, “tinuvin 328” and the like.
These ultraviolet absorbers may be used alone or in combination of two or more.
[0066]
Although it does not specifically limit as a light stabilizer, For example, a hindered amine type thing is preferable, for example, Asahi Denka Kogyo Co., Ltd. brand name "ADK STAB LA-57" etc. are mentioned.
These light stabilizers may be used alone or in combination of two or more.
[0067]
Although it does not specifically limit as antioxidant (antiaging agent), For example, a phenol-type thing is preferable, for example, Sumitomo Chemical Co., Ltd. brand name "Sumilyzer BHT" and Ciba Examples include trade name “Irganox 1010” manufactured by Specialty Chemicals Co., Ltd.
These antioxidants (anti-aging agents) may be used alone or in combination of two or more.
[0068]
The surfactant is not particularly limited, and examples thereof include sodium lauryl sulfate and sodium alkylbenzene sulfonate.
These surfactants may be used alone or in combination of two or more.
[0069]
The intermediate film according to the present invention may be used as a single layer or in a state where two or more layers are laminated.
[0070]
The overall average film thickness of the intermediate film according to the present invention is not particularly limited, but in consideration of the minimum necessary penetration resistance, shock absorption, weather resistance, etc. as laminated glass, practically, It is preferably in the range of about 0.2 to 1.6 mm, more preferably in the range of about 0.3 to 0.8 mm, similar to the average film thickness in a normal interlayer film for laminated glass.
[0071]
The laminated glass according to the present invention is formed by integrating the above-described intermediate film according to the present invention between at least a pair of glasses.
However, in order to improve penetration resistance, the intermediate film of the present invention and other intermediate films may be laminated and used as desired.
[0072]
The kind of the glass is not particularly limited, and a commonly used transparent plate glass can be used.
Specifically, for example, various inorganic glasses such as float plate glass, polished plate glass, mold plate glass, mesh plate glass, wire plate glass or colored plate glass, or organic glass such as a polycarbonate plate or a polymethylmethacrylate plate can be used.
These glasses may be used alone or in combination of two or more. Moreover, the thickness of glass should just be selected suitably by a use, and is not specifically limited.
[0073]
The glass used for the laminated glass according to the present invention is preferably a heat ray absorbing glass having a transmittance of about 65% or less in the entire wavelength region of 900 nm to 1300 nm.
Such heat ray absorbing glass preferably has a visible light transmittance of 75% or more at a wavelength of 380 to 780 nm.
This is because the infrared cut property of tin-doped indium oxide or antimony-doped tin oxide is larger on the longer wavelength side than 1300 nm, and relatively small in the region of 900 nm to 1300 nm. Therefore, by combining the interlayer film of the present invention with the heat ray absorbing glass, the solar radiation transmittance can be lowered even for the same visible light transmittance compared to the case of combining with the clear glass, that is, the solar radiation cut rate can be mentioned. it can.
As the heat ray absorbing glass, green glass is preferable. As the green glass, a known glass may be used.
The said heat ray absorption glass may be used for both sides among a pair of glass which pinches | interposes the intermediate film in this invention, and may be used only for one side.
[0074]
The production method of the laminated glass according to the present invention is not particularly limited, and may be the same production method as in the case of ordinary laminated glass. For example, the interlayer film of the present invention is interposed between two transparent glass plates. This is put in a vacuum bag such as a rubber bag, pre-adhered at a temperature of about 70 to 110 ° C. while sucking under reduced pressure, and then at a temperature of about 120 to 150 ° C. using an autoclave or a press. , About 1 to 1.5 MPa (about 10 to 15 kg / cm²The desired laminated glass can be obtained by performing the main adhesion at a pressure of) and integrating them.
[0075]
As a preferable aspect of the laminated glass according to the present invention, the visible light transmittance (Tv) for light with a wavelength of 380 to 780 nm is 65% or more, and the solar light transmittance (Ts) for light with a wavelength of 300 to 2500 nm is the visible light. A laminated glass having a transmittance (Tv) of 80% or less and a haze (H) [cloudiness value] of 1.0% or less.
[0076]
The laminated glass according to the present invention preferably further has an electromagnetic wave shielding property (ΔdB) against an electromagnetic wave having a frequency of 10 to 2000 MHz of 10 dB or less.
[0077]
As another preferable aspect of the laminated glass according to the present invention, the visible light transmittance (Tv) at a wavelength of 380 to 780 nm is 75% or more, and the solar light transmittance (Ts) at 300 to 2500 nm is the visible light transmittance ( A laminated glass having a Tv) of 80% or less, a haze (H) of 1.0% or less, an electromagnetic wave shielding performance (ΔdB) at 10 to 2000 MHz of 10 dB or less, and a Pummel (P) of about 3 to 7 is exemplified. .
[0078]
The visible light transmittance (Tv), the solar radiation transmittance (Ts), the haze (H), and the electromagnetic wave shielding property (ΔdB) mentioned here are the visible light transmittance (Tv) and the solar radiation transmission measured by the following methods, respectively. It means rate (Ts), haze (H), and electromagnetic wave shielding property (ΔdB).
[0079]
[Measurement method of visible light transmittance (Tv)]
Using a self-recording spectrophotometer (trade name “U4000”, manufactured by Hitachi, Ltd.), JIS R-3106 (1998) “Test method for transmittance, reflectance, emissivity, and solar heat gain of plate glass” In conformity, the visible light transmittance (Tv) of the laminated glass with respect to light having a wavelength of 380 to 780 nm is measured.
If the Tv is less than about 65%, the transparency of the laminated glass is small, which is not preferable for practical use.
[0080]
[Measurement method of solar transmittance (Ts)]
Using a self-recording spectrophotometer “U4000”, the solar transmittance (Ts) of the laminated glass with respect to light having a wavelength of 300 to 2500 nm is measured according to JIS R-3106 (1998).
When the Ts exceeds about 80% of the visible light transmittance (Tv), the heat shielding property of the laminated glass is not sufficient.
[0081]
[Measurement method of haze]
Using an integral turbidimeter (manufactured by Tokyo Denshoku), the haze (H) of the laminated glass with respect to light having a wavelength of 340 to 1800 nm is measured according to JIS K-6714 “Methacrylic resin plate for aircraft”.
If the H content exceeds about 1.0%, the transparency of the laminated glass is small, which is not preferable for practical use.
[0082]
[Measurement method of electromagnetic wave shielding property (ΔdB)]
By KEC method (electromagnetic wave shielding effect test method), the reflection loss value (dB) for electromagnetic waves with a frequency of 10 to 2000 MHz is measured for each of laminated glass and ordinary float glass single plate (thickness 3 mm), and the maximum value of the difference between the two Let (ΔdBmax) be an electromagnetic wave shielding property (ΔdB).
When the above ΔdB exceeds about 10 dB, the electromagnetic wave permeability becomes insufficient.
[0083]
[Measurement method of Pummel value]
A laminated glass prepared by allowing it to stand at a temperature of −18 ± 0.6 ° C. for 16 hours was hit with a hammer having a head of 0.45 kg and crushed until the particle diameter of the glass became 6 mm or less. Subsequently, the exposure degree of the intermediate film after partial peeling of the glass was graded in advance. The determination was made with a limit sample, and the result was expressed as a Pummel value according to the determination criteria shown in Table 1 below.
The greater the Pummel value, the greater the adhesion between the interlayer and the glass, and the smaller the Pummel value, the smaller the adhesion between the interlayer and the glass.
[0084]
[Table 1]

[0085]
【Example】
In order to describe the present invention in more detail, examples are given below, but the present invention is not limited to these examples.
In the examples, ITO represents tin-doped indium oxide, and 3GO represents triethylene glycol di-2-ethylhexanoate.
[0086]
Examples were evaluated by the following methods.
(1) ITO particle size distribution in solution
The particle size distribution of the ITO particles in the 3GO solution was measured with a Microtrac UPA particle size analyzer manufactured by Nikkiso Co., Ltd.
[0087]
(2) ITO fine particle distribution in the film
After the production of the ultrathin piece of the intermediate film, the dispersion state of the ITO fine particles was photographed and observed under the following measurement conditions using the following transmission electron microscope (TEM). The image was taken in the 3 μm × 4 μm range at × 20,000 magnification, and was enlarged three times by printing the photo.
The particle diameter of the ITO fine particles was the longest diameter of the ITO fine particles in the photograph obtained by the above photographing. Moreover, the particle diameter of all the ITO fine particles in the said imaging | photography range 3 micrometers x 4 micrometers was measured, and the average particle diameter was calculated | required by the volume conversion average. Further, the number of fine particles having a particle diameter of 100 nm or more existing in the photographing range is obtained, and the photographing area is 12 μm.²1 μm by dividing by²The number per hit was calculated.
[Device and measurement conditions]
Transmission electron microscope
Observation device: Transmission electron microscope H-7100FA, manufactured by Hitachi, Ltd.
Acceleration voltage: 100 kV
Section preparation device: EM-ULTRACUT ・ S made by Ultra Microtome Leica
: FC-S type Freezing cutting system Leica Co., Ltd.
REICHERT-NISSEI-FCS
Knife: DIATOME ULTRA CRYO DRY made by DIATOME
[0088]
(3) Laminated glass characteristics
(A) Optical characteristics
Using a self-recording spectrophotometer (trade name “U4000”, manufactured by Hitachi, Ltd.), the transmittance of laminated glass at 300 to 2500 nm was measured, and visible at 380 to 780 nm according to JIS Z 8722 and JIS R 3106 (1998). The light transmittance Tv and the solar transmittance Ts of 300 to 2500 nm were determined.
(B) Haze (H)
The measurement was performed according to JIS K 6714.
(C) Electromagnetic wave permeability
By the KEC method measurement (electromagnetic wave shielding effect test), the reflection loss value (dB) in the range of 10 to 2000 MHz is compared with a normal float glass single plate having a thickness of 2.5 mm, and the maximum difference (ΔdBmax) at the above frequency. ) As ΔdB.
[0089]
(D) Pummel value
The adhesion of the interlayer film to glass is evaluated by the Pummel value. The details of the test method are as follows. The greater the Pummel value, the greater the adhesion with the glass, and the smaller the Pummel value, the smaller the adhesion.
The laminated glass was adjusted by allowing it to stand at a temperature of −18 ± 0.6 ° C. for 16 hours, and this was crushed with a hammer having a head of 0.45 kg until the particle size of the glass became 6 mm or less. The degree of exposure of the film after partial peeling of the glass was determined using a limit sample that had been graded in advance, and the result was expressed as a Pummel value according to Table 2.
[Table 2]

[0090]
[Example 1]
(1) Synthesis of polyvinyl butyral
To 2890 g of pure water, 275 g of polyvinyl alcohol having an average polymerization degree of 1700 and a saponification degree of 99.2 mol% was added and dissolved by heating. The temperature of the reaction system was adjusted to 15 ° C., 201 g of 35 wt% hydrochloric acid and 157 g of n-butyraldehyde were added, and this temperature was maintained to precipitate the reaction product. Thereafter, the reaction system is maintained at 60 ° C. for 3 hours to complete the reaction, washed with excess water to wash away unreacted n-butyraldehyde, and the hydrochloric acid catalyst is washed with a general-purpose neutralizing agent, sodium hydroxide aqueous solution. The mixture was neutralized, washed with excess water for 2 hours and dried to obtain a white powdery polyvinyl butyral resin. The average butyralization degree of this resin was 68.5 mol%.
[0091]
(2) Preparation of ITO dispersion plasticizer
The ITO fine particles were dispersed in 3GO with a horizontal microbead mill using 0.3 parts by weight of ITO powder with respect to 40 parts by weight of 3GO, using polyphosphate ester salt as a dispersant. Thereafter, 0.1 part by weight of acetylacetone was added to the solution under stirring to produce an ITO dispersion plasticizer. The average particle diameter of the ITO fine particles in the solution was 35 nm.
[0092]
(3) Manufacture of interlayer film for laminated glass
40 parts by weight of the ITO dispersion plasticizer is added to 100 parts by weight of the polyvinyl butyral resin obtained above, and a suitable amount of magnesium 2-ethylbutyrate is added so that the magnesium content is 60 ppm with respect to the entire system. Was sufficiently melt-kneaded and then press molded at 150 ° C. for 30 minutes using a press molding machine to obtain an intermediate film having an average film thickness of 0.76 mm. The average particle diameter of the ITO fine particles in the film was 56 nm, and particles having a particle diameter of 100 nm or more were not observed.
[0093]
(4) Manufacture of laminated glass
The interlayer film for laminated glass obtained above is sandwiched from both ends with transparent float glass (length 30 cm × width 30 cm × thickness 2.5 mm), and this is put into a rubber bag, and 2.7 kPa (20 torr) After deaeration at a vacuum degree for 20 minutes, it was transferred to an oven while being deaerated, and further vacuum-pressed while being kept at 90 ° C. for 30 minutes. The laminated glass preliminarily pressure-bonded in this manner is 135 ° C. and pressure 1.2 MPa (12 kg / cm 2) in an autoclave.²) For 20 minutes to obtain a laminated glass. As a result of evaluating the obtained laminated glass by the above-mentioned method, visible light transmittance (Tv) 87.3%, solar radiation transmittance (Ts) 63.2%, haze (H) 0.5%, electromagnetic wave transmittance ( ΔdB) 3 and Pummel (P) 5.
Moreover, using the green glass of thickness 2.5mm whose visible light transmittance | permeability 85%, solar radiation transmittance | permeability 70%, and the minimum spectral transmittance in 900-1300nm area is 52%, the same laminated glass as above is produced, As a result of the evaluation, the visible light transmittance (Tv) was 76.7%, the solar radiation transmittance (Ts) was 43.6%, and the haze (H) was 0.5%.
[0094]
[Examples 2 to 10]
Film formation and evaluation were performed in the same manner as in Example 1 except that the compounds shown in Tables 3 to 8 were added in place of acetylacetone to produce an ITO dispersion plasticizer. In Examples 7 to 10, 0.1 part by weight of each of the chelating reagent and the carboxylic acid compound was added.
[0095]
Example 11
In the production of the interlayer film for laminated glass, film formation and evaluation were carried out in the same manner as in Example 8, except that the film was formed by a plastmill with two axes in the same direction.
[0096]
[Examples 12 to 14]
In the production of the interlayer film for laminated glass, film formation and evaluation were performed in the same manner as in Example 8 except that the metal salt shown in the table was used instead of 2-ethyl magnesium butyrate.
[0097]
[Examples 15 to 18]
Instead of adding a chelating reagent and / or carboxylic acid compound to a plasticizer in which ITO fine particles before kneading with the resin are dispersed, the compound alone is added at the same time when the plasticizer and resin are added to the mixing roll. Except that, film formation and evaluation were performed in the same manner as in Examples 1, 4, 5, and 9, respectively.
[0098]
Example 19
Film formation and evaluation were performed in the same manner as in Example 18 except that an ITO dispersed plasticizer in which ITO fine particles in the plasticizer were aggregated and dispersion was not sufficient was used.
[0099]
[Examples 20 to 23]
The same as in Example 9 except that, in order to disperse the ITO powder in the plasticizer, sulfate ester salt, polycarboxylate salt, organic sulfonate salt, polyol ester was used instead of polyphosphate salt as the dispersant. It was done by the method.
[0100]
[Examples 24-43]
Film formation and evaluation were performed in the same manner as in Examples 1 to 19 except that the number of ITO parts was 1.0 part by weight. Examples 42 and 43 were performed in the same manner as Example 19.
[0101]
Example 44
Film formation and evaluation were performed in the same manner as in Example 32, except that an intermediate film having an average film thickness of 0.4 mm was obtained by preparation of press molding in the production of the intermediate film.
[0102]
[Examples 45 to 48]
Film formation and evaluation were performed in the same manner as in Examples 7 to 10 except that the number of ITO parts was 2.0 parts by weight.
[0103]
[Comparative Example 1]
Film formation and evaluation were performed in the same manner as in Example 1 except that ITO and acetylacetone were not added.
[0104]
[Comparative Example 2]
Film formation and evaluation were performed in the same manner as in Example 8 except that the number of ITO parts was 0.05 parts by weight.
[0105]
[Comparative Examples 3 to 5]
Film formation and evaluation were performed in the same manner as in Examples 4 to 6, except that the number of ITO parts was 5 parts by weight.
[0106]
[Comparative Example 6]
Film formation and evaluation were performed in the same manner as in Example 1 except that acetylacetone was not added.
[0107]
[Comparative Example 7]
Film formation and evaluation were performed in the same manner as in Example 1 except that carboxy-modified silicon was added instead of adding acetylacetone.
[0108]
[Comparative Example 8]
Film formation and evaluation were performed in the same manner as in Comparative Example 6 except that an ITO dispersed plasticizer in which ITO fine particles were finely dispersed in a plasticizer was used.
[0109]
[Comparative Example 9]
Film formation and evaluation were performed in the same manner as in Example 24 except that acetylacetone was not added.
[0110]
[Comparative Example 10]
Film formation and evaluation were performed in the same manner as in Comparative Example 9 except that an ITO dispersed plasticizer in which ITO fine particles were finely dispersed in a plasticizer was used.
[0111]
[Comparative Example 11]
Film formation and evaluation were performed in the same manner as in Example 45 except that acetylacetone was not added.
[0112]
[Comparative Example 12]
One float glass used when producing a laminated glass using a normal intermediate film (average thickness 0.76 mm) to which ITO was not added was used as a heat ray reflective glass, and evaluation was performed after producing the laminated glass.
[0113]
[Comparative Example 13]
Heat-reflective PET (polyethylene terephthalate coated with heat-reflective coating) is sandwiched between two normal interlayer films (average thickness 0.38 mm) to which ITO is not added. Went.
[0114]
[Table 3]

[0115]
[Table 4]

[0116]
[Table 5]

[0117]
[Table 6]

[0118]
[Table 7]

[0119]
[Table 8]

[0120]
Example 49
(Synthesis of polyvinyl butyral resin)
To 2890 g of pure water, 275 g of polyvinyl alcohol having an average polymerization degree of 1700 and a saponification degree of 99.2 mol% was added and dissolved by heating. The temperature of the reaction system was adjusted to 15 ° C., 201 g of 35% by weight hydrochloric acid and 157 g of n-butyraldehyde were added, and this temperature was maintained to precipitate the reaction product.
Thereafter, the reaction system is maintained at 60 ° C. for 3 hours to complete the reaction, washed with excess water to wash away unreacted n-butyraldehyde, and the hydrochloric acid catalyst is washed with a general-purpose neutralizing agent, sodium hydroxide aqueous solution. The mixture was neutralized, washed with excess water for 2 hours and dried to obtain a white powdery polyvinyl butyral resin. The average butyralization degree of this resin was 68.5 mol%.
[0121]
(Preparation of dispersion)
As a dispersant, a commercially available phosphate ester salt was used in a plasticizer solution so as to be 0.5% by weight, in a 3GO solution containing 5% by weight of ITO particles, 2-ethylhexanoic acid was added to 100 parts by weight of ITO. 10 parts by weight were added and stirred well. The heat stability evaluation of the ITO particles in the obtained 3GO solution was evaluated by the method (1) below, and the results are shown in Table 9.
[0122]
(Production of interlayer film for laminated glass and laminated glass)
41 parts by weight of the obtained 3GO solution is added to 100 parts by weight of the polyvinyl butyral resin obtained above, the mixture is supplied to a mixing roll, and the kneaded product obtained by kneading is press molded at 150 ° C. for 30 minutes. An intermediate film having a thickness of 0.8 mm was obtained. This interlayer film was sandwiched between two sheets of float plate glass having a thickness of 2.4 mm and preliminarily adhered by a roll method. Subsequently, it was pressure-bonded at a pressure of 1.2 MPa with a 140 ° C. autoclave to obtain a laminated glass. The performance of the obtained laminated glass was evaluated by the methods (2) and (3) below, and the results are shown in Table 9.
[0123]
(1) Particle size distribution measurement
The particle size distribution of the ITO particles in the 3GO solution was measured with a Nikkiso Microtrack UPA particle size analyzer. First, measurement was performed at room temperature, and then the 3GO solution was heated to 200 ° C. and then returned to room temperature for measurement.
(2) Optical characteristics
The visible light transmittance (Tv) of 380 to 780 nm and the solar radiation transmittance (Ts) of 300 to 2500 nm were evaluated by the same method as described above.
(3) Haze (H)
The measurement was performed according to JIS K 6714.
[0124]
[Comparative Example 14]
Film formation and evaluation were performed in the same manner as in Example 49 except that 2-ethylhexanoic acid was not used. The results are shown in Table 9.
[0125]
[Table 9]

[0126]
Example 50
(1) Synthesis of polyvinyl acetal resin
A reactor equipped with a stirrer was charged with 2890 g of ion-exchanged water, 275 g of polyvinyl alcohol having an average degree of polymerization of 1700 and a saponification degree of 99.2 mol%, and was heated and dissolved while stirring. Next, after the temperature of this solution was adjusted to 15 ° C., 201 g of 35 wt% hydrochloric acid as a catalyst and 157 g of n-butyraldehyde as an aldehyde were added, and the reaction product was precipitated while maintaining this temperature.
Subsequently, the liquid temperature of the reaction system was raised to 60 ° C. and held for 3 hours to complete the reaction. Thereafter, washing with excess water is performed to wash away unreacted n-butyraldehyde, a sodium hydroxide aqueous solution is added as a neutralizing agent to neutralize the hydrochloric acid catalyst, and further washing with excess water for 2 hours is followed by drying. To obtain a white powdery polyvinyl butyral resin. The average degree of butyralization of the obtained polyvinyl butyral resin was 68.5 mol%.
[0127]
(2) Preparation of tin-doped indium oxide (ITO) plasticizer dispersion
Using triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer, add ITO powder so that the addition amount is 1.4% by weight with respect to this 3GO. By dispersing, a 3GO dispersion of ITO was prepared. The particle diameter of ITO in the obtained dispersion was a minimum particle diameter of 11 nm, a maximum particle diameter of 60 nm, and an average particle diameter in terms of weight was 20 nm.
The particle diameter of ITO was measured by a dynamic light scattering method using a light scattering measuring device (trade name “DLS-6000AL”, manufactured by Otsuka Electronics Co., Ltd.) and using an Ar laser as a light source.
[0128]
(3) Manufacture of interlayer film for laminated glass
To 100 parts by weight of the polyvinyl butyral resin obtained in (1), 40 parts by weight of the ITO 3GO dispersion obtained in (2) is added and mixed, and after sufficiently melt-kneaded with a mixing roll, a press molding machine is used. Using this, press molding was carried out at 150 ° C. for 30 minutes to produce an interlayer film for laminated glass having an average film thickness of 0.76 mm.
[0129]
(4) Manufacture of laminated glass
The intermediate film obtained in (3) is cut into 300 mm × 300 mm, and sandwiched between two float plate glasses (length 300 mm × width 300 mm × thickness 3 mm), and the sandwiched product is attached to a vacuum bag (rubber bag). Then, after deaeration by holding for 20 minutes at a degree of vacuum of 2.7 kPa (20 Torr), it was placed in an oven at 90 ° C. in a vacuum state and pre-adhered by holding for 30 minutes. Next, the pre-bonded sandwich was taken out of the vacuum bag, and the temperature was 150 ° C. and the pressure was 1.3 MPa (13 kg / cm 3) in an autoclave.²This bonding was performed under the conditions of) to produce a laminated glass.
[0130]
Example 51
In the production of the ITO plasticizer dispersion, the intermediate particle for laminated glass was prepared in the same manner as in Example 50 except that the ITO particle size was 15 nm, the maximum particle size was 80 nm, and the weight-average particle size was 30 nm. Membranes and laminated glass were produced.
[0131]
Example 52
In the production of the ITO plasticizer dispersion, ITO having a minimum particle diameter of 13 nm, a maximum particle diameter of 75 nm, and a weight-converted average particle diameter of 25 nm was added to 3 GO (plasticizer) so that the addition amount was 2.5% by weight. Except that, an interlayer film for laminated glass and a laminated glass were produced in the same manner as in Example 50.
[0132]
Example 53
In the preparation of the ITO plasticizer dispersion, the dispersion time of the ITO attritor was set to 5 hours, and the ITO particle size was set to a minimum particle size of 30 nm, a maximum particle size of 100 nm, and a weight-converted average particle size of 50 nm. In the same manner as in the case of No. 50, an interlayer film for laminated glass and a laminated glass were produced.
[0133]
[Comparative Example 15]
In the production of the interlayer film for laminated glass, ITO is directly added to the polyvinyl butyral resin so that the added amount of ITO in the interlayer film becomes 0.4% by weight without preparing a plasticizer dispersion of ITO in advance. An interlayer film for laminated glass and a laminated glass were produced in the same manner as in Example 50 except that the dispersion was performed. When the particle diameter of ITO in the obtained intermediate film was directly observed with a transmission electron microscope, the minimum particle diameter was 10 nm, the maximum particle diameter was 30 nm, and the number average particle diameter was 15 nm.
[0134]
Performance of the five types of laminated glass obtained in Example 50 to Example 53 and Comparative Example 15 {1} Visible light transmittance (Tv) for light with a wavelength of 380 to 780 nm, {circle around (2)} Wavelength of 300 to 2500 nm The solar radiation transmittance (Ts) with respect to the light beam, (3) haze (H) [cloudiness value] with respect to the light beam having a wavelength of 340 to 1800 nm, and (4) electromagnetic wave shielding property (ΔdB) with respect to the electromagnetic wave with a frequency of 10 to 2000 MHz. It was measured by. The results are shown in Table 10.
[0135]
[Table 10]

[0136]
Example 54
(1) Synthesis of polyvinyl butyral resin
275 g of polyvinyl acetal having an average polymerization degree of 1700 and a saponification degree of 99.2 mol% was added to 2890 g of pure water and dissolved by heating. Next, the temperature of the solution reaction system was adjusted to 15 ° C., and 201 g of 35% by weight hydrochloric acid and 157 g of n-butyraldehyde were added to precipitate the reaction product while maintaining this temperature. Thereafter, the reaction temperature is maintained at 60 ° C. for 3 hours to complete the reaction, washing with excess water to wash away unreacted n-butyraldehyde, neutralizing the hydrochloric acid catalyst with aqueous sodium hydroxide, Further, after washing with excess water for 2 hours, drying was performed to obtain a white powdery polyvinyl butyral resin. The degree of butyralization of the obtained polyvinyl butyral resin was 68.5 mol%.
[0137]
(2) Preparation of additive dispersion
A tin-doped indium oxide powder was added to 3GO to 10 wt%, and at the same time, a butyralization degree of 65.3 mol% synthesized from polyvinyl acetal having an average polymerization degree of 1700 and a saponification degree of 99.2 mol% was used as a dispersant. The polyvinyl butyral resin powder was charged into an attritor so as to be 50 parts by weight with respect to 100 parts by weight of tin-doped indium oxide, and dispersed for 10 hours to prepare an additive dispersion.
[0138]
(3) Production of interlayer film
39 parts by weight of 3GO in which 1.0 part by weight of tin-doped indium oxide is dispersed, 20 ppm of magnesium acetate and 40 ppm of 2-ethylbutyrate are added to 100 parts by weight of the polyvinyl butyral resin obtained above. After sufficiently melt-kneading, it was press molded at 150 ° C. for 30 minutes using a press molding machine to obtain an interlayer film having a thickness of 0.76 mm.
[0139]
(4) Manufacture of laminated glass
The intermediate film obtained above was sandwiched by transparent float glass (length 30 cm × width 30 cm × thickness 3 mm) from both sides, placed in a rubber bag, and deaerated at a vacuum degree of 2.7 kPa for 20 minutes. Then, it moved to oven in the state deaerated, and also hold | maintained at 90 degreeC for 30 minutes, and vacuum-pressed. The laminated glass preliminarily pressure-bonded in this manner was heated and pressed for 20 minutes in an autoclave under conditions of 135 ° C. and a pressure of 1.2 MPa to obtain a laminated glass.
[0140]
(5) Evaluation
Among the performances of the laminated glass obtained in (4), optical properties, haze, electromagnetic wave permeability, and Pummel values were evaluated by the methods described above. The results were as shown in Table 11.
[0141]
[Peeling after moisture resistance test]
The laminated glass was left in an atmosphere of 80 ° C. and relative humidity of 95% for 2 weeks, then taken out and immediately observed at the edge of the laminated glass. The results were as shown in Table 11.
[0142]
Example 55
In the production of the interlayer film, a laminated glass was obtained in the same manner as in Example 54 except that 1.0 part by weight of antimony-doped tin oxide was used instead of 1.0 part by weight of tin-doped indium oxide.
[0143]
Example 56
In the production of the interlayer film, a laminated glass was obtained in the same manner as in Example 54 except that the amount of tin-doped indium oxide added was 1.6 parts by weight.
[0144]
Example 57
In the production of the intermediate film, a laminated glass was obtained in the same manner as in Example 54 except that the amount of tin-doped indium oxide added was 2.8 parts by weight.
[0145]
Example 58
In the preparation of the additive dispersion, Example 54 and Example 54 were used except that 10 parts by weight of carboxy-modified silicone oil was used as a dispersant instead of 50 parts by weight of polyvinyl butyral resin powder with respect to 100 parts by weight of tin-doped indium oxide. A laminated glass was obtained in the same manner.
[0146]
[Comparative Example 16]
In the production of the intermediate film, a laminated glass was obtained in the same manner as in Example 54 except that tin-doped indium oxide was not added.
[0147]
[Comparative Example 17]
In Example 54, an interlayer film was produced without adding tin-doped indium oxide, and a laminated glass was obtained using a glass on which tin-doped indium oxide was deposited instead of transparent float glass.
[0148]
[Comparative Example 18]
In Example 54, an intermediate film having a thickness of 0.38 mm was manufactured without adding tin-doped indium oxide, and a 50 μm-thick polyester film in which tin-doped indium oxide was evaporated was sandwiched between the two intermediate films. A laminated glass was obtained using the obtained one.
[0149]
[Comparative Example 19]
In the production of the interlayer film, a laminated glass was obtained in the same manner as in Example 54 except that the amount of tin-doped indium oxide added was 0.03 part by weight.
[0150]
[Comparative Example 20]
In the production of the interlayer film, a laminated glass was obtained in the same manner as in Example 54 except that the addition amount of tin-doped indium oxide was 3.6 parts by weight.
[0151]
The performance of the laminated glasses obtained in Examples 54 to 58 and Comparative Examples 16 to 20 was evaluated in the same manner as in Example 54. The results were as shown in Table 11.
[0152]
[Table 11]

[0153]
【The invention's effect】
Since the present invention includes tin-doped indium oxide or antimony-doped tin oxide having an excellent infrared (heat ray) cutting function, an intermediate film having excellent heat shielding properties can be provided.
Moreover, an intermediate film suitable for obtaining a laminated glass exhibiting excellent heat shielding properties and transparency can be provided by adding and dispersing particles having an average particle size of tin-doped indium oxide or antimony-doped tin oxide in a specific range.
Furthermore, the intermediate film suitable for obtaining the laminated glass excellent also in the basic performance required as laminated glass, such as appropriate adhesive strength of glass and an intermediate film, penetration resistance, shock absorption property, and weather resistance can be provided.
[0154]
Since the intermediate film of the present invention does not require a complicated multilayer coating or protective film, it is suitable for obtaining a laminated glass excellent in electromagnetic wave permeability and transparency and is also inexpensive.
[0155]
Since the laminated glass of the present invention is produced using the above-described interlayer film of the present invention, it exhibits excellent heat shielding properties and electromagnetic wave transparency, and has transparency, proper adhesion between the glass and the interlayer film, Excellent basic performance required for laminated glass such as penetrability, impact absorption, and weather resistance. Further, whitening due to moisture absorption is less likely to occur.
[0156]
In particular, the visible light transmittance (Tv) with respect to a light beam having a wavelength of 380 to 780 nm is set to a specific value or more, and the electromagnetic wave shield against an electromagnetic wave having a solar transmittance (Ts) and a haze (H) with a wavelength of 300 to 2500 nm and an electromagnetic wave with a frequency of 10 to 2000 MHz. By setting the property (ΔdB) to a specific value or less, the heat shielding property, transparency, and electromagnetic wave permeability are remarkably excellent.
[0157]
Therefore, the laminated glass of the present invention is suitably used for an automobile windshield, a side glass, a building window glass, and the like.

Claims (11)

An adhesive resin in which tin-doped indium oxide and / or antimony-doped tin oxide having an average particle size of more than 0 and not more than 80 nm is dispersed ;
The number of tin-doped indium oxide or antimony-doped tin oxide particles having a particle size of 100 nm or more is 1 or less per 1 μm ² ,
0.1 to 3.0 parts by weight of tin-doped indium oxide and / or antimony-doped tin oxide is included with respect to 100 parts by weight of the adhesive resin,
An interlayer film for laminated glass comprising one or more dispersants selected from the following group together with tin-doped indium oxide and / or antimony-doped tin oxide .
(A) β diketones
(B) C2-C18 carboxylic acid
(C) Hydroxycarboxylic acid having 2 to 18 carbon atoms The interlayer film for laminated glass according to claim 1, wherein the adhesive resin contains a plasticizer. The interlayer film for laminated glass according to claim 1 or 2 , wherein the adhesive resin is a polyvinyl acetal resin. The interlayer film for laminated glass according to claim 1 , wherein the β-diketone is acetylacetone. The interlayer film for laminated glass according to claim 1 , wherein the carboxylic acid having 2 to 18 carbon atoms is 2-ethylbutyric acid or 2-ethylhexanoic acid. A dispersion obtained by dispersing tin-doped indium oxide and / or antimony-doped tin oxide in an organic solvent with a dispersant was added to an adhesive resin containing a plasticizer, melt-kneaded, and then formed into a film The interlayer film for laminated glass according to claim 1 . The interlayer film for laminated glass according to claim 6 , wherein the organic solvent is a plasticizer of the same type as the plasticizer added to the adhesive resin. The interlayer film for laminated glass according to claim 6 or 7 , wherein the film is formed by an extrusion method using a biaxially parallel extruder. The average particle diameter of tin-doped indium oxide and / or antimony-doped tin oxide in the dispersion is 10~80nm at room temperature, and characterized in that it is a 10~80nm after heating the dispersion to 200 ° C. The interlayer film for laminated glass according to claim 6 or 7 . A laminated glass comprising an interlayer film for laminated glass according to any one of claims 1 to 9 interposed between at least a pair of glasses and integrated. The laminated glass according to claim 10 , wherein the electromagnetic wave shielding performance ΔdB at 10 to 2000 MHz is 10 dB or less.