JPH0224862B2 - - Google Patents
Info
- Publication number
- JPH0224862B2 JPH0224862B2 JP20633688A JP20633688A JPH0224862B2 JP H0224862 B2 JPH0224862 B2 JP H0224862B2 JP 20633688 A JP20633688 A JP 20633688A JP 20633688 A JP20633688 A JP 20633688A JP H0224862 B2 JPH0224862 B2 JP H0224862B2
- Authority
- JP
- Japan
- Prior art keywords
- aluminum borate
- borate whiskers
- chloride resin
- vinyl chloride
- whiskers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 claims description 37
- 229920005989 resin Polymers 0.000 claims description 29
- 239000011347 resin Substances 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 22
- 239000007822 coupling agent Substances 0.000 claims description 17
- 239000011342 resin composition Substances 0.000 claims description 14
- 239000004800 polyvinyl chloride Substances 0.000 claims description 13
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 8
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 27
- 239000000047 product Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 14
- 239000000945 filler Substances 0.000 description 11
- 239000002585 base Substances 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000003365 glass fiber Substances 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- -1 ethylene, propylene Chemical group 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000004381 surface treatment Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000012763 reinforcing filler Substances 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 description 3
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- GGSRTHRSSCWGGK-UHFFFAOYSA-L 2,2-dibutyl-5-hydroxy-1,3,2-dioxastannepane-4,7-dione Chemical compound CCCC[Sn]1(CCCC)OC(=O)CC(O)C(=O)O1 GGSRTHRSSCWGGK-UHFFFAOYSA-L 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- MOWNZPNSYMGTMD-UHFFFAOYSA-N oxidoboron Chemical class O=[B] MOWNZPNSYMGTMD-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
（産業上の利用分野）
本発明は、ホウ酸アルミニウムウイスカーを配
合してなる塩化ビニル樹脂組成物に関する。ホウ
酸アルミニウムウイスカーを充填材として配合す
ることによつて、ベースの塩化ビニル樹脂に比し
て強度、弾性率が大幅に増大する。しかも小さな
形状の製品に対しても補強可能で、製品の表面に
充填材の露出することがない成形品を得ることが
できる。
（従来の技術）
塩化ビニル樹脂は古くから知られる汎用樹脂で
生活用品から電気部品、建材など幅広い用途に使
用されている。
一般に塩化ビニル樹脂のような熱可塑性樹脂の
組成物には強度、弾性率の増大や耐熱性の向上、
または増量効果（製品のコスト低減）を目的とし
て無機充填材が配合されることが多い。
特に、繊維強化熱可塑性プラスチツク
（FRTP）の例に見られるように、樹脂系構造用
複合材における繊維状充填材の占める位置は極め
て重要であり、例えばガラス繊維などが補強性充
填材として開発され応用されてきた。繊維長の比
較的短いチタン酸カリウムなどのウイスカーも同
じく補強性充填材として利用されている。
また、これらの繊維強化熱可塑性プラスチツク
などの樹脂系構造用複合材の強度は、充填材であ
る繊維とマトリツクスを形成するプラスチツクと
の間の結合の存在に左右される。強い結合を作る
ために充填材の表面を化学的に処理することが行
われており、このとき使用する処理材料がカツプ
リング剤で、シリコン系、チタン系、アルミニウ
ム系、ジルコニウム系、ジルコアルミニウム系、
クロム系、ボロン系、リン系、アミノ酸系等の
種々のものが使用されている。
（発明が解決しようとする課題）
一般に、塩化ビニル樹脂のような熱可塑性樹脂
を高強度、高弾性率の要求される用途に使用する
場合、通常充填材の添加量を増やす方法とガラス
繊維等の高強度、高弾性の充填材を使用する方法
とがある。
しかし、前者の充填材の添加量を増やす方法は
熱可塑性樹脂組成物の溶融時の粘度の上昇によつ
て作業効率が悪くなるばかりか、耐衝撃性の低
下、比重の上昇、耐水性の低下等の弊害がある。
従来、塩化ビニル樹脂に対してはタルク、炭酸カ
ルシウム等が使用されてきたが、これらの粉状充
填材では前記の要求を十分満たすことが困難であ
つた。
後者のガラス繊維等を使用する方法は、ガラス
繊維が他の充填材に比べてサイズが大きいため小
さな形状の製品に対しては補強が出来ない。また
成形後に製品の表面に露出して外観上好ましくな
い。
（課題を解決するための手段）
本発明者等はこのような事情に鑑み、鋭意研究
を重ねた結果、ホウ酸アルミニウムウイスカーが
高強度・高弾性を有していることから、これを充
填材として配合することによつて、ベースの塩化
ビニル樹脂に比して高強度、高弾性率を持ち、し
かも小さな形状の製品に対しても補強可能で、製
品の表面に充填材の露出することがない成形品を
得ることができるポリ塩化ビニル樹脂組成物を発
明するに至つた。
本発明で用いる塩化ビニル樹脂（PVC）は塩
化ビニルモノマーを単独で重合したポリ塩化ビニ
ル単独重合体及び塩化ビニルモノマーと共重合可
能な他のモノマーとを共重合させた塩化ビニル共
重合体のいずれをも用いることができる。一般に
は前者、即ちポリ塩化ビニル単独重合体が最も広
く用いられる。また後者、即ちポリ塩化ビニル共
重合体は特に限定されず公知のものが使用できる
が、一般には塩化ビニルモノマーと共重合可能な
他のモノマー、例えば、エチレン、プロピレン、
酢酸ビニル、アクリル酸エステル、アクリロニト
リル等を50％以下共重合させたポリ塩化ビニル共
重合体が好適に使用される。
本発明のポリ塩化ビニル樹脂組成物は、上記の
塩化ビニル樹脂にホウ酸アルミニウムウイスカー
を配合して成るものであり、代表的なホウ酸アル
ミニウムウイスカーは、2Al2O3・B2O3，
9Al2O3・2B2O3で表わされる組成を持ち、特願昭
62−152418号及び特願昭62−152419号で紹介され
ているものである。具体的には、2Al2O3・B2O3
で表わされる組成を持つホウ酸アルミニウムウイ
スカーはアルミニウム水酸化物、及びアルミニウ
ム無機塩の中から選ばれた少なくとも一種のアル
ミニウム供給成分と、ホウ素の酸化物、酸素酸、
及びそのアルカリ金属塩の中から選ばれた少なく
とも一種のホウ素供給成分とをアルカリ金属の塩
化物、アルカリ金属の硫酸塩及びアルカリ金属の
炭酸塩の中から選ばれた少なくとも一種の溶融剤
の存在下600〜1000℃の温度に加熱して反応、育
成させることによつて得られる。また、
9Al2O3・2B2O3で表わされる組成を持つホウ酸ア
ルミニウムウイスカーはアルミニウム水酸化物、
及びアルミニウム無機塩の中から選ばれた少なく
とも一種のアルミニウム供給成分と、ホウ素の酸
化物、酸素酸、及びそのアルカリ金属塩の中から
選ばれた少なくとも一種のホウ素供給成分とをア
ルカリ金属の塩化物、アルカリ金属の硫酸塩及び
アルカリ金属の炭酸塩の中から選ばれた少なくと
も一種の溶融剤の存在下900〜1200℃の温度に加
熱して反応、育成させることによつて得られる。
これらの方法によつて得られるホウ酸アルミニ
ウムウイスカーは繊維径0.05〜5μm、繊維長２〜
100μmのものであり、ガラス繊維と比較して著し
く小さいため、小さな形状の製品に対する補強も
可能で、製品の表面に充填材の露出することがな
い。
これらのホウ酸アルミニウムウイスカーに対し
て更に補強効果を向上させるためには、カツプリ
ング剤による表面処理によつてホウ酸アルミニウ
ムウイスカーとマトリツクスである塩化ビニル樹
脂との濡れ性、結合性を改良することが有効であ
る。このとき使用するカツプリング剤は、シリコ
ン系、チタン系、アルミニウム系、ジルコニウム
系、ジルコアルミニウム系、クロム系、ボロン
系、リン系、アミノ酸系等の公知のものがある。
また、アミノ基を有する高分子化合物をホウ酸ア
ルミニウムウイスカー表面にグラフトする方法も
有効なカツプリング剤処理となるものである。
具体的に上記のシリコン系、チタン系、アルミ
ニウム系、ジルコニウム系、ジルコアルミニウム
系、クロム系、ボロン系、リン系、アミノ酸系等
の公知のカツプリング剤を使用してホウ酸アルミ
ニウムウイスカーの表面処理を行う方法として
は、任意の方法を採用することができるが、一般
にはスプレー装置のついたブレンダー中にホウ酸
アルミニウムウイスカーを添加し高速撹拌しなが
らカツプリング剤をスプレーする方法、水または
有機溶媒にカツプリング剤を溶解してこの溶液中
にホウ酸アルミニウムウイスカーを浸漬後溶媒を
除去して乾燥する方法、室温〜250℃の範囲内の
乾燥状態でカツプリング剤とホウ酸アルミニウム
ウイスカーとを混合する方法等がある。また、こ
れらカツプリング剤の使用量については、ホウ酸
アルミニウムウイスカーの100重量部に対して通
常0.01〜10重量部、好ましくは0.1〜５重量部で
ある。なお、これらのカツプリング剤は塩化ビニ
ル樹脂とホウ酸アルミニウムウイスカー及びその
他の添加剤を混合して塩化ビニル樹脂組成物を調
製する際に配合して混合することもできる。
また、アミノ基を有する高分子化合物をホウ酸
アルミニウムウイスカー表面にグラフトする方法
は、まず分子内に２個以上の酸無水物を有する有
機成分、あるいは１個以上の酸無水物と１個以上
のカルボン酸基を有する有機成分と、金属アルコ
キシドを無機成分とする有機−無機複合物を加水
分解して形成するゲルを、ホウ酸アルミニウムウ
イスカー表面にコーテイングし、その後、このコ
ーテイング層に１級または２級のアミノ基を持つ
高分子化合物を反応導入することによつて処理で
きる。この方法によるとホウ酸アルミニウムウイ
スカーの表面に反応性の高いアミノ基の導入が可
能であるため、一般のカツプリング剤と比較して
も強固な結合が作られ、良好な濡れ性を有する。
本発明の組成物中の主成分をなす塩化ビニル樹
脂に対する前記ホウ酸アルミニウムウイスカーの
量は、本発明の塩化ビニル樹脂組成物の用途によ
つて適宜変更され得る。しかしながら、一般的に
は、ホウ酸アルミニウムウイスカーの添加量が塩
化ビニル樹脂に対して５重量％未満では該ウイス
カーによる補強効果が十分に発現され得ないおそ
れがあり、また塩化ビニル樹脂に対して100重量
％を超えると補強材の分散性が悪くなり均一な成
形用組成物が得られないので、前記ウイスカーは
通常塩化ビニル樹脂の５〜100重量％、好ましく
は10〜80重量％の範囲内で使用すべきである。
本発明の実施に当つては、安定剤、可塑剤、滑
剤、着色剤、分散剤、酸化防止剤、老化防止剤、
ガラス繊維等を含む補強性充填材、非補強性充填
材、難燃剤乃至防燃剤等通常用いられる各種添加
剤を併用してもよい。
塩化ビニル樹脂、ホウ酸アルミニウムウイスカ
ー及びその他の添加剤を含有する塩化ビニル樹脂
組成物の調製は適宜のブレンダー等を用いて常法
により、均一に混合することによつてなされる。
また、このようにして調製された塩化ビニル樹脂
組成物は、通常の押出成形や射出成形等により所
望の製品に成形される。
（実施例）
以下実施例及び比較例に基づき本発明を詳しく
説明する。
実施例１ （表面処理なし）
塩化ビニル樹脂（商品名GEON−103EP 日本
ゼオン製 平均重合度1050）100重量部に対して
滑剤、安定剤を表−１の如く配合したものをベー
ス樹脂とし、これに9Al2O3・2B2O3の組成を持つ
繊維径0.5ないし1.0μ、繊維長10ないし30μのホウ
酸アルミニウムウイスカーを25重量部加えたもの
と50重量部加えたものを用意し、撹拌機にて撹拌
混合する。これを165℃の熱ロールにて均一に混
練し、シート状にしてから冷却した後、175℃で
プレス成形しその特性を測定した。
引張強度の測定はJIS Ｋ−7113により、曲げ弾
性率はJIS Ｋ−7203により、またシヤルピー衝撃
試験はJIS K7111により測定を行つた。それらの
結果を表−１に示す。
本例において9Al2O3・2B2O3の組成を持つホウ
酸アルミニウムウイスカーの代りに、2Al2O3・
B2O3の組成を持つ繊維径0.3ないし0.6μ、繊維長
10ないし20μのホウ酸アルミニウムウイスカーを
用い、同様の処理を行なつて調製した塩化ビニル
樹脂組成物を前記と同じ条件で加熱成型し、その
特性を調べたところ、9Al2O3・2B2O3のホウ酸ア
ルミニウムウイスカーを用いた場合とほぼ同じ結
果であつた。
比較例 １
タルク（富士タルク工業製）を実施例１で調製
したベース樹脂に25重量部加えたものと50重量部
加えたものとを用意した。以下実施例１と同様に
配合物を調製しそれぞれの物性を測定した。（表
−１）
比較例 ２
炭酸カルシウム（白石工業製）を実施例１で調
製したベース樹脂に25重量部加えたものと50重量
部加えたものとを用意した。以下実施例１と同様
に配合物を調製しそれぞれの物性を測定した。
（表−１）
実施例２ （シリコン系カツプリング剤による表
面処理）
メタノール２の中にγ−アミノプロピルトリ
エトキシシラン（商品名KBE−903、信越シリコ
ーン製）を10g加え撹拌のしたのち、9Al2O3・
2B2O3の組成を持つウイスカー500gを加え、室温
で更に15分撹拌したのち、濾過を行い表面にカツ
プリング処理をしたウイスカーを得た。濾別した
ウイスカーを110℃で３時間乾燥した後、実施例
１で調製したベース樹脂に25重量部加えたものと
50重量部加えたものを用意した。以下実施例１と
同様に配合物を調製しそれぞれの物性を測定し
た。（表−２）
実施例３ （アミノ基を有する高分子化合物をグ
ラフトする表面処理）
テトラヒドロフラン100ml中、無水トリメリツ
ト酸4.2gとチタン酸テトラブチル15mlを混合反応
させ、これを9Al2O3・2B2O3の組成からなるウイ
スカー300gに均一にスプレーし、次いでこのウ
イスカーを５％ポリエチレンイミン水溶液200ml
に直ちに加えて、30℃の温度で１時間加熱反応さ
せた後一夜静置し、この反応物を濾過し、水で洗
浄し乾燥させて、ポリエチレンイミンをグラフト
したホウ酸アルミニウムウイスカーを得た。これ
を実施例１で調製したベース樹脂に25重量部加え
たものと50重量部加えたものを用意した。以下実
施例１と同様に配合物を調製しそれぞぞれの物性
を測定した。（表−２）
（発明の効果）
表−１が示すように、本発明のホウ酸アルミニ
ウムウイスカーを配合した組成物は、ベース樹脂
単独、タルク配合組成物、炭酸カルシウム配合組
成に比較して、引張強度、曲げ弾性率が大幅に向
上しているのがわかる。
また、表−２が示すように通常のシリコン系カ
ツプリング処理をホウ酸アルミニウムウイスカー
に施すことによつて塩化ビニル樹脂に対する補強
効果が一層向上することがわかつた。
更に、アミノ基を有する高分子化合物をホウ酸
アルミニウムウイスカー表面にグラフトする方法
は、通常のシリコン系カツプリング剤処理法と比
較して組成物の引張強度、曲げ弾性率が大幅に向
上し、かつ耐衝撃性の低下率が小さく、塩化ビニ
ル樹脂に対して有効なカツプリング剤処理法であ
る。
このように塩化ビニル樹脂にホウ酸アルミニウ
ムウイスカーを配合することによつて、少量の添
加で高強度、高弾性を有する成型物が得られるた
め、溶融時の粘度の上昇による作業効率の悪化、
耐衝撃性の低下、比重の上昇、耐水性の低下等の
弊害が少ない。また、塩化ビニル樹脂の熱安定性
を阻害する傾向が少なく、ホウ酸成分を含むウイ
スカーであることから、成形品の難燃性を向上さ
せることもできる。
また、ホウ酸アルミニウムウイスカーは、微小
な大きさであるため、ガラス繊維を使用した時の
ように小さな形状の製品の補強が不可能であつた
り、成形後に製品の表面に露出することがない。
(Industrial Application Field) The present invention relates to a vinyl chloride resin composition containing aluminum borate whiskers. By incorporating aluminum borate whiskers as a filler, the strength and elastic modulus are significantly increased compared to the base vinyl chloride resin. Moreover, it is possible to reinforce even small-shaped products, and it is possible to obtain molded products without exposing the filler on the surface of the product. (Prior Art) Vinyl chloride resin is a general-purpose resin that has been known for a long time and is used in a wide range of applications, from daily necessities to electrical parts and building materials. In general, thermoplastic resin compositions such as vinyl chloride resin have increased strength, increased modulus of elasticity, improved heat resistance,
Alternatively, inorganic fillers are often added for the purpose of increasing the volume (reducing the cost of the product). In particular, as seen in the example of fiber-reinforced thermoplastics (FRTP), the role of fibrous fillers in resin-based structural composites is extremely important; for example, glass fibers have been developed as reinforcing fillers. It has been applied. Whiskers such as potassium titanate, which have relatively short fiber lengths, are also used as reinforcing fillers. Furthermore, the strength of resin-based structural composites such as these fiber-reinforced thermoplastics depends on the presence of bonds between the filler fibers and the matrix-forming plastics. In order to create a strong bond, the surface of the filler is chemically treated, and the treatment material used at this time is a coupling agent, which includes silicon-based, titanium-based, aluminum-based, zirconium-based, zircoaluminum-based,
Various types such as chromium-based, boron-based, phosphorus-based, and amino acid-based are used. (Problems to be Solved by the Invention) Generally, when thermoplastic resins such as vinyl chloride resins are used for applications that require high strength and high modulus, there is a method of increasing the amount of fillers added, glass fibers, etc. There is a method of using high-strength, high-elasticity filler. However, the former method of increasing the amount of filler added not only reduces work efficiency due to an increase in the viscosity of the thermoplastic resin composition when it is melted, but also decreases impact resistance, increases specific gravity, and decreases water resistance. There are other disadvantages.
Conventionally, talc, calcium carbonate, etc. have been used for vinyl chloride resin, but it has been difficult to sufficiently satisfy the above requirements with these powdered fillers. The latter method of using glass fiber or the like cannot reinforce small-shaped products because glass fiber is larger than other fillers. Moreover, it is exposed on the surface of the product after molding, which is unfavorable in terms of appearance. (Means for Solving the Problems) In view of the above circumstances, the inventors of the present invention have conducted intensive research and found that aluminum borate whiskers have high strength and high elasticity. By blending it with PVC resin, it has higher strength and higher modulus than the base vinyl chloride resin, and can also be used to reinforce products with small shapes, eliminating the need for the filler to be exposed on the surface of the product. The inventors have now invented a polyvinyl chloride resin composition that allows molded products to be obtained. The vinyl chloride resin (PVC) used in the present invention is either a polyvinyl chloride homopolymer obtained by polymerizing vinyl chloride monomer alone or a vinyl chloride copolymer obtained by copolymerizing vinyl chloride monomer with another monomer that can be copolymerized. can also be used. Generally, the former, ie, polyvinyl chloride homopolymer, is most widely used. The latter, that is, a polyvinyl chloride copolymer, is not particularly limited and any known one can be used, but generally other monomers copolymerizable with the vinyl chloride monomer, such as ethylene, propylene,
A polyvinyl chloride copolymer obtained by copolymerizing 50% or less of vinyl acetate, acrylic ester, acrylonitrile, etc. is preferably used. The polyvinyl chloride resin composition of the present invention is made by blending aluminum borate whiskers with the above-mentioned vinyl chloride resin. Typical aluminum borate whiskers include 2Al 2 O 3・B 2 O 3 ,
It has a composition expressed as 9Al 2 O 3・2B 2 O 3 , and the patent application
This is introduced in No. 62-152418 and Japanese Patent Application No. 62-152419. Specifically, 2Al 2 O 3・B 2 O 3
Aluminum borate whiskers having a composition represented by include at least one aluminum supply component selected from aluminum hydroxide and aluminum inorganic salts, boron oxide, oxygen acid,
and at least one boron supply component selected from alkali metal salts thereof in the presence of at least one melting agent selected from alkali metal chlorides, alkali metal sulfates, and alkali metal carbonates. It is obtained by heating to a temperature of 600 to 1000°C to react and grow. Also,
Aluminum borate whiskers with a composition represented by 9Al 2 O 3・2B 2 O 3 are aluminum hydroxide,
and at least one aluminum supplying component selected from aluminum inorganic salts, and at least one boron supplying component selected from boron oxides, oxyacids, and alkali metal salts thereof, and an alkali metal chloride. , alkali metal sulfates, and alkali metal carbonates by heating to a temperature of 900 to 1200°C to react and grow in the presence of at least one type of melting agent selected from alkali metal sulfates and alkali metal carbonates. The aluminum borate whiskers obtained by these methods have a fiber diameter of 0.05 to 5 μm and a fiber length of 2 to 5 μm.
It is 100 μm, which is significantly smaller than glass fiber, so it can be used to strengthen products with small shapes, and there is no need to expose the filler material on the surface of the product. In order to further improve the reinforcing effect of these aluminum borate whiskers, it is possible to improve the wettability and bonding properties between the aluminum borate whiskers and the vinyl chloride resin matrix by surface treatment with a coupling agent. It is valid. The coupling agents used at this time include known coupling agents such as silicon-based, titanium-based, aluminum-based, zirconium-based, zircoaluminum-based, chromium-based, boron-based, phosphorus-based, and amino acid-based.
Furthermore, a method of grafting a polymeric compound having an amino group onto the surface of aluminum borate whiskers is also an effective coupling agent treatment. Specifically, the surface treatment of aluminum borate whiskers was performed using known coupling agents such as silicon-based, titanium-based, aluminum-based, zirconium-based, zircoaluminum-based, chromium-based, boron-based, phosphorus-based, and amino acid-based. Any method can be used to do this, but in general, aluminum borate whiskers are added to a blender equipped with a spray device and a coupling agent is sprayed while stirring at high speed, or coupling agent is added to water or an organic solvent. A method of dissolving a coupling agent and immersing aluminum borate whiskers in this solution, removing the solvent and drying the solution, and a method of mixing a coupling agent and aluminum borate whiskers in a dry state within the range of room temperature to 250°C, etc. be. The amount of these coupling agents used is usually 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the aluminum borate whiskers. In addition, these coupling agents can also be blended and mixed when preparing a vinyl chloride resin composition by mixing the vinyl chloride resin, aluminum borate whiskers, and other additives. In addition, the method of grafting a polymeric compound having an amino group onto the surface of aluminum borate whiskers involves first grafting an organic component having two or more acid anhydrides in the molecule, or one or more acid anhydrides and one or more A gel formed by hydrolyzing an organic component having a carboxylic acid group and an organic-inorganic composite containing a metal alkoxide as an inorganic component is coated on the surface of aluminum borate whiskers, and then this coating layer is coated with primary or secondary This treatment can be carried out by introducing a polymer compound having a class amino group. According to this method, it is possible to introduce highly reactive amino groups onto the surface of aluminum borate whiskers, so that a stronger bond is created compared to general coupling agents, and the product has good wettability. The amount of the aluminum borate whiskers relative to the vinyl chloride resin that is the main component in the composition of the present invention may be changed as appropriate depending on the use of the vinyl chloride resin composition of the present invention. However, in general, if the amount of aluminum borate whiskers added is less than 5% by weight based on the vinyl chloride resin, there is a risk that the reinforcing effect of the whiskers may not be sufficiently expressed. If it exceeds 5% by weight, the dispersibility of the reinforcing material will deteriorate and a uniform molding composition will not be obtained. Should be used. In carrying out the present invention, stabilizers, plasticizers, lubricants, colorants, dispersants, antioxidants, anti-aging agents,
Various commonly used additives such as reinforcing fillers containing glass fibers, non-reinforcing fillers, flame retardants and flame retardants may be used in combination. A vinyl chloride resin composition containing a vinyl chloride resin, aluminum borate whiskers, and other additives is prepared by uniformly mixing them in a conventional manner using an appropriate blender or the like.
Further, the vinyl chloride resin composition thus prepared is molded into a desired product by conventional extrusion molding, injection molding, or the like. (Example) The present invention will be described in detail below based on Examples and Comparative Examples. Example 1 (No surface treatment) A base resin was prepared by blending a lubricant and a stabilizer as shown in Table 1 with 100 parts by weight of vinyl chloride resin (trade name GEON-103EP manufactured by Nippon Zeon, average degree of polymerization 1050). Prepare 25 parts by weight and 50 parts by weight of aluminum borate whiskers with a fiber diameter of 0.5 to 1.0 μ and fiber length of 10 to 30 μ having a composition of 9Al 2 O 3 2B 2 O 3 and stir them. Mix by stirring in a machine. This was uniformly kneaded using hot rolls at 165°C, formed into a sheet, cooled, and then press-molded at 175°C to measure its properties. The tensile strength was measured according to JIS K-7113, the flexural modulus was measured according to JIS K-7203, and the Charpy impact test was measured according to JIS K7111. The results are shown in Table-1. In this example, instead of the aluminum borate whiskers having the composition 9Al 2 O 3 .2B 2 O 3 , 2Al 2 O 3 .
Fiber diameter 0.3 to 0.6μ, fiber length with composition B 2 O 3
A vinyl chloride resin composition prepared using 10 to 20 μm aluminum borate whiskers and subjected to the same treatment was heat molded under the same conditions as above, and its properties were investigated . The results were almost the same as in the case of No. 3 using aluminum borate whiskers. Comparative Example 1 Two types were prepared in which 25 parts by weight and 50 parts by weight of talc (manufactured by Fuji Talc Industries) were added to the base resin prepared in Example 1. Thereafter, formulations were prepared in the same manner as in Example 1, and the physical properties of each were measured. (Table 1) Comparative Example 2 Two samples were prepared in which 25 parts by weight and 50 parts by weight of calcium carbonate (manufactured by Shiraishi Kogyo) were added to the base resin prepared in Example 1. Thereafter, formulations were prepared in the same manner as in Example 1, and the physical properties of each were measured.
(Table 1) Example 2 (Surface treatment with silicone coupling agent) 10 g of γ-aminopropyltriethoxysilane (trade name KBE-903, manufactured by Shin-Etsu Silicone) was added to methanol 2 and stirred, followed by 9Al 2 O3・
500 g of whiskers having a composition of 2B 2 O 3 were added, and the mixture was further stirred at room temperature for 15 minutes, followed by filtration to obtain whiskers whose surfaces were subjected to coupling treatment. After drying the filtered whiskers at 110°C for 3 hours, 25 parts by weight of the whiskers were added to the base resin prepared in Example 1.
A sample containing 50 parts by weight was prepared. Thereafter, formulations were prepared in the same manner as in Example 1, and the physical properties of each were measured. (Table 2) Example 3 (Surface treatment for grafting a polymer compound having an amino group) 4.2 g of trimellitic anhydride and 15 ml of tetrabutyl titanate were mixed and reacted in 100 ml of tetrahydrofuran . Spray the whiskers evenly onto 300g of O3 composition, then spray the whiskers with 200ml of 5% polyethyleneimine aqueous solution.
The reaction product was heated at 30° C. for 1 hour and then allowed to stand overnight. The reaction product was filtered, washed with water, and dried to obtain aluminum borate whiskers grafted with polyethyleneimine. 25 parts by weight and 50 parts by weight of this were added to the base resin prepared in Example 1, respectively. Thereafter, formulations were prepared in the same manner as in Example 1, and the physical properties of each were measured. (Table 2) (Effects of the Invention) As shown in Table 1, the composition containing the aluminum borate whiskers of the present invention has the following effects compared to the base resin alone, the composition containing talc, and the composition containing calcium carbonate. It can be seen that the tensile strength and flexural modulus are significantly improved. Furthermore, as shown in Table 2, it was found that the reinforcing effect on the vinyl chloride resin was further improved by subjecting the aluminum borate whiskers to a common silicone coupling treatment. Furthermore, the method of grafting a polymer compound having an amino group onto the surface of aluminum borate whiskers significantly improves the tensile strength and flexural modulus of the composition compared to the usual silicone-based coupling agent treatment method, and improves durability. This is an effective coupling agent treatment method for vinyl chloride resins, with a small reduction in impact resistance. By blending aluminum borate whiskers into vinyl chloride resin in this way, molded products with high strength and high elasticity can be obtained with the addition of a small amount, which reduces work efficiency due to increased viscosity during melting.
There are few negative effects such as a decrease in impact resistance, an increase in specific gravity, and a decrease in water resistance. Furthermore, since the whisker contains a boric acid component and has little tendency to inhibit the thermal stability of vinyl chloride resin, it can also improve the flame retardancy of molded products. In addition, since aluminum borate whiskers are minute in size, they cannot be used to reinforce products with small shapes, unlike when glass fibers are used, and they are not exposed on the surface of products after molding.
【表】【table】
【表】
＊３ ジブチル錫マレート
[Table] *3 Dibutyltin malate
Claims (1)
イスカーを配合してなるポリ塩化ビニル樹脂組成
物。 ２ ホウ酸アルミニウムウイスカーがカツプリン
グ剤によつて表面処理されていることを特徴とす
る請求項１に記載のポリ塩化ビニル樹脂組成物。 ３ ホウ酸アルミニウムウイスカーが9Al2O3・
2B2O3で示される組成からなることを特徴とする
請求項１及び２に記載のポリ塩化ビニル樹脂組成
物。 ４ ホウ酸アルミニウムウイスカーが2Al2O3・
B2O3で示される組成からなることを特徴とする
請求項１に記載のポリ塩化ビニル樹脂組成物。[Scope of Claims] 1. A polyvinyl chloride resin composition prepared by blending aluminum borate whiskers with polyvinyl chloride resin. 2. The polyvinyl chloride resin composition according to claim 1, wherein the aluminum borate whiskers are surface-treated with a coupling agent. 3 Aluminum borate whiskers are 9Al 2 O 3
The polyvinyl chloride resin composition according to claim 1 or 2, characterized in that it has a composition represented by 2B 2 O 3 . 4 Aluminum borate whiskers are 2Al 2 O 3 .
The polyvinyl chloride resin composition according to claim 1 , characterized in that it consists of a composition represented by B2O3 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20633688A JPH0255753A (en) | 1988-08-22 | 1988-08-22 | Polyvinyl chloride resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20633688A JPH0255753A (en) | 1988-08-22 | 1988-08-22 | Polyvinyl chloride resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0255753A JPH0255753A (en) | 1990-02-26 |
| JPH0224862B2 true JPH0224862B2 (en) | 1990-05-30 |
Family
ID=16521614
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20633688A Granted JPH0255753A (en) | 1988-08-22 | 1988-08-22 | Polyvinyl chloride resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0255753A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH064765B2 (en) * | 1988-12-20 | 1994-01-19 | 四国化成工業株式会社 | Resin composition |
| JPH03212454A (en) * | 1990-01-18 | 1991-09-18 | Nichias Corp | Fiber-reinforced synthetic resin composite material |
-
1988
- 1988-08-22 JP JP20633688A patent/JPH0255753A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0255753A (en) | 1990-02-26 |
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