JPS6255522B2 - - Google Patents
Info
- Publication number
- JPS6255522B2 JPS6255522B2 JP16599381A JP16599381A JPS6255522B2 JP S6255522 B2 JPS6255522 B2 JP S6255522B2 JP 16599381 A JP16599381 A JP 16599381A JP 16599381 A JP16599381 A JP 16599381A JP S6255522 B2 JPS6255522 B2 JP S6255522B2
- Authority
- JP
- Japan
- Prior art keywords
- polyvinyl butyral
- temperature
- weight
- parts
- laminated glass
- 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
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 56
- 238000006243 chemical reaction Methods 0.000 claims description 23
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000003377 acid catalyst Substances 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 9
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims 1
- 239000011229 interlayer Substances 0.000 description 20
- 239000005340 laminated glass Substances 0.000 description 18
- 239000004014 plasticizer Substances 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 12
- 230000000704 physical effect Effects 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 229910001622 calcium bromide Inorganic materials 0.000 description 8
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000005070 ripening Effects 0.000 description 5
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000000181 anti-adherent effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- JEYLQCXBYFQJRO-UHFFFAOYSA-N 2-[2-[2-(2-ethylbutanoyloxy)ethoxy]ethoxy]ethyl 2-ethylbutanoate Chemical compound CCC(CC)C(=O)OCCOCCOCCOC(=O)C(CC)CC JEYLQCXBYFQJRO-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011978 dissolution method Methods 0.000 description 2
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 2
- 229910001623 magnesium bromide Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明はポリビニルブチラールの製造方法に関
し、詳しくは、可塑剤を加えて合せガラス用中間
膜を製造すると常温における中間膜同志の粘着性
(以下中間膜の自着性という。)が大巾に改善され
た合せガラス用中間膜が得られるポリビニルブチ
ラールの製造方法に関するものである。
今日、広く工業的に利用されているポリビニル
ブチラールの製法は沈澱法と溶解法とに大別され
る。この内沈澱法は、例えば、酸触媒の存在下で
ポリビニルアルコールの水溶液にブチルアルデヒ
ドを加え20℃以下の比較的低温でブチラール化反
応を行いポリビニルブチラールの微細沈澱を生ぜ
しめた後、更に長時間撹拌、加熱する方法であ
る。又溶解法は、例えばイソプロピルアルコール
等の有機溶剤中にポリビニルアルコールを分散さ
せ酸触媒の存在下にブチルアルデヒドを加えて加
熱し長時間反応させる方法である。
然し乍ら、これら従来の方法によつて製造され
たポリビニルブチラールに可塑剤を加えて得られ
た合せガラス用中間膜は、膜表面の粘着性が強い
為製膜後の捲回時に膜同志が粘着するという問題
を有し、かかる粘着を防ぐ為に膜表面に重炭酸ソ
ーダ等の粘着防止剤を散布したり、10℃以下の温
度に中間膜を冷却することが行なわれている。
しかし粘着防止剤を散布する方法はポリビニル
ブチラール膜とガラスとを接着する際に、事前に
粘着防止剤除去の為の水洗工程及び乾燥工程を経
なければならないという難点を有し、また冷凍法
は中間膜の製造から包装、輸送、保存そして使用
時まで冷凍装置が必要であり高価につくという難
点を有し、実質的に常温における自着性が無い中
間膜の出現が待たれていた。
本発明はポリビニルブチラールの製造方法の上
述の現状に鑑み、得られたポリビニルブチラール
に可塑剤を加えて合せガラス用中間膜を製造する
と自着性が大巾に改善された合せガラス用中間膜
が得られるポリビニルブチラールの製造方法を提
供することを目的とするもので、その要旨は、酸
触媒の存在下に水相中でポリビニルアルコールと
ブチルアルデヒドを縮合せしめてポリビニルブチ
ラールを製造する方法において、塩酸、臭化水素
酸及び硝酸のそれぞれの水溶性塩の少くとも1種
の存在下に沈澱物を析出させたのち、強酸性領域
で反応系を30℃以上の温度に保つて熟成すること
を特徴とするポリビニルブチラールの製造方法に
存する。
本発明に用いられる酸触媒についてはポリビニ
ルアルコールとブチルアルデヒドを縮合せしめる
作用を有することが知られている酸を適宜用いる
ことができ、例えば硫酸、硝酸、塩酸等の無機酸
やパラトルエンスルホン酸等の有機酸が挙げられ
る。酸触媒の使用量は、反応の最終時における濃
度が0.5乃至5重量%となる量が望ましい。触媒
は所要量を一度に添加しても良いが、微細なポリ
ビニルブチラールを沈澱析出せしめる為には適当
な回数に分割添付するのが好ましい。例えば塩酸
の場合は、沈澱物の析出前に全所要重量の1/20乃
至1/3を添加し残りを沈澱物の析出後に添加する
のが好ましい。
本発明において用いられるポリビニルアルコー
ルの平均重合度は800〜3000が好適であり、また
そのケン化度は透明性の良いポリビニルブチラー
ルを得る為に好ましくは95モル%以上、特に好適
には98モル%以上である。ポリビニルアルコール
の水溶液濃度はアセタール化反応を行うことが出
来る濃度であれば特に限定されないが通常3乃至
20重量%とされる。
本発明においてポリビニルアルコールと縮合せ
しめるブチルアルデヒドの使用量は目的とするポ
リビニルアルコールのブチラール化度に応じて適
宜決定されるが、ポリビニルブチラールを合せガ
ラス用中間膜に用いる場合はブチラール化度が60
乃至75モル%であることが望ましくその為にはポ
リビニルアルコール100重量部に対し、49乃至74
重量部のブチルアルデヒドを加えるのが好適であ
る。
本発明における塩酸、臭化水素酸及び硝酸のそ
れぞれの水溶性塩の好適な例としては、それぞれ
の陽性成分がマグネシウム、カルシウム、亜鉛、
アルミニウム、鉄、チタン等の2価以上の原子価
を有するものがあげられる。これらの塩はそれぞ
れ単独で又は適宜組合わせて用いられ、その使用
量は通常、使用したポリビニルアルコール100重
量部に対して2〜100重量部、好ましくは7〜50
重量部とされる。
本発明における強酸性領域とは、ポリビニルブ
チラール分散液の温度にもよるがPH2以下とさ
れ、好ましくはPH1以下とされる。
又、ポリビニルブチラールの熟成の温度の上限
は特に定められないが、アルデヒドの過度の蒸発
を防ぐ為一般に90℃以下とされ、30℃以上の温度
に保つ熟成時間は、分散液の昇温及び降温の時間
を含め通常は1〜20時間とされる。
本発明方法によりポリビニルブチラールを製造
するには、通常は、20℃を越える温度のポリビニ
ルアルコール水溶液に酸触媒を加え、次いで上記
水溶性塩の少くとも1種を加えたのち、反応系を
冷却し、ブチルアルデヒドを加えて縮合反応させ
てポリビニルブチラールの沈澱を20℃以下の如く
低温で析出せしめる。
この様に沈澱析出時に反応系の温度を低く保つ
のは沈澱物を微小な粒子状又は粉状で得るためで
あり、温度の下限は反応系が凍結しない様な温度
であればよく特に制限されるものではないが、通
常−6℃以上の温度が採用される。
次にポリビニルブチラールの沈澱析出後、上記
水溶性塩の存在下に、反応系を昇温し30℃以上の
温度に保つて反応を更に進行せしめて熟成を行つ
た後、酸触媒を塩基で中和し、反応生成物を取り
出して常法により洗浄、精製を行うのである。
この様に、塩酸、臭化水素酸及び硝酸の夫々の
水溶性塩の少くとも1種の存在下にポリビニルブ
チラールの沈澱物を水相中に析出させたのち、強
酸性領域で反応系の温度を30℃以上に保つて熟成
することにより、可塑剤を加えて合せガラス用中
間膜を製造すると実質的に常温における自着性が
ない中間膜が得られるのであり、その理由につい
ては未だ充分には明らかではないが、次の通り推
測される。
ブチラール化反応は平衡反応であるので、反応
が或る程度進行した平衡状態においてブチラール
化度はほぼ一定となる。従来公知の製造方法では
一般に、ブチラール化度が一定の状態に達する前
に反応を停止していたのであり、この時のポリビ
ニルブチラール中の残水酸基はランダムな配列を
していると考えられる。しかして上記水溶性塩の
存在下にこのポリビニルブチラールを水相中に沈
澱析出させ、強酸性領域で反応系の温度を30℃以
上に保つて熟成を行うと、該熟成中に逆ブチラー
ル化反応により生成する水酸基は水素結合による
会合を示す傾向があり、一方ブチラール化反応
は、会合の傾向の強い水酸基よりもそうでない水
酸基に選択的に起り易くなる。従つて最終的平衡
状態に近ずくと、分子内に水酸基が連鎖的に残る
傾向が強まり、これによつて得られたポリビニル
ブチラールの剛性が増加し、これが中間膜の自着
性の減少に寄与するものと考えられる。
本発明者等は、上記水溶性塩の不存在下でも析
出したポリビニルブチラールを比較的高温で長時
間熟成することにより、得られたポリビニルブチ
ラールに可塑剤を加えると自着性が改善された中
間膜が得られるという知見をすでに得たものであ
るが、本発明における水溶性塩を使用すると、上
記熟成時間が著しく短くて済みかつより低い温度
による熟成が可能となるのである。
又上記水溶性塩は酸触媒の存在下でブチラール
化反応を促進させる傾向を有するのであり、その
存在下でブチラール化反応を行うと、不存在下の
場合に比較してポリビニルブチラールが沈澱析出
する迄の時間も短縮されるのである。
又、上記水溶性塩の不存在下でポリビニルブチ
ラールの微細粒子を析出せしめた後、昇温して高
温で長時間熟成すると沈澱粒子の凝集等による粗
大化が生じ易くなり、粗大化した粒子中には酸触
媒やその中和に用いた塩基等が残留して透明性更
には熱安定性を低下せしめる傾向があつたが、上
記水溶性塩には微粒子の粗大化を防止する作用が
あり透明性や熱安定性を低下せしめることが殆ん
どないのである。
本発明方法により得られたポリビニルブチラー
ルに用いる可塑剤は従来よりポリビニルブチラー
ルの為の可塑剤として用いられるものをいずれも
使用することができ、例えばトリエチレングリコ
ール=ジ2エチルブチレート、トリエチレングリ
コール=ジ2エチルヘキソエートなどの汎用可塑
剤が挙げられる。更にジブトキシジエチレングリ
コールアジペートなどが好適に使用される。可塑
剤の添加量はポリビニルブチラール100重量部に
対し、30乃至60重量部が望ましい。可塑剤が30重
量部未満では合せガラス用中間膜とした時の耐貫
通性が低下し、可塑剤が60重量部を越えるものは
可塑剤が膜表面にしみ出すいわゆるブリード現象
が生じ、合わせガラス用中間膜とした時の透明性
及び接着性に悪影響を及ぼすからである。
本発明方法は上述の通りの構成になされてお
り、本発明によれば、可塑剤を加えて合せガラス
用中間膜を製造すると常温における自着性が顕著
に改善された合せガラス用中間膜が得られるポリ
ビニルブチラールが、塩酸、臭化水素酸及び硝酸
のそれぞれの水溶性塩の何れをも用いない場合に
比較して上記の如く工業的に有利な温度・時間の
条件下で得ることができるのである。
又本発明において微細なポリビニルブチラール
粒子を沈澱析出せしめた場合は粗大化粒子が殆ん
ど残留していない透明性、熱安定性の良好なポリ
ビニルブチラールを得ることができるのである。
以下に本発明の実施例を示す。単に%とあるの
は重量%を意味する。尚、実施例における各物性
値は次の測定法によつた。
1 透明性
ポリビニルブチラールを二枚のガラス板の間
に挾んで得られた試料を加熱されたオーブン中
に入れてポリビニルブチラールを溶融した後に
室温で放冷した。得られた試料を白色光のもと
で観察し、青味、濁り等のないものを良好とし
た。
2 熱安定性
ポリビニルブチラールを入れた試験管を加温
された油浴に浸し、120℃にて所定時間を経て
もポリビニルブチラールが変色しない場合を熱
安定性が良好であるとした。
一般に中和又は水洗が不完全な場合にはポリ
ビニルブチラール中に塩酸等の触媒が残存し、
本試験を行うとポリビニルブチラールは黄色に
着色する。
3 自着性
ポリビニルブチラール100重量部に所定の可
塑剤42重量部を加えライカイ機で混合し、加熱
ロールを用いて混練した後プレスし、表面の平
滑な厚さ0.76mmの均一なフイルムを作成した。
このフイルムを3cm×10cmの長方形状に切り取
り、2枚重ね合わせ6Kgの荷重をかけた状態で
20℃の温度に保つたデシケーター中にて48時間
放置した。
この様にして得られた試料の一端を互に剥
し、剥されたフイルムを90゜方向に曲げて全体
をT字形にした後、剥されたフイルムの両方の
端を引張試験機でつかみ20℃にて500mm/分の
引張速度でT型剥離強度を測定した。
4 耐衝撃性
ポリビニルブチラール100重量部に可塑剤42
重量部を添加混練し、押し出し機にて、厚さ
0.76mmの可塑化ポリビニルブチラールを得た。
このフイルムを厚さ3.0mm、30cm×30cmのガラ
ス板2枚の間に挾み込み、従来公知の条件で加
熱加圧して合わせガラスを得た。この合せガラ
スを所定温度に8時間以上保管した後、外枠が
31cm×31cm、内枠が26cm×26cm、高さ20cmのマ
ス型鉄枠上に水平に置き、2.268Kg(5ポン
ド)の鋼球を指定された高さから合わせガラス
の中心に落下させた。
合せガラスを鋼球が貫通する割合が50%とな
る高さを耐貫通強度とした。
尚、合せガラスの試料としては、予め金属石
けんを適宜量添加混合した可塑剤を用いること
により後述するパンメル値を製品として通常使
用される範囲の6に設定したものを用いた。
5ラスに対する接着性
合せガラスを−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
ーで打つてガラスの粒径が6mm以下になる迄粉
砕した。ガラスが剥離した后の膜の露出度をあ
らかじめグレード付けした限度見本で判定し、
その結果を第1表に従いパンメル値として表わ
した。
The present invention relates to a method for producing polyvinyl butyral, and more specifically, when an interlayer film for laminated glass is produced by adding a plasticizer, the adhesion of the interlayer films to each other at room temperature (hereinafter referred to as self-adhesion of the interlayer film) is greatly improved. The present invention relates to a method for producing polyvinyl butyral that yields a polyvinyl butyral interlayer film for laminated glass. The methods for producing polyvinyl butyral that are widely used industrially today are broadly divided into precipitation methods and dissolution methods. In this internal precipitation method, for example, butyraldehyde is added to an aqueous solution of polyvinyl alcohol in the presence of an acid catalyst, a butyralization reaction is carried out at a relatively low temperature of 20°C or less to produce fine precipitates of polyvinyl butyral, and then the precipitation is continued for a long time. This method involves stirring and heating. The dissolution method is, for example, a method in which polyvinyl alcohol is dispersed in an organic solvent such as isopropyl alcohol, and butyraldehyde is added in the presence of an acid catalyst, and the mixture is heated and reacted for a long time. However, interlayer films for laminated glass obtained by adding plasticizers to polyvinyl butyral produced by these conventional methods have strong adhesion on the film surface, so the films tend to stick to each other during winding after film formation. In order to prevent such adhesion, methods include spraying an anti-adhesive agent such as sodium bicarbonate on the film surface or cooling the interlayer film to a temperature of 10° C. or less. However, the method of spraying an anti-adhesive agent has the disadvantage that it requires a washing process and a drying process to remove the anti-adhesive agent before bonding the polyvinyl butyral film and glass. The problem is that a refrigeration device is required for the production, packaging, transportation, storage, and use of the interlayer film, which is expensive, and the emergence of an interlayer film that is substantially free of self-adhesion at room temperature has been awaited. In view of the above-mentioned current state of the method for producing polyvinyl butyral, the present invention provides an interlayer film for laminated glass with greatly improved self-adhesion by adding a plasticizer to the obtained polyvinyl butyral to produce an interlayer film for laminated glass. The purpose of the present invention is to provide a method for producing polyvinyl butyral obtained by condensing polyvinyl alcohol and butyraldehyde in an aqueous phase in the presence of an acid catalyst. , a precipitate is precipitated in the presence of at least one water-soluble salt of each of hydrobromic acid and nitric acid, and then the reaction system is maintained at a temperature of 30°C or higher in a strongly acidic region to ripen. The present invention relates to a method for producing polyvinyl butyral. As for the acid catalyst used in the present invention, acids known to have the effect of condensing polyvinyl alcohol and butyraldehyde can be appropriately used, such as inorganic acids such as sulfuric acid, nitric acid, and hydrochloric acid, and para-toluenesulfonic acid. Examples include organic acids. The amount of acid catalyst used is preferably such that the concentration at the end of the reaction is 0.5 to 5% by weight. The required amount of the catalyst may be added at once, but in order to precipitate fine polyvinyl butyral, it is preferable to add the catalyst in portions at an appropriate number of times. For example, in the case of hydrochloric acid, it is preferable to add 1/20 to 1/3 of the total required weight before precipitation, and add the rest after precipitation. The average degree of polymerization of the polyvinyl alcohol used in the present invention is preferably 800 to 3000, and the degree of saponification is preferably 95 mol% or more, particularly preferably 98 mol%, in order to obtain polyvinyl butyral with good transparency. That's all. The concentration of the aqueous solution of polyvinyl alcohol is not particularly limited as long as it can carry out the acetalization reaction, but it is usually 3 to 3.
It is said to be 20% by weight. In the present invention, the amount of butyraldehyde to be condensed with polyvinyl alcohol is appropriately determined depending on the degree of butyralization of the target polyvinyl alcohol, but when polyvinyl butyral is used for an interlayer film for laminated glass, the degree of butyralization is 60%.
It is desirable that the content is from 49 to 75 mol%, and for that purpose, 49 to 74 parts by weight per 100 parts by weight of polyvinyl alcohol.
It is preferred to add parts by weight of butyraldehyde. Preferred examples of water-soluble salts of hydrochloric acid, hydrobromic acid and nitric acid in the present invention include magnesium, calcium, zinc,
Examples include those having a valence of two or more, such as aluminum, iron, and titanium. These salts are used alone or in appropriate combinations, and the amount used is usually 2 to 100 parts by weight, preferably 7 to 50 parts by weight, per 100 parts by weight of the polyvinyl alcohol used.
Parts by weight. In the present invention, the strongly acidic region refers to a pH of 2 or lower, preferably a pH of 1 or lower, although it depends on the temperature of the polyvinyl butyral dispersion. Furthermore, although there is no particular upper limit to the temperature for ripening polyvinyl butyral, it is generally set at 90°C or lower to prevent excessive evaporation of aldehyde, and the aging time at which the temperature is maintained at 30°C or higher depends on the temperature rise and fall of the dispersion liquid. Usually, the duration is 1 to 20 hours, including the time for . To produce polyvinyl butyral by the method of the present invention, an acid catalyst is usually added to an aqueous polyvinyl alcohol solution at a temperature of over 20°C, then at least one of the above water-soluble salts is added, and then the reaction system is cooled. , butyraldehyde is added and a condensation reaction is carried out to precipitate polyvinyl butyral at a low temperature such as 20° C. or lower. In this way, the temperature of the reaction system is kept low during precipitation in order to obtain the precipitate in the form of fine particles or powder, and the lower limit of the temperature is not particularly limited as long as it does not freeze the reaction system. Although it is not always necessary, a temperature of -6°C or higher is usually employed. Next, after precipitation of polyvinyl butyral, the reaction system was heated in the presence of the above-mentioned water-soluble salt and kept at a temperature of 30°C or higher to further advance the reaction for ripening, and then the acid catalyst was neutralized with a base. The reaction product is extracted and washed and purified using conventional methods. In this way, a precipitate of polyvinyl butyral is precipitated in the aqueous phase in the presence of at least one water-soluble salt of hydrochloric acid, hydrobromic acid, and nitric acid, and then the temperature of the reaction system is set in a strongly acidic region. If an interlayer film for laminated glass is manufactured by adding a plasticizer by aging it by keeping it at 30℃ or higher, an interlayer film that has virtually no self-adhesion at room temperature can be obtained, and the reason for this is still not fully understood. Although it is not clear, it is assumed as follows. Since the butyralization reaction is an equilibrium reaction, the degree of butyralization becomes approximately constant in an equilibrium state where the reaction has progressed to a certain extent. In conventional production methods, the reaction was generally stopped before the degree of butyralization reached a certain level, and the remaining hydroxyl groups in the polyvinyl butyral at this time are thought to be randomly arranged. If this polyvinyl butyral is precipitated in the aqueous phase in the presence of the above-mentioned water-soluble salt and then aged in a strongly acidic region while maintaining the temperature of the reaction system at 30°C or higher, the reverse butyralization reaction occurs during the ripening. The hydroxyl groups produced by this process tend to exhibit association by hydrogen bonding, while the butyralization reaction tends to occur selectively to hydroxyl groups that do not have a strong tendency to associate rather than to hydroxyl groups that have a strong tendency to associate. Therefore, as the final equilibrium state approaches, the tendency for hydroxyl groups to remain in chains in the molecule increases, which increases the rigidity of the obtained polyvinyl butyral, which contributes to a decrease in the self-adhesion of the interlayer film. It is considered that The present inventors have found that by aging polyvinyl butyral precipitated even in the absence of the above-mentioned water-soluble salt at a relatively high temperature for a long time, adding a plasticizer to the resulting polyvinyl butyral results in an intermediate product with improved self-adhesion. Although it has already been found that a film can be obtained, the use of the water-soluble salt in the present invention allows the above-mentioned aging time to be significantly shortened and allows aging to be performed at a lower temperature. In addition, the above-mentioned water-soluble salt has a tendency to accelerate the butyralization reaction in the presence of an acid catalyst, and when the butyralization reaction is carried out in the presence of an acid catalyst, polyvinyl butyral is precipitated compared to the case in its absence. It also shortens the time it takes. In addition, if fine particles of polyvinyl butyral are precipitated in the absence of the above-mentioned water-soluble salt and then heated and aged for a long time at high temperature, coarsening due to agglomeration of the precipitated particles is likely to occur, and in the coarsened particles. However, the water-soluble salts mentioned above have the effect of preventing the coarsening of fine particles and are transparent. There is almost no decrease in properties or thermal stability. As the plasticizer used for the polyvinyl butyral obtained by the method of the present invention, any of those conventionally used as a plasticizer for polyvinyl butyral can be used, such as triethylene glycol di2-ethyl butyrate, triethylene glycol Examples include general-purpose plasticizers such as di-2-ethylhexoate. Furthermore, dibutoxydiethylene glycol adipate and the like are preferably used. The amount of plasticizer added is preferably 30 to 60 parts by weight per 100 parts by weight of polyvinyl butyral. If the plasticizer content is less than 30 parts by weight, the penetration resistance will decrease when used as an interlayer film for laminated glass, and if the plasticizer content exceeds 60 parts by weight, a so-called bleed phenomenon will occur in which the plasticizer seeps onto the film surface, resulting in poor performance of laminated glass. This is because it has an adverse effect on transparency and adhesion when used as an interlayer film. The method of the present invention is configured as described above, and according to the present invention, when an interlayer film for laminated glass is manufactured by adding a plasticizer, an interlayer film for laminated glass with significantly improved self-adhesion at room temperature can be obtained. The resulting polyvinyl butyral can be obtained under industrially advantageous temperature and time conditions as described above, compared to when none of the water-soluble salts of hydrochloric acid, hydrobromic acid, and nitric acid are used. It is. Further, in the present invention, when fine polyvinyl butyral particles are precipitated, it is possible to obtain polyvinyl butyral having good transparency and thermal stability with almost no remaining coarse particles. Examples of the present invention are shown below. % simply means weight %. In addition, each physical property value in Examples was based on the following measuring method. 1 Transparency A sample obtained by sandwiching polyvinyl butyral between two glass plates was placed in a heated oven to melt the polyvinyl butyral, and then allowed to cool at room temperature. The obtained sample was observed under white light, and those without bluishness, turbidity, etc. were evaluated as good. 2. Thermal stability A test tube containing polyvinyl butyral was immersed in a heated oil bath, and the thermal stability was determined to be good if the polyvinyl butyral did not change color even after a predetermined period of time at 120°C. Generally, when neutralization or water washing is incomplete, catalysts such as hydrochloric acid remain in polyvinyl butyral.
When this test is performed, polyvinyl butyral is colored yellow. 3 Self-adhesiveness Add 42 parts by weight of a specified plasticizer to 100 parts by weight of polyvinyl butyral, mix in a Laikai machine, knead using heated rolls, and press to create a uniform film with a smooth surface and a thickness of 0.76 mm. did.
Cut this film into a rectangular shape of 3cm x 10cm, stack the two pieces together and apply a load of 6kg.
It was left for 48 hours in a desiccator kept at a temperature of 20°C. One end of the sample obtained in this way was peeled off from each other, and the peeled film was bent in a 90° direction to form a T-shape. Then, both ends of the peeled film were held in a tensile tester and heated at 20°C. The T-peel strength was measured at a tensile speed of 500 mm/min. 4 Impact resistance 100 parts by weight of polyvinyl butyral and 42 parts by weight of plasticizer
Add and knead parts by weight, and use an extruder to measure the thickness.
0.76 mm of plasticized polyvinyl butyral was obtained.
This film was sandwiched between two glass plates of 3.0 mm thickness and 30 cm x 30 cm, and heated and pressed under conventionally known conditions to obtain a laminated glass. After storing this laminated glass at the specified temperature for more than 8 hours, the outer frame
A steel ball weighing 2.268 kg (5 pounds) was dropped from the specified height onto the center of the laminated glass, which was placed horizontally on a square steel frame with a size of 31 cm x 31 cm, an inner frame of 26 cm x 26 cm, and a height of 20 cm. The height at which 50% of the steel balls penetrate the laminated glass is defined as the penetration resistance. The laminated glass sample used was one in which the pummel value, which will be described later, was set to 6, which is within the range normally used as a product, by using a plasticizer mixed with an appropriate amount of metal soap. Adhesion to 5 laths The laminated glass was adjusted by leaving it at a temperature of -18°C ± 0.6°C for 16 hours, and was crushed by hitting it with a hammer with a head weighing 0.45 kg until the particle size of the glass became 6 mm or less. After the glass has peeled off, the degree of exposure of the film is determined using pre-graded limit samples.
The results were expressed as pummel values according to Table 1.
【表】【table】
【表】
実施例 1
ケン化度99.6モル%、重合度2100のポリビニル
アルコールの13%水溶液100Kgに濃塩酸(濃度35
%)1Kgと臭化カルシウムの16%水溶液15.3Kgと
を加え(臭化カルシウムの量は仕込んだポリビニ
ルアルコール100重量部に対して19重量部であつ
た。)13℃にて撹拌しつつ30分間要してブチルア
ルデヒド6.7Kgを滴下したところ白色微粒子状の
ポリビニルブチラールの沈澱が析出した。さらに
35%濃塩酸7Kgを加えて反応系のPHを0.5以下に
したのち20℃/時間の昇温速度で40℃まで昇温
し、更に6時間その温度を保つて熟成を行なつた
後水酸化ナトリウムを加えて反応系を中和しPHを
9.6とした。30℃以上の温度で熟成した時間は6.8
時間であつた。
得られた樹脂を常法に従い水洗、乾燥を行ない
白色微粉末を得た。このポリビニルブチラールの
ブチラール化度は66.4モル%であつた。
この様にして得られたポリビニルブチラール、
該ポリビニルブチラール100Kgに可塑剤としてト
リエチレングリコール=ジ2エチルブチレート42
Kgを加えて得られた中間膜及び該中間膜から得ら
れた合せガラスの物性は第2表に示す通りであつ
た。
実施例 2
実施例1において臭化カルシウムの代りに塩化
アルミニウムを用いた以外は全て実施例1と同様
にしてポリビニルブチラールの粉末を得た。その
物性等は第2表に示す通りであつた。
実施例 3
実施例1において臭化カルシウムの代りに塩化
第二鉄を用いた以外は全て実施例1と同様にして
ポリビニルブチラールの粉末を得た。その物性等
は第2表に示す通りであつた。
実施例 4
実施例1において臭化カルシウムの代りに臭化
マグネシウムを用い、反応系を20℃/時間で昇温
した後熟成温度60℃にて3時間保つた以外はすべ
て実施例1と同様にしてポリビニルブチラールの
粉末を得た。その物性等は第2表に示す通りであ
つた。
実施例 5
実施例1において臭化カルシウムの代りに臭化
亜鉛を用い、反応系を20℃/時間で昇温した後熟
成温度38℃にて6時間保つた以外はすべて実施例
1と同様にしてポリビニルブチラールの粉末を得
た。その物性等は第2表に示す通りであつた。
実施例 6
実施例1において臭化カルシウムの代りに硝酸
亜鉛を用いた以外はすべて実施例1と同様にして
ポリビニルブチラールの粉末を得た。その物性等
は第2表に示す通りであつた。
比較例 1
実施例1において臭化カルシウムを加えない以
外はすべて実施例1と同様にしてポリビニルブチ
ラールの粉末を得た。その物性等は第2表に示す
通りであつた。
比較例 2
実施例4において臭化マグネシウムを加えない
以外はすべて実施例4と同様にしてポリビニルブ
チラールの粉末を得た。その物性等は第2表に示
す通りであつた。[Table] Example 1 Concentrated hydrochloric acid (concentration 35
%) and 15.3 kg of a 16% aqueous solution of calcium bromide were added (the amount of calcium bromide was 19 parts by weight per 100 parts by weight of polyvinyl alcohol charged) for 30 minutes at 13°C with stirring. When 6.7 kg of butyraldehyde was added dropwise, fine white particles of polyvinyl butyral were precipitated. moreover
After adding 7 kg of 35% concentrated hydrochloric acid to bring the pH of the reaction system below 0.5, the temperature was raised to 40°C at a rate of 20°C/hour, and the temperature was maintained for an additional 6 hours for ripening, followed by hydroxylation. Add sodium to neutralize the reaction system and lower the pH.
It was set at 9.6. The time of ripening at a temperature above 30℃ is 6.8
It was time. The obtained resin was washed with water and dried according to a conventional method to obtain a white fine powder. The degree of butyralization of this polyvinyl butyral was 66.4 mol%. Polyvinyl butyral obtained in this way,
Triethylene glycol di-2-ethyl butyrate 42 as a plasticizer to 100 kg of the polyvinyl butyral.
The physical properties of the interlayer film obtained by adding Kg and the laminated glass obtained from the interlayer film were as shown in Table 2. Example 2 Polyvinyl butyral powder was obtained in the same manner as in Example 1 except that aluminum chloride was used instead of calcium bromide. Its physical properties were as shown in Table 2. Example 3 Polyvinyl butyral powder was obtained in the same manner as in Example 1 except that ferric chloride was used instead of calcium bromide. Its physical properties were as shown in Table 2. Example 4 Everything was the same as in Example 1, except that magnesium bromide was used instead of calcium bromide in Example 1, and the reaction system was heated at a rate of 20°C/hour and then kept at an aging temperature of 60°C for 3 hours. A polyvinyl butyral powder was obtained. Its physical properties were as shown in Table 2. Example 5 Everything was the same as in Example 1 except that zinc bromide was used instead of calcium bromide and the reaction system was heated at a rate of 20°C/hour and then kept at an aging temperature of 38°C for 6 hours. A polyvinyl butyral powder was obtained. Its physical properties were as shown in Table 2. Example 6 Polyvinyl butyral powder was obtained in the same manner as in Example 1 except that zinc nitrate was used instead of calcium bromide. Its physical properties were as shown in Table 2. Comparative Example 1 Polyvinyl butyral powder was obtained in the same manner as in Example 1 except that calcium bromide was not added. Its physical properties were as shown in Table 2. Comparative Example 2 Polyvinyl butyral powder was obtained in the same manner as in Example 4 except that magnesium bromide was not added. Its physical properties were as shown in Table 2.
Claims (1)
ールとブチルアルデヒドを縮合せしめてポリビニ
ルブチラールを製造する方法において、塩酸、臭
化水素酸及び硝酸のそれぞれの水溶性塩の少くと
も1種の存在下に沈澱物を析出させたのち、強酸
性領域で反応系を30℃以上の温度に保つて熟成す
ることを特徴とするポリビニルブチラールの製造
方法。 2 水溶性塩の量が使用したポリビニルアルコー
ル100重量部に対して2重量部以上である第1項
記載の製造方法。 3 水溶性塩の陽性成分がマグネシウム、カルシ
ウム、亜鉛、アルミニウム、鉄、チタンのうちの
少くとも一つである第1項又は第2項記載の製造
方法。 4 熟成の時間が1〜20時間である第1項〜第3
項何れか1項に記載の製造方法。[Claims] 1. A method for producing polyvinyl butyral by condensing polyvinyl alcohol and butyraldehyde in an aqueous phase in the presence of an acid catalyst, comprising: 1. A method for producing polyvinyl butyral, which comprises precipitating a precipitate in the presence of one type of polyvinyl butyral, and then aging the reaction system in a strongly acidic region while maintaining a temperature of 30°C or higher. 2. The manufacturing method according to item 1, wherein the amount of the water-soluble salt is 2 parts by weight or more based on 100 parts by weight of the polyvinyl alcohol used. 3. The manufacturing method according to item 1 or 2, wherein the positive component of the water-soluble salt is at least one of magnesium, calcium, zinc, aluminum, iron, and titanium. 4 Items 1 to 3 where the aging time is 1 to 20 hours
1. The manufacturing method according to any one of the above.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16599381A JPS5867701A (en) | 1981-10-16 | 1981-10-16 | Preparation of polyvinyl butyral |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16599381A JPS5867701A (en) | 1981-10-16 | 1981-10-16 | Preparation of polyvinyl butyral |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5867701A JPS5867701A (en) | 1983-04-22 |
JPS6255522B2 true JPS6255522B2 (en) | 1987-11-20 |
Family
ID=15822871
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP16599381A Granted JPS5867701A (en) | 1981-10-16 | 1981-10-16 | Preparation of polyvinyl butyral |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5867701A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07109610A (en) * | 1993-08-16 | 1995-04-25 | Tokai Kensetsu:Kk | Helmet |
-
1981
- 1981-10-16 JP JP16599381A patent/JPS5867701A/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07109610A (en) * | 1993-08-16 | 1995-04-25 | Tokai Kensetsu:Kk | Helmet |
Also Published As
Publication number | Publication date |
---|---|
JPS5867701A (en) | 1983-04-22 |
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