JP3634577B2 - Polyvinyl acetal resin composition - Google Patents
Polyvinyl acetal resin composition Download PDFInfo
- Publication number
- JP3634577B2 JP3634577B2 JP19567297A JP19567297A JP3634577B2 JP 3634577 B2 JP3634577 B2 JP 3634577B2 JP 19567297 A JP19567297 A JP 19567297A JP 19567297 A JP19567297 A JP 19567297A JP 3634577 B2 JP3634577 B2 JP 3634577B2
- Authority
- JP
- Japan
- Prior art keywords
- polyvinyl acetal
- resin composition
- polyvinyl
- solution
- acetal resin
- 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 - Lifetime
Links
- 229920002554 vinyl polymer Polymers 0.000 title claims description 84
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 title claims description 80
- 239000000203 mixture Substances 0.000 title claims description 42
- 239000011354 acetal resin Substances 0.000 title claims description 38
- 229920006324 polyoxymethylene Polymers 0.000 title claims description 38
- 150000001241 acetals Chemical class 0.000 claims description 43
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 37
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 37
- 238000000034 method Methods 0.000 description 23
- 239000011342 resin composition Substances 0.000 description 22
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 14
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000006359 acetalization reaction Methods 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- -1 various coatings Substances 0.000 description 3
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- RKLRVTKRKFEVQG-UHFFFAOYSA-N 2-tert-butyl-4-[(3-tert-butyl-4-hydroxy-5-methylphenyl)methyl]-6-methylphenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 RKLRVTKRKFEVQG-UHFFFAOYSA-N 0.000 description 1
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000005010 epoxy-amino resin Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- SQYNKIJPMDEDEG-UHFFFAOYSA-N paraldehyde Chemical compound CC1OC(C)OC(C)O1 SQYNKIJPMDEDEG-UHFFFAOYSA-N 0.000 description 1
- 229960003868 paraldehyde Drugs 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000005336 safety glass Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/38—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an acetal or ketal radical
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、ポリビニルアセタール樹脂組成物に関し、特に、耐熱性と共に透明性の向上したポリビニルアセタール樹脂組成物に関する。
【０００２】
【従来の技術】
ポリビニルアセタールは、従来より塗料、安全ガラス用中間膜、接着剤、各種コーティング、各種バインダーとして広く工業的に使用されている。しかしながら、ポリビニルアセタールは耐熱性が不十分であり、これを補うために種々の方法が提案されている。例えば、特公昭５７ー５７０８３号公報には、ポリビニルアルコールを水性媒体中でアセタール化する際に、特定の化合物を添加することによってポリビニルアセタールの好ましい性質が全く失われることなく、良好な耐熱性を有するポリビニルアセタールが得られることが開示されている。
【０００３】
しかしながら、この方法による耐熱性の改良は、樹脂自体の劣化はほとんど起こらないものの加熱後に着色する場合があり、得られたポリビニルアセタールは、例えば、反射シートバインダー用樹脂、透明性を必要とする各種コーティング用樹脂としては十分満足なものとは言えない。
【０００４】
【発明が解決しようとする課題】
本発明は上記現状に鑑みてなされたものであり、その目的は、耐熱性と共に透明性の向上したポリビニルアセタール樹脂組成物を提供することにある。
【０００５】
【課題を解決するための手段】
請求項１記載のポリビニルアセタール樹脂組成物は、合成後のｐＨが５〜７に調整されたポリビニルアセタール及び下記一般式（Ｉ）の化合物を含有することを特徴とする。
【化２】
【０００６】
請求項２記載のポリビニルアセタール樹脂組成物は、ポリビニルアセタールが、ポリビニルブチラールであることを特徴とする請求項１記載のポリビニルアセタール樹脂組成物である。
【０００７】
請求項３記載のポリビニルアセタール樹脂組成物は、ポリビニルアセタールが、分子内にホルマール結合、アセトアセタール結合及びブチラール結合から選ばれる少なくとも２種以上の結合を有するものであることを特徴とする請求項１記載のポリビニルアセタール樹脂組成物である。
【０００８】
請求項４記載のポリビニルアセタール樹脂組成物は、一般式（Ｉ）の化合物の含有量が、ポリビニルアセタール１００重量部に対して０．０１〜１０重量部であることを特徴とする請求項１〜３のいずれかに記載のポリビニルアセタール樹脂組成物である。
【０００９】
本発明のポリビニルアセタール樹脂組成物は、ポリビニルアセタール及び上記一般式（Ｉ）の化合物を含有する。
【００１０】
上記一般式（Ｉ）の化合物としては、例えば、２， ２’ −メチレン−ビス−（４−メチル−６−ターシャリーブチルフェノール）、２， ２’ −メチレン−ビス−（４−エチル−６−ターシャリーブチルフェノール）、４， ４’ −メチレン−ビス−（６−ターシャリーブチルオルトクレゾール）、４， ４’ −メチレン−ビス−（２， ６−ジターシャリーブチルフェノール）等が挙げられる。
【００１１】
上記ポリビニルアセタールは、いずれも使用可能であり、ポリビニルアルコールを原料としアルデヒドを酸触媒でビニルアセタール化することにより得ることができる。また酢酸ビニルを出発原料として酸触媒によりケン化とビニルアセタール化を連続して行う方法で得られたものでも良い。これらの場合、原料ポリビニルアルコールは共重合または後変性等により変性されたポリビニルアルコールを用いても良い。ポリビニルアルコールの重合度としては２００〜５０００のものが好ましく用いられ、ポリビニルアルコールのケン化度としては８０〜９９．９のものが一般的に用いられる。またこれらポリビニルアルコールを２種以上混合したものを用いることもできる。
【００１２】
上記アセタール化に使用するアルデヒドとしては、ホルムアルデヒド、アセトアルデヒド、パラアセトアルデヒド、ブチルアルデヒドなどが挙げられる。これらのうち、特に、ブチルアルデヒドが好ましい。また、ホルムアルデヒド、アセトアルデヒド及びブチルアルデヒドから選ばれる少なくとも２種以上のアルデヒドを用いるのも好ましい。
【００１３】
ポリビニルアセタールを合成する方法としては、沈殿法、溶解法、均一法等が一般的であるがこれらの方法のみに限定されるわけではない。
【００１４】
本発明のポリビニルアセタール樹脂組成物の製造法としては、特に限定はなく、例えば、ポリビニルアセタールの合成時に一般式（Ｉ）の化合物をあらかじめ存在させる方法；ポリビニルアセタールと一般式（Ｉ）の化合物を混合する方法などが挙げられる。
【００１５】
上記、ポリビニルアセタールの合成時に一般式（Ｉ）の化合物をあらかじめ存在させる方法としては、ポリビニルアルコール溶液に分散させても良いし、用いるアルデヒドに分散させても良い。
【００１６】
上記、ポリビニルアセタールに一般式（Ｉ）の化合物を混合する方法としては、ポリビニルアセタールにパウダーでドライブレンドする方法；ポリビニルアセタール含有溶液、組成物調製時に必要に応じて添加される溶剤、可塑剤その他の薬剤にブレンドし混合する方法、等どのような方法でも良い。
【００１７】
本発明のポリビニルアセタール樹脂組成物において、一般式（Ｉ）の化合物の含有量は、少なくなると組成物の耐熱性が十分でなくなり、多くなると耐熱性は十分であるが、樹脂の着色がわずかながら発生してくる（しかしながら、そのレベルは従来よりもはるかに改善されたものである）ので、ポリビニルアセタール１００重量部に対して０．０１〜１０重量部が好ましく、０．０１〜５重量部が特に好ましい。
【００１８】
本発明のポリビニルアセタール樹脂組成物には、必要に応じて、種々の物質を配合、含有することができる。このような物質としては、例えば、未硬化又は部分硬化した熱硬化性樹脂（フェノール系樹脂、メラミン系樹脂、エポキシ系樹脂、アミノ系樹脂、又はこれらの変性樹脂）、無機系若しくは有機系の充填材、可塑剤、顔料、染料、安定剤、界面活性剤、帯電防止剤などが挙げられる。
【００１９】
本発明で用いられるポリビニルアセタールは、合成後のｐＨが５〜７に調整されたものに限定され、好ましくは６〜７に調整されたものである。ｐＨが５より小さい場合はポリビニルアセタールの分解が発生し、黄変、重合度低下等ポリビニルアセタールの劣化が起こり、ｐＨが７を越えると本発明の組成物に上記一般式（Ｉ）の化合物による着色が発生する。
【００２０】
本発明で用いられるポリビニルアセタールのｐＨは、酸、アルカリ、緩衝剤、等を用いて５〜７に調整される。該ｐＨ調整は、合成直後に調整されても良いし、組成物を作成する直前に調整されてもよい。
【００２１】
ポリビニルアセタールのｐＨを調整するには、ポリビニルアセタール合成後の酸触媒を中和する際に過剰のアルカリを添加せずに目的の範囲内に制御するか、過剰のアルカリで中和処理した後、水洗等の洗浄処理によって過剰のアルカリを除去するか、再びここに酸を添加して調整する方法でもよい。また合成後に酸触媒を除去する方法としてエチレンオキサイド、メチレンオキサイド等の触媒除去剤を使用して樹脂中の酸分を減らし目的ｐＨに調整する方法でも良い。最も好ましくは後水洗や触媒除去剤等により樹脂中の不純分を減らす方法により、ｐＨを目的範囲内に調整する方法が好ましい。
【００２２】
【発明の実施の形態】
以下、本発明を実施例、比較例により具体的に説明する。
【００２３】
実施例１
（１）ポリビニルブチラール樹脂組成物の製造
重合度８００のポリビニルアルコール１００ｇを７００ｇの蒸留水に加温溶解した後、５℃に保ち、これに３５％塩酸５５ｇを加え、さらに、２， ２’ −メチレン−ビス−（４−メチル−６−ターシャリーブチルフェノール）０．１５ｇを溶解したブチルアルデヒド６０ｇを添加した。ポリビニルブチラールが析出した後、１２０分間保持し、その後、３５℃に昇温して４時間保った。反応終了後、蒸留水にて洗浄し、水洗後のポリビニルブチラール分散液に水酸化ナトリウムを添加し溶液のｐＨを７に調整した。溶液を５０℃で３時間保持した後、溶液を冷却した。このとき溶液のｐＨは６．７であった。溶液を再び蒸留水により水洗した後、乾燥した。このようにして得られたポリビニルブチラールのブチラール化度は６６ｍｏｌ％であった。このようにして、ポリビニルブチラールの合成と同時にポリビニルブチラール樹脂組成物を製造した。
【００２４】
なお、得られたポリビニルブチラール樹脂組成物のｐＨは、上記ポリビニルブチラール樹脂組成物５ｇをサンプル瓶に入れ、同時にｐＨ試験紙を入れふたをして、８０℃のギヤオーブンに１時間入れる方法により測定すると、６．５であった。
【００２５】
（２）ポリビニルブチラール樹脂組成物中の２， ２’ −メチレン−ビス−（４−メチル−６−ターシャリーブチルフェノール）の含有量
上記の方法で得られたポリビニルブチラール樹脂組成物をエタノールに溶解し、高速液体クロマトグラフィーを用いて、２， ２’ −メチレン−ビス−（４−メチル−６−ターシャリーブチルフェノール）の含有量をあらかじめ作成した検量線により定量した。なお、検出は、波長２８０ｎｍの紫外線吸収強度によった。その結果、２， ２’ −メチレン−ビス−（４−メチル−６−ターシャリーブチルフェノール）含有量は、ポリビニルブチラール１００重量部に対して０．１重量部であった。
【００２６】
（３）ポリビニルブチラール樹脂組成物の耐熱性試験
得られたポリビニルブチラール樹脂組成物をエタノールに溶解し、キャスティングにより厚さ０．５ｍｍのフィルムを作成した。このフィルムを１５０℃のギヤオーブンに入れ、加熱前、加熱５時間後、加熱１０時間後の黄色度の変化を求めた。なお、上記樹脂組成物の透明性は黄色度で評価した。黄色度は多光源分光測色計（スガ試験機社製）を用いて測定し、数値の小さい方が透明性が良好であることを示す。結果は、表２に示す通りであった。
【００２７】
（４）耐熱性試験前後のポリビニルブチラール樹脂組成物の溶液粘度の測定
上記耐熱性試験前後（すなわち、加熱前、加熱５時間後、加熱１０時間後）のポリビニルブチラール樹脂組成物のフィルムを、ポリビニルブチラール樹脂組成物濃度が１０重量％となるように、エタノール／トルエン（１／１）混合溶液に溶解し、得られた溶液の粘度をＢ型回転粘度計を用い２０℃で測定した。得られた結果を表２に示した。
【００２８】
実施例２
（１）ポリビニルブチラールの合成
重合度８００のポリビニルアルコール１００ｇを７００ｇの蒸留水に加温溶解した後、５℃に保ち、これに３５％塩酸５５ｇを加えた。次にブチルアルデヒド６０ｇを添加した。ポリビニルブチラールが析出した後、１２０分間保持し、その後、３５℃に昇温して４時間保った。反応終了後、蒸留水にて洗浄し、水洗後のポリビニルブチラール分散液に水酸化ナトリウムを添加し溶液のｐＨを７に調整した。溶液を５０℃で３時間保持した後、溶液を冷却した。このとき溶液のｐＨは６．７であった。溶液を再び蒸留水により水洗した後、乾燥した。このようにして得られたポリビニルブチラールのブチラール化度は６６ｍｏｌ％であった。
【００２９】
（２）ポリビニルブチラール樹脂組成物の製造
次に、得られたポリビニルブチラール２０ｇと２， ２’ −メチレン−ビス−（４−メチル−６−ターシャリーブチルフェノール）０．０２ｇとをエタノール１８０ｇに溶解し、ポリビニルブチラール樹脂組成物を製造した（ポリビニルブチラール１００重量部に対する２， ２’ −メチレン−ビス−（４−メチル−６−ターシャリーブチルフェノール）の比率は０．１重量部となる）。
【００３０】
（３）ポリビニルブチラール樹脂組成物の耐熱性試験
上記（１）で得られたポリビニルブチラール樹脂組成物溶液を用いてキャスティングにより厚みが０．５ｍｍのフィルムを作成した。次に実施例１（３）と同様の方法で耐熱性試験を行い、結果を表２に示した。
【００３１】
（４）耐熱性試験前後のポリビニルブチラール樹脂組成物の溶液粘度の測定
実施例１（４）と同様の方法で、上記耐熱性試験前後のポリビニルブチラール樹脂組成物の溶液粘度の測定を行い、得られた結果を表２に示した。
【００３２】
実施例３〜８、比較例１〜７
実施例２（１）ポリビニルブチラールの合成における、冷却後のポリビニルブチラール溶液のｐＨ、及び実施例２（２）ポリビニルブチラール樹脂組成物の製造における、ポリビニルブチラール１００重量部に対する２， ２’ −メチレン−ビス−（４−メチル−６−ターシャリーブチルフェノール）の添加量（重量部）を、それぞれ表１のように変えたことの他は、実施例２と同様に操作し、結果を表２に示した。なお、比較例１及び２については、２， ２’ −メチレン−ビス−（４−メチル−６−ターシャリーブチルフェノール）を添加しなかった。
【００３３】
【表１】
【表２】
実施例９
（１）ポリビニルアセタール樹脂組成物の製造
重合度８００のポリビニルアルコール１００ｇを７００ｇの蒸留水に加温溶解した後、２０℃に保ち、これに３５％塩酸５５ｇを加え、さらに、２， ２’ −メチレン−ビス−（４−メチル−６−ターシャリーブチルフェノール）０．１５ｇを溶解したアセトアルデヒド２３ｇを添加した。次に１２℃まで冷却し、ブチルアルデヒド２８ｇを加えた。ポリビニルアセタールが析出した後、３０分間保持し、その後、６０℃に昇温して３時間保った。反応終了後、蒸留水にて洗浄し、水洗後のポリビニルアセタール分散液に水酸化ナトリウムを添加し溶液のｐＨを７に調整した。溶液を７０℃で３時間保持した後、溶液を冷却した。このとき溶液のｐＨは６．７であった。溶液を再び蒸留水により水洗した後、乾燥した。このようにして得られたポリビニルアセタールのアセタール化度は７０ｍｏｌ％であった。このようにして、ポリビニルアセタールの合成と同時にポリビニルアセタール樹脂組成物を製造した。
【００３６】
なお、得られたポリビニルアセタール樹脂組成物のｐＨは、上記ポリビニルアセタール樹脂組成物５ｇをサンプル瓶に入れ、同時にｐＨ試験紙を入れふたをして、８０℃のギヤオーブンに１時間入れる方法により測定すると、６．５であった。
【００３７】
（２）ポリビニルアセタール樹脂組成物中の２， ２’ −メチレン−ビス−（４−メチル−６−ターシャリーブチルフェノール）の含有量
実施例１（２）における、ポリビニルブチラール樹脂組成物の代わりに、上記で得られたポリビニルアセタール樹脂組成物を用い、実施例１（２）と同様に操作した。その結果、２， ２’ −メチレン−ビス−（４−メチル−６−ターシャリーブチルフェノール）含有量は、ポリビニルアセタール１００重量部に対して０．１重量部であった。
【００３８】
（３）ポリビニルアセタール樹脂組成物の耐熱性試験
実施例１（３）における、ポリビニルブチラール樹脂組成物の代わりに、上記で得られたポリビニルアセタール樹脂組成物を用い、実施例１（３）と同様に操作した。得られた結果は、表４に示す通りであった。
【００３９】
（４）耐熱性試験前後のポリビニルアセタール樹脂組成物の溶液粘度の測定
実施例１（４）における、ポリビニルブチラール樹脂組成物の代わりに、上記で得られたポリビニルアセタール樹脂組成物を用い、実施例１（４）と同様に操作した。得られた結果は、表４に示す通りであった。
【００４０】
実施例１０
（１）ポリビニルアセタールの合成
重合度８００のポリビニルアルコール１００ｇを７００ｇの蒸留水に加温溶解した後、５℃に保ち、これに３５％塩酸５５ｇを加えた。次にアセトアルデヒド２３ｇを添加し、１２℃まで冷却し、ブチルアルデヒド２８ｇを加えた。ポリビニルアセタールが析出した後、３０分間保持し、その後、６０℃に昇温して３時間保った。反応終了後、蒸留水にて洗浄し、水洗後のポリビニルアセタール分散液に水酸化ナトリウムを添加し溶液のｐＨを７に調整した。溶液を５０℃で３時間保持した後、溶液を冷却した。このとき溶液のｐＨは６．７であった。溶液を再び蒸留水により水洗した後、乾燥した。このようにして得られたポリビニルアセタールのアセタール化度は７０．５ｍｏｌ％であった。
【００４１】
（２）ポリビニルアセタール樹脂組成物の製造
次に、得られたポリビニルアセタール２０ｇと２， ２’ −メチレン−ビス−（４−メチル−６−ターシャリーブチルフェノール）０．０２ｇとをエタノール１８０ｇに溶解し、ポリビニルアセタール樹脂組成物を製造した（ポリビニルアセタール１００重量部に対する２， ２’ −メチレン−ビス−（４−メチル−６−ターシャリーブチルフェノール）の比率は０．１重量部となる）。
【００４２】
（３）ポリビニルアセタール樹脂組成物の耐熱性試験
上記（１）で得られたポリビニルアセタール樹脂組成物溶液を用いてキャスティングにより厚みが０．５ｍｍのフィルムを作成した。次に実施例９（３）と同様の方法で耐熱性試験を行い、結果を表４に示した。
【００４３】
（４）耐熱性試験前後のポリビニルアセタール樹脂組成物の溶液粘度の測定
実施例９（４）と同様の方法で、上記耐熱性試験前後のポリビニルアセタール樹脂組成物の溶液粘度の測定を行い、得られた結果を表４に示した。
【００４４】
実施例１１〜１６、比較例８〜１４
実施例１０（１）ポリビニルアセタールの合成における、冷却後のポリビニルアセタール溶液のｐＨ、及び実施例１０（２）ポリビニルアセタール樹脂組成物の製造における、ポリビニルアセタール１００重量部に対する２， ２’ −メチレン−ビス−（４−メチル−６−ターシャリーブチルフェノール）の添加量（重量部）を、それぞれ表３のように変えたことの他は、実施例１０と同様に操作し、結果を表４に示した。なお、比較例８及び９については、２， ２’ −メチレン−ビス−（４−メチル−６−ターシャリーブチルフェノール）を添加しなかった。
【００４５】
【表３】
【表４】
【発明の効果】
本発明のポリビニルアセタール樹脂組成物の構成は、上記の通りであるので、ポリビニルアセタールの好ましい特性を損なうことなく、耐熱性と共に透明性の向上したポリビニルアセタール樹脂組成物を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyvinyl acetal resin composition, and particularly relates to a polyvinyl acetal resin composition having improved heat resistance and transparency.
[0002]
[Prior art]
Polyvinyl acetals have been widely used industrially as paints, safety glass interlayers, adhesives, various coatings, and various binders. However, polyvinyl acetal has insufficient heat resistance, and various methods have been proposed to compensate for this. For example, Japanese Patent Publication No. 57-57083 discloses that when polyvinyl alcohol is acetalized in an aqueous medium, by adding a specific compound, the favorable properties of polyvinyl acetal are not lost at all, and good heat resistance is obtained. It is disclosed that the polyvinyl acetal which has is obtained.
[0003]
However, the improvement of heat resistance by this method may be colored after heating although the resin itself hardly deteriorates. The obtained polyvinyl acetal is, for example, a resin for a reflection sheet binder, various kinds of materials that require transparency. It cannot be said that the resin for coating is sufficiently satisfactory.
[0004]
[Problems to be solved by the invention]
This invention is made | formed in view of the said present condition, The objective is to provide the polyvinyl acetal resin composition which improved transparency with heat resistance.
[0005]
[Means for Solving the Problems]
The polyvinyl acetal resin composition according to claim 1 is characterized by containing a polyvinyl acetal whose pH after synthesis is adjusted to 5 to 7 and a compound of the following general formula (I).
[Chemical formula 2]
[0006]
The polyvinyl acetal resin composition according to claim 2, wherein the polyvinyl acetal resin composition is polyvinyl butyral.
[0007]
The polyvinyl acetal resin composition according to claim 3 is characterized in that the polyvinyl acetal has at least two bonds selected from a formal bond, an acetoacetal bond and a butyral bond in the molecule. It is a polyvinyl acetal resin composition of description.
[0008]
The polyvinyl acetal resin composition according to claim 4, wherein the content of the compound of the general formula (I) is 0.01 to 10 parts by weight with respect to 100 parts by weight of the polyvinyl acetal. 3. The polyvinyl acetal resin composition according to any one of 3 above.
[0009]
The polyvinyl acetal resin composition of the present invention contains polyvinyl acetal and the compound of the above general formula (I).
[0010]
Examples of the compound of the general formula (I) include 2,2′-methylene-bis- (4-methyl-6-tertiarybutylphenol), 2,2′-methylene-bis- (4-ethyl-6-). Tertiary butylphenol), 4,4′-methylene-bis- (6-tertiarybutyl orthocresol), 4,4′-methylene-bis- (2,6-ditertiarybutylphenol), and the like.
[0011]
Any of the polyvinyl acetals can be used, and can be obtained by converting polyvinyl aldehyde into a vinyl acetal with an acid catalyst using polyvinyl alcohol as a raw material. Further, it may be obtained by a method in which vinyl acetate is used as a starting material and saponification and vinyl acetalization are successively performed with an acid catalyst. In these cases, the raw material polyvinyl alcohol may be polyvinyl alcohol modified by copolymerization or post-modification. The polymerization degree of polyvinyl alcohol is preferably 200 to 5000, and the saponification degree of polyvinyl alcohol is generally 80 to 99.9. Moreover, what mixed 2 or more types of these polyvinyl alcohol can also be used.
[0012]
Examples of the aldehyde used for the acetalization include formaldehyde, acetaldehyde, paraacetaldehyde, butyraldehyde and the like. Of these, butyraldehyde is particularly preferable. It is also preferable to use at least two aldehydes selected from formaldehyde, acetaldehyde and butyraldehyde.
[0013]
As a method for synthesizing polyvinyl acetal, a precipitation method, a dissolution method, a uniform method and the like are common, but are not limited to these methods.
[0014]
The method for producing the polyvinyl acetal resin composition of the present invention is not particularly limited. For example, a method in which a compound of the general formula (I) is present in advance during the synthesis of polyvinyl acetal; a polyvinyl acetal and a compound of the general formula (I) The method of mixing etc. is mentioned.
[0015]
As a method of preexisting the compound of the general formula (I) during the synthesis of the polyvinyl acetal, it may be dispersed in a polyvinyl alcohol solution or in an aldehyde to be used.
[0016]
As a method of mixing the compound of the general formula (I) with the polyvinyl acetal, a method of dry blending the polyvinyl acetal with powder; a polyvinyl acetal-containing solution, a solvent added as necessary when preparing the composition, a plasticizer, and the like Any method may be used such as blending and mixing with other drugs.
[0017]
In the polyvinyl acetal resin composition of the present invention, if the content of the compound of the general formula (I) decreases, the composition has insufficient heat resistance, and if it increases, the heat resistance is sufficient, but the resin is slightly colored. (However, the level is much improved from the conventional level), so 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of polyvinyl acetal. Particularly preferred.
[0018]
In the polyvinyl acetal resin composition of the present invention, various substances can be blended and contained as necessary. Examples of such substances include uncured or partially cured thermosetting resins (phenolic resins, melamine resins, epoxy resins, amino resins, or modified resins thereof), inorganic or organic fillings. Examples thereof include materials, plasticizers, pigments, dyes, stabilizers, surfactants, and antistatic agents.
[0019]
The polyvinyl acetal used in the present invention is limited to those adjusted to a pH of 5 to 7 after synthesis, and preferably adjusted to 6 to 7. When the pH is less than 5, the polyvinyl acetal is decomposed, and the polyvinyl acetal is deteriorated such as yellowing or lowering the polymerization degree. When the pH exceeds 7, the composition of the present invention depends on the compound of the above general formula (I). Coloring occurs.
[0020]
The pH of the polyvinyl acetal used in the present invention is adjusted to 5 to 7 using an acid, an alkali, a buffering agent, or the like. The pH adjustment may be adjusted immediately after the synthesis or may be adjusted immediately before preparing the composition.
[0021]
In order to adjust the pH of the polyvinyl acetal, after neutralizing the acid catalyst after synthesis of the polyvinyl acetal, it is controlled within the target range without adding excess alkali, or neutralized with excess alkali, A method may be used in which excess alkali is removed by a washing treatment such as washing with water, or an acid is added here again for adjustment. Further, as a method of removing the acid catalyst after synthesis, a method of adjusting the target pH by reducing the acid content in the resin using a catalyst removing agent such as ethylene oxide or methylene oxide may be used. Most preferably, a method of adjusting the pH within a target range by a method of reducing impurities in the resin by post-water washing, a catalyst removing agent, or the like is preferable.
[0022]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.
[0023]
Example 1
(1) Production of polyvinyl butyral resin composition 100 g of polyvinyl alcohol having a polymerization degree of 800 was dissolved in 700 g of distilled water by heating and maintained at 5 ° C., 55 g of 35% hydrochloric acid was added thereto, and 2, 2 ′ − 60 g of butyraldehyde in which 0.15 g of methylene-bis- (4-methyl-6-tertiary butylphenol) was dissolved was added. After the polyvinyl butyral was deposited, it was kept for 120 minutes, and then heated to 35 ° C. and kept for 4 hours. After completion of the reaction, the solution was washed with distilled water, and sodium hydroxide was added to the polyvinyl butyral dispersion after washing to adjust the pH of the solution to 7. After holding the solution at 50 ° C. for 3 hours, the solution was cooled. At this time, the pH of the solution was 6.7. The solution was again washed with distilled water and then dried. The degree of butyralization of the polyvinyl butyral thus obtained was 66 mol%. In this way, a polyvinyl butyral resin composition was produced simultaneously with the synthesis of polyvinyl butyral.
[0024]
The pH of the obtained polyvinyl butyral resin composition was measured by a method in which 5 g of the polyvinyl butyral resin composition was put in a sample bottle, and at the same time a pH test paper was put in the lid and put in a gear oven at 80 ° C. for 1 hour. Then, it was 6.5.
[0025]
(2) Content of 2,2′-methylene-bis- (4-methyl-6-tert-butylphenol) in the polyvinyl butyral resin composition The polyvinyl butyral resin composition obtained by the above method was dissolved in ethanol. Using high performance liquid chromatography, the content of 2,2′-methylene-bis- (4-methyl-6-tertiary butylphenol) was quantified using a calibration curve prepared in advance. The detection was based on the ultraviolet absorption intensity at a wavelength of 280 nm. As a result, the content of 2,2′-methylene-bis- (4-methyl-6-tertiarybutylphenol) was 0.1 part by weight with respect to 100 parts by weight of polyvinyl butyral.
[0026]
(3) Heat resistance test of polyvinyl butyral resin composition The obtained polyvinyl butyral resin composition was dissolved in ethanol, and a film having a thickness of 0.5 mm was prepared by casting. This film was put in a gear oven at 150 ° C., and the change in yellowness after heating, after 5 hours of heating, and after 10 hours of heating was determined. The transparency of the resin composition was evaluated by yellowness. The yellowness is measured using a multi-light source spectrophotometer (manufactured by Suga Test Instruments Co., Ltd.), and the smaller the value, the better the transparency. The results were as shown in Table 2.
[0027]
(4) Measurement of solution viscosity of polyvinyl butyral resin composition before and after heat resistance test Polyvinyl butyral resin composition film before and after the above heat resistance test (that is, before heating, after 5 hours of heating and after 10 hours of heating) It melt | dissolved in the ethanol / toluene (1/1) mixed solution so that the butyral resin composition density | concentration might be 10 weight%, and the viscosity of the obtained solution was measured at 20 degreeC using the B-type rotational viscometer. The results obtained are shown in Table 2.
[0028]
Example 2
(1) Synthesis of polyvinyl butyral 100 g of polyvinyl alcohol having a degree of polymerization of 800 was dissolved in 700 g of distilled water by heating and maintained at 5 ° C., and 55 g of 35% hydrochloric acid was added thereto. Next, 60 g of butyraldehyde was added. After the polyvinyl butyral was deposited, it was kept for 120 minutes, and then heated to 35 ° C. and kept for 4 hours. After completion of the reaction, the solution was washed with distilled water, and sodium hydroxide was added to the polyvinyl butyral dispersion after washing to adjust the pH of the solution to 7. After holding the solution at 50 ° C. for 3 hours, the solution was cooled. At this time, the pH of the solution was 6.7. The solution was again washed with distilled water and then dried. The degree of butyralization of the polyvinyl butyral thus obtained was 66 mol%.
[0029]
(2) Production of polyvinyl butyral resin composition Next, 20 g of the obtained polyvinyl butyral and 0.02 g of 2,2′-methylene-bis- (4-methyl-6-tert-butylphenol) were dissolved in 180 g of ethanol. A polyvinyl butyral resin composition was produced (the ratio of 2,2′-methylene-bis- (4-methyl-6-tert-butylphenol) to 100 parts by weight of polyvinyl butyral was 0.1 parts by weight).
[0030]
(3) Heat resistance test of polyvinyl butyral resin composition A film having a thickness of 0.5 mm was prepared by casting using the polyvinyl butyral resin composition solution obtained in (1) above. Next, a heat resistance test was conducted in the same manner as in Example 1 (3), and the results are shown in Table 2.
[0031]
(4) Measurement of the solution viscosity of the polyvinyl butyral resin composition before and after the heat resistance test In the same manner as in Example 1 (4), the solution viscosity of the polyvinyl butyral resin composition before and after the heat resistance test was measured. The results obtained are shown in Table 2.
[0032]
Examples 3-8, Comparative Examples 1-7
Example 2 (1) pH of the polyvinyl butyral solution after cooling in the synthesis of polyvinyl butyral, and 2, 2'-methylene- relative to 100 parts by weight of polyvinyl butyral in the production of Example 2 (2) polyvinyl butyral resin composition The procedure was the same as in Example 2 except that the addition amount (parts by weight) of bis- (4-methyl-6-tert-butylphenol) was changed as shown in Table 1, and the results are shown in Table 2. It was. In Comparative Examples 1 and 2, 2,2′-methylene-bis- (4-methyl-6-tertiary butylphenol) was not added.
[0033]
[Table 1]
[Table 2]
Example 9
(1) Production of polyvinyl acetal resin composition 100 g of polyvinyl alcohol having a polymerization degree of 800 was dissolved in 700 g of distilled water by heating and then kept at 20 ° C, to which 55 g of 35% hydrochloric acid was added, and 2, 2'- 23 g of acetaldehyde in which 0.15 g of methylene-bis- (4-methyl-6-tertiarybutylphenol) was dissolved was added. Then it was cooled to 12 ° C. and 28 g of butyraldehyde was added. After the polyvinyl acetal was deposited, it was kept for 30 minutes, and then heated to 60 ° C. and kept for 3 hours. After completion of the reaction, the solution was washed with distilled water, and sodium hydroxide was added to the polyvinyl acetal dispersion after washing to adjust the pH of the solution to 7. After holding the solution at 70 ° C. for 3 hours, the solution was cooled. At this time, the pH of the solution was 6.7. The solution was again washed with distilled water and then dried. The degree of acetalization of the polyvinyl acetal thus obtained was 70 mol%. Thus, the polyvinyl acetal resin composition was manufactured simultaneously with the synthesis of the polyvinyl acetal.
[0036]
The pH of the obtained polyvinyl acetal resin composition was measured by a method in which 5 g of the polyvinyl acetal resin composition was put in a sample bottle, and at the same time a pH test paper was put on the lid and placed in a gear oven at 80 ° C. for 1 hour. Then, it was 6.5.
[0037]
(2) Content of 2,2′-methylene-bis- (4-methyl-6-tertiarybutylphenol) in the polyvinyl acetal resin composition Instead of the polyvinyl butyral resin composition in Example 1 (2), Using the polyvinyl acetal resin composition obtained above, the same operation as in Example 1 (2) was performed. As a result, the content of 2,2′-methylene-bis- (4-methyl-6-tertiarybutylphenol) was 0.1 part by weight with respect to 100 parts by weight of polyvinyl acetal.
[0038]
(3) Heat resistance test of polyvinyl acetal resin composition The polyvinyl acetal resin composition obtained above was used instead of the polyvinyl butyral resin composition in Example 1 (3), and the same as in Example 1 (3). Operated. The obtained results were as shown in Table 4.
[0039]
(4) Measurement of the solution viscosity of the polyvinyl acetal resin composition before and after the heat resistance test In Example 1 (4), the polyvinyl acetal resin composition obtained above was used instead of the polyvinyl butyral resin composition. The same operation as in 1 (4) was performed. The obtained results were as shown in Table 4.
[0040]
Example 10
(1) Synthesis of polyvinyl acetal 100 g of polyvinyl alcohol having a polymerization degree of 800 was dissolved in 700 g of distilled water by heating and maintained at 5 ° C., and 55 g of 35% hydrochloric acid was added thereto. Next, 23 g of acetaldehyde was added and cooled to 12 ° C., and 28 g of butyraldehyde was added. After the polyvinyl acetal was deposited, it was kept for 30 minutes, and then heated to 60 ° C. and kept for 3 hours. After completion of the reaction, the solution was washed with distilled water, and sodium hydroxide was added to the polyvinyl acetal dispersion after washing to adjust the pH of the solution to 7. After holding the solution at 50 ° C. for 3 hours, the solution was cooled. At this time, the pH of the solution was 6.7. The solution was again washed with distilled water and then dried. The degree of acetalization of the polyvinyl acetal thus obtained was 70.5 mol%.
[0041]
(2) Production of polyvinyl acetal resin composition Next, 20 g of the obtained polyvinyl acetal and 0.02 g of 2,2′-methylene-bis- (4-methyl-6-tertiary butylphenol) were dissolved in 180 g of ethanol. A polyvinyl acetal resin composition was produced (the ratio of 2,2′-methylene-bis- (4-methyl-6-tertiary butylphenol) to 100 parts by weight of polyvinyl acetal was 0.1 parts by weight).
[0042]
(3) Heat resistance test of polyvinyl acetal resin composition A film having a thickness of 0.5 mm was prepared by casting using the polyvinyl acetal resin composition solution obtained in (1) above. Next, a heat resistance test was conducted in the same manner as in Example 9 (3), and the results are shown in Table 4.
[0043]
(4) Measurement of the solution viscosity of the polyvinyl acetal resin composition before and after the heat resistance test In the same manner as in Example 9 (4), the solution viscosity of the polyvinyl acetal resin composition before and after the heat resistance test was measured. The results obtained are shown in Table 4.
[0044]
Examples 11-16, Comparative Examples 8-14
Example 10 (1) pH of the polyvinyl acetal solution after cooling in the synthesis of polyvinyl acetal, and Example 2 (2) 2,2′-methylene-based on 100 parts by weight of polyvinyl acetal in the production of a polyvinyl acetal resin composition The procedure was the same as in Example 10 except that the addition amount (parts by weight) of bis- (4-methyl-6-tert-butylphenol) was changed as shown in Table 3, and the results are shown in Table 4. It was. In Comparative Examples 8 and 9, 2,2′-methylene-bis- (4-methyl-6-tertiary butylphenol) was not added.
[0045]
[Table 3]
[Table 4]
【The invention's effect】
Since the configuration of the polyvinyl acetal resin composition of the present invention is as described above, a polyvinyl acetal resin composition having improved heat resistance and transparency can be provided without impairing the preferable properties of the polyvinyl acetal.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19567297A JP3634577B2 (en) | 1997-07-22 | 1997-07-22 | Polyvinyl acetal resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19567297A JP3634577B2 (en) | 1997-07-22 | 1997-07-22 | Polyvinyl acetal resin composition |
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| Publication Number | Publication Date |
|---|---|
| JPH1135775A JPH1135775A (en) | 1999-02-09 |
| JP3634577B2 true JP3634577B2 (en) | 2005-03-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19567297A Expired - Lifetime JP3634577B2 (en) | 1997-07-22 | 1997-07-22 | Polyvinyl acetal resin composition |
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| Country | Link |
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| JP (1) | JP3634577B2 (en) |
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- 1997-07-22 JP JP19567297A patent/JP3634577B2/en not_active Expired - Lifetime
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| JPH1135775A (en) | 1999-02-09 |
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