JP2594329B2 - Low-gloss fluororesin-based outdoor film or sheet and method for producing the same - Google Patents
Low-gloss fluororesin-based outdoor film or sheet and method for producing the sameInfo
- Publication number
- JP2594329B2 JP2594329B2 JP63174890A JP17489088A JP2594329B2 JP 2594329 B2 JP2594329 B2 JP 2594329B2 JP 63174890 A JP63174890 A JP 63174890A JP 17489088 A JP17489088 A JP 17489088A JP 2594329 B2 JP2594329 B2 JP 2594329B2
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- sheet
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- weight
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- gloss
- Prior art date
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- Shaping Of Tube Ends By Bending Or Straightening (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、表面低光沢を有し、耐候性、耐汚染性及び
耐薬品性にすぐれた低光沢フツ素樹脂系屋外用フイルム
またはシート及びその製造方法に関するものである。The present invention relates to a low-gloss fluororesin-based outdoor film or sheet having a low surface gloss and having excellent weather resistance, stain resistance and chemical resistance. The present invention relates to the manufacturing method.
（従来の技術） 現在フツ化ビニリデン樹脂フイルムまたはシートは、
耐候性、耐汚染性及び耐薬品性等にすぐれているため、
プラスチツク、ガラス、スレート、ゴム、金属板、木
板、その他の基材表面の保護、装飾等の目的で半永久ま
たは永久的に貼合せる表面保護フイルムとして広く使用
されている。そして近年これらフイルムまたはシート
は、高品質化、高機能化、特殊化といつた傾向が強くな
り、このため低光沢なフイルムまたはシートの必要性が
増してきた。(Prior art) Currently, vinylidene fluoride resin film or sheet is
Because it has excellent weather resistance, stain resistance and chemical resistance,
It is widely used as a surface protection film that can be semi-permanently or permanently bonded for the purpose of protecting and decorating the surface of plastic, glass, slate, rubber, metal plates, wood plates, and other base materials. In recent years, these films or sheets tend to be of high quality, high functionality, and specialization, and thus the necessity of low gloss films or sheets has increased.
一般にプラスチツクフイルムまたはシートの低光沢化
の方法は、エンボスロールによりエンボス加工する方
法、フイルムの表面を化学薬品の作用あるいは固体粒子
の吹き付けなどにより化学的あるいは物理的に粗面化す
る方法等がある。しかしながらフツ化ビニリデン系樹脂
単独では、融点から結晶化開始温度までの幅が狭い、結
晶化開始温度が高い、結晶化が速い等のためフイルムま
たはシートの表面に均一なエンボスをかけて低光沢化す
ることが困難であつた。In general, methods for reducing the gloss of a plastic film or sheet include a method of embossing with an embossing roll, and a method of chemically or physically roughening the surface of a film by the action of a chemical agent or spraying solid particles. . However, vinylidene fluoride resin alone has a narrow width from the melting point to the crystallization start temperature, a high crystallization start temperature, and a fast crystallization. It was difficult to do.
（発明が解決しようとする課題） 本発明は、かかる欠点を解決するものであり、フツ化
ビニリデン系樹脂と相溶性にすぐれた樹脂とによる樹脂
組成物を用いることにより、低光沢性、耐候性、耐汚染
性及び耐薬品性にすぐれたフイルムまたはシート及びそ
の製造方法を完成するに至つた。(Problems to be Solved by the Invention) The present invention solves the above-mentioned drawbacks, and uses a resin composition composed of a vinylidene fluoride resin and a resin having excellent compatibility to provide low gloss and weather resistance. Thus, a film or sheet having excellent stain resistance and chemical resistance and a method for producing the same have been completed.
（課題を解決するための手段） すなわち本発明は、フツ化ビニリデン系樹脂95〜50重
量部とメタクリル酸エステル系樹脂５〜50重量部とを主
成分とする樹脂組成物からなるフイルムまたはシートで
あつて、該フイルムまたはシートの表面に凹凸を形成さ
せて、その表面光沢がJIS Z−8741の測定による光沢度
で25％以下であることを特徴とするフッ素樹脂系屋外用
フイルムまたはシート及びその製造方法である。(Means for Solving the Problems) That is, the present invention relates to a film or sheet comprising a resin composition containing 95 to 50 parts by weight of a vinylidene fluoride resin and 5 to 50 parts by weight of a methacrylate resin. A fluororesin outdoor film or sheet, characterized in that irregularities are formed on the surface of the film or sheet, and the surface gloss of the film or sheet is 25% or less as measured by JIS Z-8741. It is a manufacturing method.
本発明で使用するフル化ビニリデン系樹脂（以下PVDF
という）とは、フツ化ビニリデンのホモポリマー、又は
フツ化ビニリデンと共重合可能な単量体との共重合体を
いう。共重合可能な単量体としては例えば４フツ化エチ
レン、６フル化プロピレン、３フツ化塩化エチレン、フ
ツ化ビニルなどがある。Vinylidene fluoride resin (hereinafter referred to as PVDF) used in the present invention.
") Means a homopolymer of vinylidene fluoride or a copolymer of vinylidene fluoride with a monomer copolymerizable therewith. Examples of the copolymerizable monomer include ethylene tetrafluoride, propylene hexafluoride, ethylene trifluoride chloride, and vinyl fluoride.
次にメタクリル酸エステル系樹脂（以下PMMAという）
とは、メタクリル酸メチルのホモポリマー又はメタクリ
ル酸メチルと共重合可能な単量体との共重合体、例えば
ポリメタクリル酸メチルとアクリル系ゴムとのブレンド
物等をいう。共重合可能な単量体としては、炭素数２〜
４のメタクリル酸エステル、アクリル酸ブチルをはじめ
とする炭素数１〜８のアクリル酸エステル、スチレン、
α−メチルスチレン、アクリロニトリル、アクリル酸、
他のエチレン性不飽和モノマー等がある。Next, methacrylate resin (hereinafter referred to as PMMA)
The term “methyl methacrylate” refers to a homopolymer of methyl methacrylate or a copolymer of a monomer copolymerizable with methyl methacrylate, such as a blend of polymethyl methacrylate and an acrylic rubber. As the copolymerizable monomer, a compound having 2 to 2 carbon atoms
4 methacrylates, acrylates having 1 to 8 carbon atoms including butyl acrylate, styrene,
α-methylstyrene, acrylonitrile, acrylic acid,
Other ethylenically unsaturated monomers and the like.
また上記樹脂組成物は、添加剤として着色剤、紫外線
吸収剤、酸化防止剤、充填剤等を適宜使用することがで
きる。着色剤は、耐候性にすぐれた複合酸化物系無機顔
料が好ましく、主な複合酸化物系無機顔料には、TiO2・
Sb2O3・BaO・NiOCr2O3を主成分とするルチル型やブリデ
ライト型結晶のチタンイエロー系、ZnO・Fe2O3・Cr2O3
を主成分とするスピネル型結晶の亜鉛−鉄系ブラウン、
CoO・Al2O3・Cr2O3を主成分とするスピネル型結晶のコ
バルトブルー系、TiO2・CoO・NiO・ZnOを主成分とする
グリーン系、CuO・Cr2O3やCuO・Fe2O3・Mn2O3を成分と
するスピネル型のブラツク系、CoOやMn2O3からなるバイ
オレツト系等がある。そしてこれらの有色顔料とともに
ルチル型酸化チタン、亜鉛華、炭酸カルシウム、硫酸バ
リウム、その他の無機系顔料が使用できる。着色剤の添
加量は、色調（顔料組成）により異なるため特に規定は
しないが、一般にはPVDFとPMMAからなる樹脂組成物100
重量部に対して５〜30重量部である。In the resin composition, a colorant, an ultraviolet absorber, an antioxidant, a filler, and the like can be appropriately used as additives. The coloring agent is preferably a composite oxide-based inorganic pigment excellent in weather resistance, and TiO 2
Sb 2 O 3 · BaO · NiOCr 2 O 3 rutile and Burideraito-type crystal titanium Yellow mainly composed of, ZnO · Fe 2 O 3 · Cr 2 O 3
Zinc-iron-based brown of spinel type crystal whose main component is
Cobalt Blue spinel crystals of CoO · Al 2 O 3 · Cr 2 O 3 as a main component, a green system mainly composed of TiO 2 · CoO · NiO · ZnO , CuO · Cr 2 O 3 and CuO · Fe There are a spinel black system containing 2 O 3 · Mn 2 O 3 as a component, a bioret system composed of CoO and Mn 2 O 3, and the like. Rutile-type titanium oxide, zinc white, calcium carbonate, barium sulfate and other inorganic pigments can be used together with these colored pigments. The amount of the colorant to be added is not particularly specified because it varies depending on the color tone (pigment composition).
It is 5 to 30 parts by weight based on parts by weight.
次に本発明のフイルム又はシートに用いる樹脂組成物
は、PVDF95〜50重量部とPMMA5〜50重量部からなり、PMM
Aが５重量部未満では、低光沢性が得られ難く、また50
重量部を超えると耐候性、耐汚染性及び耐薬品性等の堅
牢度を十分発揮することができない。Next, the resin composition used in the film or sheet of the present invention is composed of 95 to 50 parts by weight of PVDF and 5 to 50 parts by weight of PMMA.
If A is less than 5 parts by weight, it is difficult to obtain low gloss and
If the amount is more than 10 parts by weight, it is not possible to sufficiently exhibit fastness such as weather resistance, stain resistance and chemical resistance.
本発明のフイルム又はシートの表面光沢は、JIS Z−8
741で測定した光沢度で25％以下であり、その製造方法
は、押出機で溶融押出された直後のフイルム又はシート
をエンボスロールを通過させることにより凹凸を形成さ
せて得ることができる。また他の製造方法としては、前
記押出しフイルム又はシートを冷却後、再加熱してエン
ボスロールを通過させて低光沢化する方法でもよい。そ
のほか充填剤を高充填した樹脂組成物を用いてフイルム
又はシートとし、艶消しロールを通過させて得る方法も
ある。本発明のフイルム又はシートは、単独で使用する
こともできるし、他の熱可塑性樹脂、例えばメタクリル
酸エステル系樹脂、メタクリル酸エステル系樹脂とフツ
化ビニリデン系樹脂との組成物、塩化ビニル樹脂、スチ
レン樹脂、ABS樹脂、ポリエステル、ポリカーボネー
ト、ポリアミド等のフイルム又はシートとの多層化とし
ても使用することができる。The surface gloss of the film or sheet of the present invention is JIS Z-8
The glossiness measured by 741 is 25% or less, and the production method can be obtained by passing a film or sheet immediately after being melt-extruded by an extruder through an embossing roll to form irregularities. As another manufacturing method, a method may be used in which the extruded film or sheet is cooled, then reheated and passed through an embossing roll to reduce gloss. In addition, there is a method in which a film or a sheet is formed using a resin composition highly filled with a filler, and the film or sheet is obtained by passing through a matting roll. The film or sheet of the present invention can be used alone, or other thermoplastic resins, for example, a methacrylate resin, a composition of a methacrylate resin and a vinylidene fluoride resin, a vinyl chloride resin, It can also be used as a multilayer with a film or sheet of styrene resin, ABS resin, polyester, polycarbonate, polyamide and the like.
（実施例） 以下実施例により本発明をさらに詳細に説明する。(Examples) Hereinafter, the present invention will be described in more detail with reference to Examples.
実施例１ ソルベイ社ポリフツ化ビニリデン商品名「ソーレフ10
10」80重量部、三菱レイヨン（株）社メタクリル酸エス
テル系樹脂商品名「アクリペツトMD」20重量部及び顔料
混合物として調色しておいた2.5Y8.0/2.0（クリーム）
顔料20重量部をミキシングした後、２軸混練押出機で混
練し、コンパウンドとした。次に調整したコンパウンド
を原料とし、40mmφ押出機にスリツト0.4mm、幅450mmの
コートハンガーダイを備えた装置を使用し、ダイ温度26
0℃で溶融押出し、１対の冷却ロールの一方にシリコー
ンゴム100重量部に対して充填剤50重量部を配合した配
合物を被覆したエンボスロールを用いてエンボス加工
し、厚さ30μｍの表面低光沢フイルムを得た。結果を表
に示す。Example 1 Solvay polyvinylidene fluoride trade name "Soref 10
10 "80 parts by weight, Mitsubishi Rayon Co., Ltd. methacrylate-based resin trade name" Acrypet MD "20 parts by weight and 2.5Y8.0 / 2.0 (cream) toned as a pigment mixture
After mixing 20 parts by weight of the pigment, the mixture was kneaded with a twin-screw kneading extruder to obtain a compound. Next, using the prepared compound as a raw material, using a 40 mmφ extruder equipped with a coat hanger die having a slit of 0.4 mm and a width of 450 mm, a die temperature of 26 mm was used.
It is melt extruded at 0 ° C and embossed using an embossing roll coated with a mixture of 100 parts by weight of silicone rubber and 50 parts by weight of a filler on one of a pair of cooling rolls. A glossy film was obtained. The results are shown in the table.
実施例２ 実施例１においてソーレフ1010を60重量部、アクリペ
ツトMDを40重量部を用いた以外は実施例１と同様に行つ
た結果を表に示す。Example 2 The results obtained in Example 1 are shown in the table, except that 60 parts by weight of Solef 1010 and 40 parts by weight of Acrypet MD were used.
比較例１ 実施例１においてソーレフ1010、単独を用いた以外は
実施例１と同様に行つた。結果を表に示す。Comparative Example 1 The same procedure was performed as in Example 1 except that solef 1010 was used alone. The results are shown in the table.
比較例２ 実施例１においてソーレフ1010を30重量部アクリペツ
トMD70重量部を用いた以外は実施例１と同様に行つた。
結果を表に示す。Comparative Example 2 The same procedure was performed as in Example 1 except that 30 parts by weight of Solef 1010 and 70 parts by weight of Acrypet MD were used.
The results are shown in the table.
実施例３ 〔表面層用コンパウンド〕 実施例１においてソーレフ1010 65重量部、アクリペ
ツトMD35重量部を用いた以外は実施例１と同様に行いコ
ンパウンドとした。Example 3 [Compound for surface layer] A compound was prepared in the same manner as in Example 1 except that 65 parts by weight of Soref 1010 and 35 parts by weight of Acrypet MD were used.
ソルベイ社ポリフツ化ビニリデン商品名「ソーレフ10
10」20重量部、三菱レイヨン（株）社メタクリル酸エス
テル系樹脂商品名「アクリペツトMD」80重量部、紫外線
吸収剤として２−ヒドロキシ−４−ｎ−オクトオキシベ
ンゾフエノン３重量部をミキシングした後、２軸混練押
出機で混練し、コンパウンドとした。Solvay polyvinylidene fluoride
10 ", 20 parts by weight, 80 parts by weight of" Acrypet MD "(trade name of methacrylate resin, manufactured by Mitsubishi Rayon Co., Ltd.), and 3 parts by weight of 2-hydroxy-4-n-octoxybenzophenone as an ultraviolet absorber were mixed. Thereafter, the mixture was kneaded with a twin-screw kneading extruder to obtain a compound.
次に調整した２種類のコンパウンドを原料とし40mmφ
押出機２台、フイードブロツクダイ、スリツト幅0.4m
m、幅450mmのコートハンガーダイを備えた装置を使用
し、ダイ温度260℃で溶融押出し、表面層側に実施例１
と同様のエンボスロールを押し当て、エンボス加工し
た。結果を表に示す。Next, use the adjusted two kinds of compounds as raw materials, 40mmφ
2 extruders, feed block die, slit width 0.4m
Using a device equipped with a coat hanger die having a width of 450 mm and a width of 450 mm, melt extrusion was performed at a die temperature of 260 ° C., and Example 1 was formed on the surface layer side.
The same embossing roll as described above was pressed and embossed. The results are shown in the table.
実施例４ 実施例３の表面層用コンパウンドにおいてソーレフ10
10、90重量部アクリペツトMD10重量部を用い、裏面層用
コンパウンドに三菱瓦斯化学（株）社ポリカーボネート
商品名コーピロン7030Aを用いた以外は実施例３と同様
に行つた。Example 4 In the compound for the surface layer of Example 3, Solef 10 was used.
The same procedure as in Example 3 was carried out except that 10 and 90 parts by weight of Acrypet MD 10 parts by weight were used, and the compound for the back layer was Corpilon 7030A (trade name of polycarbonate manufactured by Mitsubishi Gas Chemical Company, Ltd.).
実施例５ 〔表面層用コンパウンド〕 実施例１で用いた組成物を用いた。Example 5 [Compound for surface layer] The composition used in Example 1 was used.
ソルベイ社ポリフツ化ビニリデン商品名「ソーレフ10
10」20重量部、三菱レイヨン（株）社メタクリル酸エス
テル系樹脂商品名「アクリペツトMD」80重量部、紫外線
吸収剤として２−ヒドロキシ−４−ｎ−オクトオキシベ
ンゾフエノン３重量部をミキシングした後、２軸混練押
出機で混練し、コンパウンドとした。Solvay polyvinylidene fluoride
10 ", 20 parts by weight, 80 parts by weight of" Acrypet MD "(trade name of methacrylate resin, manufactured by Mitsubishi Rayon Co., Ltd.), and 3 parts by weight of 2-hydroxy-4-n-octoxybenzophenone as an ultraviolet absorber were mixed. Thereafter, the mixture was kneaded with a twin-screw kneading extruder to obtain a compound.
三菱瓦斯化学（株）社ポリカーボネート商品名「ユー
ピロン7030A」を用いた。Mitsubishi Gas Chemical Co., Ltd. polycarbonate product name "Iupilon 7030A" was used.
次に調整した３種類のコンパウンドを原料とし65φmm
押出機１台と40φmm押出機２台とを使用した以外は実施
例３と同様にして行つた。結果を表に示す。Next, use the three kinds of adjusted compounds as raw materials, 65φmm
The procedure was performed in the same manner as in Example 3 except that one extruder and two 40 mm extruders were used. The results are shown in the table.
実施例６ 実施例３においてエンボスロールの代わりに、ゴムロ
ールを用いて光沢を有するフイルムを製造し、その後、
別工程でフイルムを150℃に加熱後、実施例１と同様の
エンボスロールを押し当て、エンボス加工をした。結果
を表に示す。Example 6 A glossy film was produced using a rubber roll instead of the embossing roll in Example 3, and thereafter,
After the film was heated to 150 ° C. in another step, the same embossing roll as in Example 1 was pressed and embossed. The results are shown in the table.
（発明の効果） 以上のとおり、本発明は特定の樹脂組成物を用いるこ
とにより、耐候性、耐汚染性、耐薬品性にすぐれ、しか
も表面光沢を低光沢化する特徴を有するものである。 (Effects of the Invention) As described above, the present invention is characterized in that by using a specific resin composition, it has excellent weather resistance, stain resistance, and chemical resistance, and has a low surface gloss.
Claims (2)
タクリル酸エステル系樹脂５〜50重量部とを主成分とす
る樹脂組成物からなるフィルムまたはシートであって、
該フィルムまたはシートの表面に凹凸を形成させて、そ
の表面光沢がJIS Ｚ−8741の測定による光沢度で25％
以下であることを特徴とするフッ素樹脂系屋外用フィル
ムまたはシート。1. A film or sheet comprising a resin composition containing 95 to 50 parts by weight of a vinylidene fluoride resin and 5 to 50 parts by weight of a methacrylate resin,
The surface of the film or sheet is made to have irregularities, and its surface gloss is 25% as measured by JIS Z-8741.
A fluororesin outdoor film or sheet characterized by the following.
タクリル酸エステル系樹脂５〜50重量部とを主成分とす
る樹脂組成物を押出機でフィルムまたはシートを押出し
た後、エンボスロールを通過させて前記フィルムまたは
シートの表面に凹凸を形成させて、その表面光沢をJIS
Ｚ−8741の測定による光沢度を25％以下にすることを
特徴とする低光沢フッ素樹脂系屋外用フィルムまたはシ
ートの製造方法。2. An extruder is used to extrude a resin composition containing 95 to 50 parts by weight of a vinylidene fluoride resin and 5 to 50 parts by weight of a methacrylate ester resin into a film or a sheet, and then emboss rolls are formed. Pass through the surface of the film or sheet to form irregularities, the surface gloss of which is JIS
A method for producing a low-gloss fluororesin-based outdoor film or sheet, wherein the glossiness measured by Z-8741 is 25% or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63174890A JP2594329B2 (en) | 1988-07-15 | 1988-07-15 | Low-gloss fluororesin-based outdoor film or sheet and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63174890A JP2594329B2 (en) | 1988-07-15 | 1988-07-15 | Low-gloss fluororesin-based outdoor film or sheet and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0228239A JPH0228239A (en) | 1990-01-30 |
| JP2594329B2 true JP2594329B2 (en) | 1997-03-26 |
Family
ID=15986468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63174890A Expired - Fee Related JP2594329B2 (en) | 1988-07-15 | 1988-07-15 | Low-gloss fluororesin-based outdoor film or sheet and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2594329B2 (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4410148A1 (en) * | 1994-03-24 | 1995-09-28 | Huels Chemische Werke Ag | Multi-layer plastic tube |
| US5848769A (en) * | 1996-08-26 | 1998-12-15 | Minnesota Mining & Manufacturing Company | Drag reduction article |
| US5965256A (en) * | 1997-10-14 | 1999-10-12 | Minnesota Mining And Manufacturing Company | Protective films and coatings |
| US6878440B1 (en) | 1999-07-02 | 2005-04-12 | 3M Innovative Properties Company | Pressure sensitive adhesive sheet and production method thereof |
| FR2842530B1 (en) * | 2002-07-17 | 2004-09-03 | Atofina | COEXTRUDABLE COMPOSITION WITH PVDF |
| US7553894B2 (en) | 2005-07-28 | 2009-06-30 | 3M Innovative Properties Company | Cold-shrink article and method of making cold-shrink article |
| JP5255191B2 (en) * | 2006-06-30 | 2013-08-07 | 電気化学工業株式会社 | Surface protective film for interior and exterior building materials and method for producing the same |
| JP4976762B2 (en) * | 2006-07-03 | 2012-07-18 | 電気化学工業株式会社 | Vinylidene fluoride resin laminated film and method for producing the same |
| US7642460B2 (en) | 2007-04-06 | 2010-01-05 | 3M Innovative Properties Company | Cold shrinkable article including a fluoroelastomer composition |
| US7705085B2 (en) | 2007-04-06 | 2010-04-27 | 3M Innovative Properties Company | Fluoroelastomer composition for cold shrink articles |
| US8188178B2 (en) | 2007-05-07 | 2012-05-29 | 3M Innovative Properties Company | Cold shrinkable article including an epichlorohydrin composition |
| US7635813B2 (en) | 2007-09-10 | 2009-12-22 | 3M Innovative Properties Company | Article and method for sealing fluid-containing cables |
| US7973241B2 (en) | 2007-09-10 | 2011-07-05 | 3M Innovative Properties Company | Pressure restraining enclosure for cables |
| GB0805713D0 (en) * | 2008-03-28 | 2008-04-30 | Blade Dynamics Ltd | A wind turbine blade |
| DE102012207100A1 (en) | 2012-04-27 | 2013-10-31 | Evonik Industries Ag | Coextruded impact-modified PMMA film |
| KR101399422B1 (en) * | 2012-12-26 | 2014-05-30 | 에스케이씨 주식회사 | MONO-LAYER PVdF FILM AND PREPARATION METHOD THEREOF |
| WO2018221643A1 (en) * | 2017-06-01 | 2018-12-06 | デンカ株式会社 | Vinylidene-fluoride resin film |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4867347A (en) * | 1971-12-17 | 1973-09-14 | ||
| JPS5122944B2 (en) * | 1972-11-06 | 1976-07-13 | ||
| JPS5017457A (en) * | 1973-06-15 | 1975-02-24 | ||
| JPS59140053A (en) * | 1983-01-31 | 1984-08-11 | カンボウプラス株式会社 | Laminated cloth having excellent contamination resistance |
| JPS59150743A (en) * | 1983-02-18 | 1984-08-29 | 平岡織染株式会社 | Resin laminate of excellent flexion resistance |
| JPS6021651A (en) * | 1983-07-18 | 1985-02-04 | Canon Inc | Network system |
| JPS6067133A (en) * | 1983-09-26 | 1985-04-17 | Kohjin Co Ltd | Biaxially oriented film of polyvinylidene fluoride and preparation thereof |
| JPS6287349A (en) * | 1985-10-14 | 1987-04-21 | 大日本印刷株式会社 | Decorative material |
| JPS62138533A (en) * | 1985-12-13 | 1987-06-22 | Dainippon Ink & Chem Inc | Production of transparent polyvinylidene fluoride film |
-
1988
- 1988-07-15 JP JP63174890A patent/JP2594329B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0228239A (en) | 1990-01-30 |
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