JPH0458497B2 - - Google Patents
Info
- Publication number
- JPH0458497B2 JPH0458497B2 JP59074876A JP7487684A JPH0458497B2 JP H0458497 B2 JPH0458497 B2 JP H0458497B2 JP 59074876 A JP59074876 A JP 59074876A JP 7487684 A JP7487684 A JP 7487684A JP H0458497 B2 JPH0458497 B2 JP H0458497B2
- Authority
- JP
- Japan
- Prior art keywords
- vinylidene fluoride
- molded product
- resin
- fluoride resin
- molded
- 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
- 229920005989 resin Polymers 0.000 claims description 45
- 239000011347 resin Substances 0.000 claims description 45
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 19
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 15
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims description 8
- 235000011613 Pinus brutia Nutrition 0.000 claims description 8
- 241000018646 Pinus brutia Species 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- PYVHTIWHNXTVPF-UHFFFAOYSA-N F.F.F.F.C=C Chemical compound F.F.F.F.C=C PYVHTIWHNXTVPF-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- -1 ethylene, hexafluoropropylene Chemical group 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229920005603 alternating copolymer Polymers 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000004049 embossing Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical compound FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 description 1
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
- B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
Description
〔産業上の利用分野〕
本発明は弗化ビニリデン系樹脂マツト成形物及
びその製造方法に関する。
〔従来の技術〕
樹脂成形物を艶消しすることは成形物より反射
される光を散乱させ、人間の眼に安らぎを与え、
成形物を高級品化をかもしだす効果もたらす。こ
の様な艶消し加工、即ちマツト加工としては従
来、たとえばエンボスされたゴムロールを通過さ
せて成形物をエンボスする方法、砂を常温の成形
物に吹きつけて、成形物の表面をエンボスする方
法（サンドブラスト法）、酸化チタン、二酸化珪
素等の無機物を成形物に添加することにより艶消
しする方法が知られている。
しかしながらこれらの方法はそれぞれ次の様な
問題を有する。即ちエンボスによる方法は成形物
がフイルムであるとき、フイルムの厚さが不均一
であると、ゴムロールに接する部位と接しない部
位が生じ、艶消しされる部位とされない部位が生
じてしまう。弗化ビニリデン系樹脂は結晶性樹脂
であり、しかもその結晶化度も約45％程度である
ため、本質的に均一な厚さが得られにくい樹脂で
あり、エンボス法では艶消しに斑を生じやすい。
またこの方法では一旦マツト加工されたフイルム
を他の樹脂面に被覆して使用する場合、接着力を
持たせる上で加熱融着させる。が、これは接着剤
を用いる方法は乾燥工程を必要とし、工業上採用
しにくいためである。しかしながらこの様な二次
加工を行なう過程でマツト加工されたフイルムの
マツトが消失するか、または斑を助長させること
となるという欠点も有する。
別のマツト加工法であるサンドラブラスト法は
成形物の表面に傷をつけることであり、外観上他
のマツト加工法に較べて劣つたマツト成形物を与
える。
更に別のマツト加工法である無機物を成形物に
添加する方法は、酸化チタンを始め吸水性の無機
物を用いるときには、添加する無機物の脱気を十
分に行わないと成形物の表面が泡だらけとなる。
また分散性の悪い無機物であると、分散が困難で
あり不均一なマツト加工となる欠点を有する。
〔発明が解決しようとする問題点〕
この発明はこの様な従来技術の現状に鑑み、弗
化ビニリデン系樹脂をマツト加工するに二次加工
性に支障なく、均一なマツト加工を可能にするマ
ツト成形物及びその製造方法を提供することにあ
る。
〔発明の構成〕
この発明は溶融成形された弗化ビニリデン系樹
脂を海基質とし、四弗化エチレン系樹脂を島粒子
とする海島型構造であり、島の平均粒子径が0.1
〜10μｍであるときに目的とするマツト成形物の
得られることを知見したことに基づいている。ま
たこの様な成形物が、弗化ビニリデン系樹脂が主
とし、四弗化エチレン系樹脂粉粒体を従とする混
合物を、弗化ビニリデン系樹脂の融点以上の温度
で成形することにより得られることにも基づいて
いる。
以下、本発明を詳細に説明する。
本発明に云う弗化ビニリデン系樹脂とは弗化ビ
ニリデンホモポリマーは勿論、フツ化ビニリデン
を構成単位として70モル％以上と、これと共重合
可能な１種または２種以上のモノマーを有する構
成単位の残部とからなる共重合体、或いはこれら
の少なくともいずれかの重合体を70重量％以上含
有する組成物、更にこれらと同効の物を指す。
また本発明に云う四弗化エチレン系樹脂とは四
弗化エチレンホモポリマー、四弗化エチレンを構
成単位として50モル％以上と、これと共重合可能
なモノマー、例えばエチレン、六弗化プロピレ
ン、パーフルオロビニルエーテルの如きモノマー
の１種または２種以上を有する構成単位の残部と
からなる共重合体、或いは四弗化エチレンの水素
基の代わりに他の基、例えば三弗化エチレン、パ
ーフルオロアルキルエーテルテトラフルオロエチ
レン等を置換した重合体、更にこれらと同効の物
を指す。
本発明による樹脂成形物はこの様な四弗化エチ
レン系樹脂を島粒子とし、溶融成形された弗化ビ
ニリデン系樹脂を海基質とする海島型構造を有し
ている。海島型構造とは高分子組成物の当業者に
は周知の用語であるが、海とする樹脂中に島状に
もう一方の樹脂が分散した組成物を指していう。
本発明においては弗化ビニリデン系樹脂は溶融成
形されていなければならないが、四弗化エチレン
系樹脂を溶融成形されていてもいなくてもよい。
四弗化エチレン系樹脂により形成される島粒子
の平均粒子径は大き過ぎても小さ過ぎてもマツト
化されにくいので、0.1μｍ〜10μｍの範囲の平均
粒径を有するものが用いられる。好ましくは0.1
〜5μｍ、より好ましくは0.1〜2μｍのものが用い
られる。ここで平均粒子径とは電子顕微鏡により
求めた粒子の数100個の径を求め、その値の最大
値より25個、最小値より25個を除き、50個の粒子
の径の算術平均値である。粒子はマツト成形物の
１部分のみが観測されない様に各部位を実質的に
均等に観測するものとし、各々の粒子の径は長径
と短径の相加平均とする。
また本発明のマツト成形物は定一方向に流動配
向した状態である方がマツト化される度合が高ま
り、好ましいマツト成形物となり、特定一方向に
流動配向している度合が高い程、好適に用いられ
る。特定一方向に流動配向している度合は、例え
ば成形物が透明であるときには平均複屈折率の大
きさで判別され、平均複屈折率が３×10-5以上の
ものが好ましく、１×10-4以上のものが一層好ま
しく、１×10-3以上のものが特に好ましい。ここ
で平均複屈折率はマツト成形物の成形方法によつ
ては成形物の部位により複屈折率が異なる場合が
あるので、成形物の平均の複屈折率を云う。複屈
折率は成形物の形状により、適宜選択された測定
法によらねばならないが、例えばフイルムの場合
にはフイルムの面に垂直に偏光を入射させて測定
される。成形物が不透明で複屈折率により流動配
向の度合を判別できないときには、JIS Z8741の
60゜鏡面光沢度の成形物への光の入射方向による
差で判別され、その差が0.2以上となるのが好ま
しく、より好ましくは0.3以上、より一層好まし
くは0.4以上となるものが用いられる。
以上の様な構成からなる本発明弗化ビニリデン
系樹脂成形物はマツト化され、JIS Z8741による
鏡面光沢度が75％以下のものが容易に得られ、好
適な構成の選択をすれば50％以下のもの得られ
る。
この様な成形物の形状はフイルム、糸、チユー
ブ等を始めとする任意のものであるが、特にフイ
ルム状とし、他の熱可塑性樹脂、代表的にはメタ
クリル酸エステル系樹脂、特にメタクリル酸メチ
ル系樹脂又はこれを接着面とする積層体、例えば
メタクリル酸メチル系樹脂と塩化ビニル系樹脂と
の積層物、メタクリル酸メチル系樹脂と熱可塑性
ポリエステルとの積層物等と積層されて壁紙、パ
ネル板に代表される内装材、外装材等の建材とし
て好適に用いられる。
上記マツト成形物は例えば弗化ビニリデン系樹
脂を主とし、四弗化エチレン系樹脂粉粒体を従と
する混合物を、弗化ビニリデン系樹脂の融点以上
の温度で成形することによつて得られる。ここで
「弗化ビニリデン系樹脂を主とし」とは、体積比
において四弗化エチレン系樹脂に対し、弗化ビニ
リデン系樹脂の方が多い割合を占めるという意味
である。また、四弗化エチレン系樹脂は粉状又は
粒状であり、その平均粒子径は高々10μｍのもの
を用い、各粒子は単独又は凝集した形でマツト成
形物中で島を形成する。
特にマツト成形物がフイルム状であり、透明性
を損わない程度にマツト化させる場合には、四弗
化エチレン系樹脂は弗化ビニリデン系樹脂100重
量部に対し、高々20重量部、好ましくは10重量部
以下、より好ましくは８重量部以下とすることに
より曇価度が80％以下のフイルムが得られる。他
方、四弗化エチレン系樹脂粉末が少な過ぎるとマ
ツト化されにくいので、成形物の厚さによつても
異なるが通常１重量部以上、好ましくは３重量部
以上が用いられる。
以下、実施例により本発明を更に詳細に説明す
る。
実施例１，２および比較例１
ポリ弗化ビニリデンホモポリマー（ηinh1dl／
ｇ：0.4ｇ／dl濃度のジメチルホルムアミド溶液
につき30℃で測定した値）100重量部と下記第１
表に示す量のポリ四弗化エチレンホモポリマーの
微粉末（JISB9921により求めた平均粒子径は
0.3μｍ）ヘンシエルミキサーで常温で10分間混合
し、50φ押出機で210℃で押出しペレツトを得た。
このペレツトを50φ押出機で240℃で押出し、フ
ラツトダイスより30μｍの厚さのフイルムを得
た。フイルムの艶消し状態はフイルム全体にわた
り一様に得られ、JIS Z8741に規定されているグ
ロスメーターで光沢度により測定し、島の径は本
文記載の通りにして求め、それぞれ第１表に示す
結果を得た。
[Industrial Field of Application] The present invention relates to a vinylidene fluoride resin mat molded product and a method for producing the same. [Prior art] Matting a resin molded product scatters the light reflected from the molded product, giving peace of mind to the human eye.
This has the effect of making molded products more luxurious. Conventionally, such matte processing, that is, matte processing, involves a method in which the molded product is embossed by passing it through an embossed rubber roll, a method in which sand is blown onto the molded product at room temperature, and the surface of the molded product is embossed ( Methods of matting the molded product by adding an inorganic substance such as titanium oxide or silicon dioxide to the molded product are known. However, each of these methods has the following problems. That is, in the embossing method, when the molded product is a film, if the thickness of the film is uneven, some parts come in contact with the rubber roll and some parts do not, resulting in some parts being matted and some not. Vinylidene fluoride resin is a crystalline resin, and its crystallinity is about 45%, so it is essentially difficult to obtain a uniform thickness, and the embossing method produces uneven matte surfaces. Cheap.
In addition, in this method, when the matted film is used to cover another resin surface, it is heated and fused to provide adhesive strength. However, this is because the method using adhesive requires a drying process and is difficult to adopt industrially. However, in the process of performing such secondary processing, the matte of the matted film may disappear or unevenness may be promoted. Another mat processing method, sandblasting, involves scratching the surface of the molded product, resulting in a mat molded product that is inferior in appearance to other mat processing methods. Another mat processing method, which involves adding inorganic substances to molded products, is that when water-absorbing inorganic materials such as titanium oxide are used, the surface of the molded product will be full of bubbles unless the added inorganic material is sufficiently degassed. Become.
In addition, inorganic substances with poor dispersibility have the disadvantage of being difficult to disperse and resulting in non-uniform matte processing. [Problems to be Solved by the Invention] In view of the current state of the prior art, the present invention provides a mat that enables uniform mat processing of vinylidene fluoride resin without hindering secondary processability. An object of the present invention is to provide a molded article and a method for manufacturing the same. [Structure of the Invention] This invention has a sea-island structure in which melt-molded vinylidene fluoride resin is used as a sea substrate and tetrafluoroethylene resin is used as island particles, and the average particle diameter of the islands is 0.1.
This is based on the finding that the desired pine molded product can be obtained when the thickness is 10 μm. Moreover, such a molded product can be obtained by molding a mixture containing mainly vinylidene fluoride resin and secondary tetrafluoroethylene resin powder at a temperature higher than the melting point of the vinylidene fluoride resin. It is also based on that. The present invention will be explained in detail below. The vinylidene fluoride resin referred to in the present invention is not only a vinylidene fluoride homopolymer, but also a constitutional unit having 70 mol% or more of vinylidene fluoride as a constitutional unit and one or more monomers copolymerizable with this. or a composition containing 70% by weight or more of at least one of these polymers, as well as products having the same effect as these. Furthermore, the tetrafluoroethylene-based resin referred to in the present invention is a tetrafluoroethylene homopolymer, a monomer copolymerizable with it, such as ethylene, hexafluoropropylene, A copolymer consisting of the remainder of the structural unit having one or more monomers such as perfluorovinyl ether, or other groups instead of the hydrogen group of tetrafluoroethylene, such as trifluoroethylene, perfluoroalkyl It refers to polymers substituted with ethertetrafluoroethylene, etc., and also to products that have the same effect as these. The resin molded article according to the present invention has a sea-island structure in which the tetrafluoroethylene resin is used as island particles and the melt-molded vinylidene fluoride resin is used as the sea substrate. The sea-island structure is a term well known to those skilled in the art of polymer compositions, and refers to a composition in which a sea resin is dispersed in the form of islands of another resin.
In the present invention, the vinylidene fluoride resin must be melt-molded, but the polyethylene fluoride resin may or may not be melt-molded. If the average particle size of the island particles formed by the tetrafluoroethylene resin is too large or too small, it will not be easily matted, so those having an average particle size in the range of 0.1 μm to 10 μm are used. Preferably 0.1
~5 μm, more preferably 0.1 to 2 μm. Here, the average particle size is the arithmetic mean value of the diameters of 50 particles, excluding 25 from the maximum value and 25 from the minimum value, after determining the diameter of 100 particles using an electron microscope. be. The particles shall be observed substantially uniformly in each part so that only one part of the pine molded product is not observed, and the diameter of each particle shall be the arithmetic average of the major axis and the minor axis. In addition, when the pine molded product of the present invention is in a state where the flow is oriented in a certain direction, the degree of matting increases and becomes a preferable pine molded product. used. The degree of fluid orientation in a specific direction is determined by the average birefringence when the molded product is transparent, for example, and the average birefringence is preferably 3 × 10 -5 or more, and 1 × 10 -4 or more is more preferable, and 1×10 -3 or more is particularly preferable. Here, the average birefringence refers to the average birefringence of the molded material, since the birefringence may vary depending on the part of the molded material depending on the method of molding the molded material. The birefringence index must be measured by an appropriately selected measuring method depending on the shape of the molded article, but for example, in the case of a film, it is measured by making polarized light incident perpendicularly to the surface of the film. If the molded product is opaque and the degree of flow orientation cannot be determined based on the birefringence, use JIS Z8741.
It is determined by the difference in 60° specular gloss depending on the direction of incidence of light on the molded product, and the difference is preferably 0.2 or more, more preferably 0.3 or more, even more preferably 0.4 or more. The vinylidene fluoride resin molded product of the present invention having the above-mentioned structure can be matted and easily have a specular gloss of 75% or less according to JIS Z8741, and if a suitable structure is selected, it can be 50% or less. You can get what you want. The shape of such a molded product can be arbitrary, including films, threads, tubes, etc., but it is particularly film-like, and is made of other thermoplastic resins, typically methacrylate ester resins, especially methyl methacrylate. based resin or a laminate using this as an adhesive surface, such as a laminate of methyl methacrylate resin and vinyl chloride resin, a laminate of methyl methacrylate resin and thermoplastic polyester, etc. to produce wallpaper, panel boards, etc. It is suitably used as building materials such as interior materials and exterior materials. The above-mentioned matte molded product can be obtained, for example, by molding a mixture containing mainly vinylidene fluoride resin and granular tetrafluoroethylene resin at a temperature higher than the melting point of the vinylidene fluoride resin. . Here, "mainly vinylidene fluoride resin" means that vinylidene fluoride resin occupies a larger volume ratio than tetrafluoroethylene resin. Further, the tetrafluoroethylene resin is in the form of powder or particles, and the average particle diameter is at most 10 μm, and each particle forms an island in the pine molded product, either singly or in aggregated form. In particular, when the matte molded product is in the form of a film and is to be matted to an extent that does not impair transparency, the ethylene tetrafluoride resin should be used at most 20 parts by weight, preferably at most 20 parts by weight, per 100 parts by weight of the vinylidene fluoride resin. By setting the amount to 10 parts by weight or less, more preferably 8 parts by weight or less, a film having a haze value of 80% or less can be obtained. On the other hand, if the amount of the tetrafluoroethylene resin powder is too small, it will be difficult to form a mat, so it is usually used in an amount of 1 part by weight or more, preferably 3 parts by weight or more, although it varies depending on the thickness of the molded product. Hereinafter, the present invention will be explained in more detail with reference to Examples. Examples 1 and 2 and Comparative Example 1 Polyvinylidene fluoride homopolymer (ηinh1dl/
g: value measured at 30°C for a dimethylformamide solution with a concentration of 0.4 g/dl) 100 parts by weight and the following 1
Fine powder of polytetrafluoroethylene homopolymer in the amount shown in the table (the average particle diameter determined according to JISB9921 is
(0.3 μm) was mixed for 10 minutes at room temperature using a Henschel mixer, and extruded at 210° C. using a 50φ extruder to obtain pellets.
This pellet was extruded at 240°C using a 50φ extruder, and a film with a thickness of 30 μm was obtained using a flat die. The matte state of the film was obtained uniformly over the entire film, and was measured by gloss using a gloss meter specified in JIS Z8741.The diameter of the islands was determined as described in the text, and the results are shown in Table 1. I got it.
【表】
実施例３，４および比較例２
前記比較例１並びに実施例１又は３で得たペレ
ツトをそれぞれ35φ押出機で245℃で押出し、メ
タクリル酸メチル70モル％とアクリル酸ブチル30
モル％との共重合体を74φ押出機で245℃で押出
し、両者を２層共押出用複合フラツトダイスから
押出して表層はポリ弗化ビニリデンホモポリマー
と四弗化エチレンホモポリマーとの組成物、基材
層はアクリル酸エステル系樹脂よりなる２層フイ
ルムを得た。表層の厚さは5μ、基材層の厚さは
45μである。２層フイルムの表面の艶消し状態は
均一であり、実施例１と同様に測定して第２表に
示す結果を得た。[Table] Examples 3 and 4 and Comparative Example 2 The pellets obtained in Comparative Example 1 and Example 1 or 3 were extruded at 245°C using a 35φ extruder, and 70 mol% of methyl methacrylate and 30% of butyl acrylate were extruded.
The copolymer with mole% is extruded at 245°C using a 74φ extruder, and both are extruded through a composite flat die for two-layer coextrusion. A two-layer film made of acrylic acid ester resin was obtained as the material layer. The surface layer thickness is 5μ, the base layer thickness is
It is 45μ. The surface of the two-layer film had a uniform matte state, and was measured in the same manner as in Example 1, and the results shown in Table 2 were obtained.
【表】
透明度、曇価度はJIS Z8714の規定に従つて測
定した。
実施例５，６および比較例３
四弗化エチレン系樹脂としてエチレンと四弗化
エチレンとの交互共重合体微粉末（JIS B9921に
より求めた平均粒子径は0.4μｍ）をポリ弗化ビニ
リデン100重量部に対しそれぞれ下記第３表に示
す量で使用し、ペレツト作成の際の押出温度を
305℃、フイルム作成の際の押出温度を310℃と
し、厚さ20μｍのフイルムを得た。その他は実施
例１と同様に行なつた。その結果を第３表に示
す。[Table] Transparency and haze were measured according to JIS Z8714. Examples 5, 6 and Comparative Example 3 Fine powder of an alternating copolymer of ethylene and tetrafluoroethylene (average particle diameter determined according to JIS B9921: 0.4 μm) was added to 100 weight polyvinylidene fluoride as a tetrafluoroethylene resin. of each pellet in the amounts shown in Table 3 below, and adjust the extrusion temperature when making pellets.
A film with a thickness of 20 μm was obtained by setting the extrusion temperature at 305° C. and 310° C. during film production. The rest was the same as in Example 1. The results are shown in Table 3.
【表】
実施例７，８および比較例４
実施例１のポリ四弗化エチレンホモポリマーの
代わりにエチレンと四弗化エチレンとの交互共重
合体微粉末（平均粒子径は実施例５と同じ）を下
記第４表に示す量で用いた他は実施例１と同様に
行なつた。その結果を第４表に示す。[Table] Examples 7, 8 and Comparative Example 4 Instead of the polytetrafluoroethylene homopolymer of Example 1, a fine powder of an alternating copolymer of ethylene and tetrafluoroethylene (average particle size is the same as Example 5) was used. ) was used in the amounts shown in Table 4 below. The results are shown in Table 4.
以上の実施例からわかる通り、本発明に係るマ
ツト成形物は二次加工性に何等支障を来すことな
く均一なマツト艶消しが可能である。
As can be seen from the above examples, the pine molded product according to the present invention can be uniformly matted without any problem in secondary processability.
Claims (1)
とし、四弗化エチレン系樹脂を島粒子とする海島
型構造であり、島の平均粒子径が0.1〜10μｍで、
JIS Ｚ 8741によ鏡面光沢度が75％以下であるこ
とを特徴とする弗化ビニリデン系樹脂マツト成形
物。 ２ 特定一方向に流動配向したことを特徴とする
特許請求の範囲第１項記載の弗化ビニリデン系樹
脂マツト成形物。 ３ 弗化ビニリデン系樹脂を主とし、四弗化エチ
レン系樹脂粉粒体を従とする混合物を、弗化ビニ
リデン系樹脂の融点以上の温度で成形することを
特徴とするJIS Ｚ 8741による鏡面光沢度が75％
以下である弗化ビニリデン系樹脂マツト成形物の
製造方法。 ４ 成形が押出成形でなされることを特徴とする
特許請求の範囲第３項記載の弗化ビニリデン系樹
脂マツト成形物の製造方法。[Scope of Claims] 1. A sea-island type structure in which melt-molded vinylidene fluoride resin is used as a sea substrate and tetrafluoroethylene resin is used as island particles, and the average particle diameter of the islands is 0.1 to 10 μm,
A vinylidene fluoride resin pine molded product characterized by having a specular gloss of 75% or less according to JIS Z 8741. 2. The vinylidene fluoride resin mat molded product according to claim 1, characterized in that the molded product is fluidized in one specific direction. 3. Specular gloss according to JIS Z 8741, which is characterized by molding a mixture consisting mainly of vinylidene fluoride resin and powdered ethylene tetrafluoride resin at a temperature higher than the melting point of the vinylidene fluoride resin. degree is 75%
The following method for producing a vinylidene fluoride resin pine molded product. 4. The method for producing a vinylidene fluoride resin mat molded product according to claim 3, wherein the molding is performed by extrusion molding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59074876A JPS60219027A (en) | 1984-04-16 | 1984-04-16 | Mat molding of vinylidene fluoride resin and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59074876A JPS60219027A (en) | 1984-04-16 | 1984-04-16 | Mat molding of vinylidene fluoride resin and manufacture thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60219027A JPS60219027A (en) | 1985-11-01 |
| JPH0458497B2 true JPH0458497B2 (en) | 1992-09-17 |
Family
ID=13559980
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59074876A Granted JPS60219027A (en) | 1984-04-16 | 1984-04-16 | Mat molding of vinylidene fluoride resin and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60219027A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4533115B2 (en) * | 2004-12-03 | 2010-09-01 | 三井・デュポンフロロケミカル株式会社 | Fluororesin molding method and fluororesin molding |
| JP5542295B2 (en) * | 2006-06-02 | 2014-07-09 | 三井・デュポンフロロケミカル株式会社 | Fluororesin molding method and fluororesin molding |
| US10661497B2 (en) | 2015-06-16 | 2020-05-26 | Nissei Electric Co., Ltd. | Heat shrink tube and method for producing the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5411155A (en) * | 1977-06-24 | 1979-01-27 | Ugine Kuhlmann | Lublicated thermoplastics compound based on polyvinyl fluoride |
-
1984
- 1984-04-16 JP JP59074876A patent/JPS60219027A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5411155A (en) * | 1977-06-24 | 1979-01-27 | Ugine Kuhlmann | Lublicated thermoplastics compound based on polyvinyl fluoride |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60219027A (en) | 1985-11-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6800999B2 (en) | 3D printed fluoropolymer structure | |
| JPH0324334B2 (en) | ||
| TWI290510B (en) | Low-orientation thermoplastic films | |
| JP2008501062A (en) | Thermoplastic article having a printable matte surface | |
| KR101040098B1 (en) | Multilayer Biaxially Oriented Polyester Film, Process for its Production and Its Use | |
| JPH0228239A (en) | Fluororesin-based outdoor film or sheet having low gloss and production thereof | |
| US6042928A (en) | Fluorocarbon resin sheet and glass laminate | |
| US6962740B2 (en) | Multilayer, biaxially oriented polyester film, process for its production and its use | |
| JPS6160717A (en) | Delustering agent and plastic material containing same | |
| EP2447321B1 (en) | A thermoplastic composition, method of producing the same, and articles made therefrom | |
| JPH0458497B2 (en) | ||
| JPH02307747A (en) | Structure having multiple polymer layer with vinylidene fluoride polymer layer combined with polar-polymer layer | |
| JPH0550566A (en) | Production of vinylidene fluoride resin type composite film | |
| JP3325666B2 (en) | Matte vinylidene fluoride resin film | |
| JPS63298201A (en) | Nonglare sheet | |
| JPS59199743A (en) | Flexible vinyl chloride resin composition | |
| JPS6067550A (en) | Vinyl chloride resin composition | |
| JP5645292B2 (en) | Light reflection sheet | |
| JP3672646B2 (en) | Method for producing surface-treated laminated polyester film | |
| JP3295804B2 (en) | Adiabatic daylighting plate and method of manufacturing the same | |
| US2608549A (en) | Interpolymers of vinyl chloride, higher alkyl acrylate and dialkenyl ester of olefinic dicarboxylic acid | |
| JP4133404B2 (en) | Embossing control method | |
| JP2019189780A (en) | Resin composition and molded body | |
| JP7223653B2 (en) | resin sheet | |
| CN115627108B (en) | Barrier coating liquid, heat-sealable barrier coated polylactic acid film and preparation method thereof |