JPH0474373B2 - - Google Patents
Info
- Publication number
- JPH0474373B2 JPH0474373B2 JP7049686A JP7049686A JPH0474373B2 JP H0474373 B2 JPH0474373 B2 JP H0474373B2 JP 7049686 A JP7049686 A JP 7049686A JP 7049686 A JP7049686 A JP 7049686A JP H0474373 B2 JPH0474373 B2 JP H0474373B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- fine powder
- inorganic fine
- surface area
- specific surface
- 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
- 239000000843 powder Substances 0.000 claims description 37
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 28
- 229920005672 polyolefin resin Polymers 0.000 claims description 18
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 13
- 239000011342 resin composition Substances 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 239000000976 ink Substances 0.000 description 16
- -1 ethylene, propylene, butene Chemical class 0.000 description 14
- 235000010216 calcium carbonate Nutrition 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000004743 Polypropylene Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 229920001155 polypropylene Polymers 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 229920001903 high density polyethylene Polymers 0.000 description 8
- 239000004700 high-density polyethylene Substances 0.000 description 8
- 238000007639 printing Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- JYIMWRSJCRRYNK-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4] JYIMWRSJCRRYNK-UHFFFAOYSA-N 0.000 description 4
- 238000007646 gravure printing Methods 0.000 description 4
- 238000007645 offset printing Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000429 sodium aluminium silicate Substances 0.000 description 2
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 2
- 210000001685 thyroid gland Anatomy 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Description
〔産業上の利用分野〕
本発明はグラビア印刷、オフセツト印刷が良好
なオレフイン系樹脂合成紙に関するものである。
〔従来技術〕
グラビア印刷は親水性基を有しないオレフイン
系樹脂フイルムでも印刷できる手段として従来よ
り用いられている。この印刷性を向上させるため
に、オレフイン系樹脂に無機微細粉末を配合して
用いることも、更に印刷性の良好さを求めてかか
る混合物から成膜されたフイルムを延伸して表面
をマツト仕上げする方法も知られている（特公昭
46−4678号、同46−34896号、同46−40794号、同
48−3902号、同60−36173号公報参照）。
この無機微細粉末を含有するフイルム、特に後
者の延伸物はグラビア印刷は勿論のこと多色オフ
セツト印刷もできる利点を有する。この延伸物は
合成紙としてポスター用紙、ステツカー用紙とし
て利用されている。
〔発明の目的〕
これら合成紙を連続オフセツト多色印刷するに
おいて、よりインキの乾燥時間の短縮が望まれて
いる。すなわち、印刷インキが乾燥していない
と、一枚目の合成紙に印刷された未乾燥のインキ
が二枚目の合成紙の裏面に転移してしまう（いわ
ゆる裏付）トラブルが発生したり、追い刷りや、
製本、製袋等の次の工程に移れない欠点がある。
本発明は、従来の無機微細粉末含有ポリオレフ
イン系樹脂の延伸物の印刷インキの乾燥性の向上
を目的とする。
〔目的を達成するための具体的手段〕
本発明においては、比表面積の大きな無機微細
粉末を使用する。
すなわち、
(A) 成分：
ポリオレフイン系樹脂 35〜92重量％
(B) 成分：
平均粒径が10ミクロン以下の無機微細粉末
65〜８重量％
上記(A)成分と(B)成分を含有する樹脂組成物（但
し、樹脂組成物中、比表面積が100m2／ｇ以上の
無機微細粉末が少なくとも２重量％含有されてい
る）よりなるフイルムを、ポリオレフイン系樹脂
の融点よりも低い温度で少なくとも１軸方向に延
伸した配向フイルムを紙状層とする合成紙を提供
するものである。
（ポリオレフイン系樹脂）
本発明において、使用されるポリオレフイン系
樹脂としては、エチレン、プロピレン、ブテン−
１等のオレフインのホモ重合体、これらオレフイ
ンの共重合体、ポリスチレン等が挙げられる。こ
れらの中でも耐薬品性、強度が要求される場合
は、ポリプロピレン、密度が0.940〜0.970ｇ／cm3
のポリエチレンが好ましい。
これらポリオレフイン系樹脂は単独で、または
２種以上併用して用いられる。必要に応じてオレ
フイン系樹脂以外の他の熱可塑性樹脂、例えば、
ポリアミド、ポリエチレンテレフタレート、塩化
ビニル・塩化ビニリデン共重合体、ポリカーボネ
ート等を樹脂分中の50重量％を越えない範囲で配
合してもよい。
（無機微細粉末）
平均粒径が10ミクロン以下の無機微細粉末とし
ては、重質炭酸カルシウム、けいそう土、焼成ク
レイ、ゼオライト、アルミノシリケート、酸化チ
タン、酸化バリウム、合成シリケート等があげら
れる。
これを無機微細粉末は合成紙に鉛筆筆記性、印
刷性を付与する。また、延伸によりこれら無機微
細粉末を核として微細ボイドがフイルム樹脂マト
リツクス中に多数形成され、合成紙を軽量にす
る。
本発明において重要なことは、比表面積が100
m2／ｇ以上、好ましくは150〜400ｇ／m2の無機微
細粉末が、フイルム組成物中に２重量％以上含有
されることである。かかる比表面積が大きい無機
微細粉末を利用することにより合成紙のインキ乾
燥性が促進される。
比表面積が100ｇ／m2以上の無機微細粉末とし
ては、合成シリケート〔例えばSiO2成分が75重
量％以上、比表面積が300m2／ｇ、平均粒径が１
ミクロン以下のものは富士デヴイソン化学(株)より
“サイロイド244”の商品名で販売されている〕、
微細硅酸〔例えば比表面積が240m2／ｇ、平均粒
径が１ミクロン以上のものは日本シリカ(株)より
“ニプシルVN3”の商品名で販売されている〕、
合成ナトリウムアルミノシリケート〔例えば比表
面積が135m2／ｇ、平均粒径が１ミクロン以下の
ものはコフラン（KOFRAN）社より“ゼオレツ
クス17S”の商品名で販売されている〕等があげ
られる。
フイルム形成樹脂組成物中の無機微細粉末の含
有量は、目的とする合成紙が透明性、半透明性、
不透明性を要求されるか否かにより大きく作用さ
れ、一般に透明、半透明性が要求される（トレー
ス用紙）ときには、８〜50重量％、好ましくは８
〜42重量％が、不透明性が要求されるとき（ポス
ター用紙、ステツカー用紙）には、35〜65重量％
の割合で用いられる。合成紙の透明性、半透明性
は無機微細粉末の含有量の他に、延伸温度、延伸
倍率にも大きく依存するので、これらを綜合して
配合量を決めるべきである。
ポリオレフイン系樹脂に比表面積が100ｇ／m2
以上の無機微細粉末(a)を配合するとき、他の比表
面積の小さい無機微細粉末(b)を併用する場合には
これらを同時に撹拌、混合するよりも、予じめ比
表面積の小さな無機微細粉末(b)100重量部に、比
表面積の大きな無機微細粉末(a)５〜40重量部を担
持させてこれをポリオレフイン系樹脂に配合して
フイルム形成用樹脂組成物を調製するのがよりイ
ンキ乾燥性の向上に効果がある。
担持する方法としては、最も簡便には(株)カワタ
製スパーミキサー“SWV−20”（商品名）に比表
面積の小さな無機微細粉末を100重量部及び比表
面積の大きな微細粉末を2.5重量部導入し１分間
撹拌した後更に(a)を2.5重量部導入して１分間撹
拌する。更に(a)の濃度を向上する場合は同様操作
を繰り返すという高速撹拌混合法があげられる。
担持する無機微細粉末(b)としては、特にインキ
の乾燥性を良好とするカルシウム成分を含有する
比表面積が0.5〜５m2／ｇの重質炭酸カルシウム
を用いるのが好ましい。
（合成紙）
本発明の実施において、オレフイン系樹脂と無
機微細粉末以外の他に、更に熱安定剤、紫外線吸
収剤、酸化防止剤、滑剤、分散剤等を配合しても
よい。
かかる樹脂組成物を押出機を用いて溶融混練
し、インフレーシヨン成形、Ｔ−ダイ成形して成
膜されたフイルムを、オレフイン系樹脂の融点よ
りも低い温度で、少くとも１軸方向に延伸して本
発明の印刷良好な合成紙を形成する。
延伸温度は、例えばホモポリプロピレンの場合
140〜162℃、好ましくは150〜160℃、高密度ポリ
エチレンの場合、120〜133℃、好ましくは125〜
130℃、低密度ポリエチレンの場合、90〜110℃、
好ましくは95〜105℃、ポリスチレンのときは120
〜140℃である。
オレフイン系樹脂を２種以上併用するときは、
少なくとも一種のオレフイン系樹脂の融点より低
い延伸温度で延伸すればよい。
延伸は縦方向、横方向の１軸、あるいは縦、横
方向の２軸方向にテンター、マンドレル、ロール
群を用いて行なわれる。
延伸便率は目的とするものの要求品質、延伸プ
ロセス、材料の種類によつて決まるものである
が、一般にテンター方式では４倍以上、マンドレ
ル方式では1.3倍以上、ロール方式では2.5倍以上
に延伸される。
延伸温度が低い程、延伸倍率が高い程、より不
透明なフイルム（合成紙）が得られる。
延伸されたフイルムの表面は必要によつてサイ
ジング処理、コーテイング処理、コロナ放電処理
される。
本発明の合成紙は、グラビア印刷は勿論のこと
オフセツト印刷、シルクスクリーン印刷も可能で
あり、アート紙、包装紙、ラベル・ステツカー用
紙、トレーシングペーパー、化粧紙、背クロス等
に使用できる。
以下、実施例により本発明を更に詳細に説明す
る。なお、実施料中の部、％は全て重量基準であ
る。また、例中の炭酸カルシウムは全て重質炭酸
カルシウムである。
実施例 １
(1) 三菱油化製ポリプロピレン“三菱ノーブレン
MA−６”（商品名、融点164℃）80部、高密度
ポリエチレン“ユカロンハードEY−40”（商品
名、融点130℃）10部および備北粉化工業(株)製
炭酸カルシウム粉末“ソフトン1800”（商品名、
比表面積２m2／ｇ、平均粒径1.5ミクロン）10
部よりなる組成物を押出機を用いて溶融混練し
た後、ダイスより200℃の温度でシート状に押
出し、約50℃迄、該シートを冷却した。次いで
このシートを約135℃に加熱した後、ロール群
の周速差を利用して縦方向に５倍延伸した。
(2) 別に、富士デヴイソン化学(株)製合成シリカ
“サイロイド244”（商品名、比表面積300m2／
ｇ）20部、高密度ポリエチレン“EY−40”５
部および三菱油化製ポリプロピレン”三菱ノー
ブレンMA−３（商品名、融点164℃）75部を(株)
カワタ製混合機“スーパーミキサーSMG−
100”（商品名）で２分間撹拌、混合後、押出機
を用いて240℃で溶融混練し、ダイスより200℃
の温度でシート状に前記(1)の縦軸延伸されたシ
ートの両側面にライネートし、一旦、室温より
20℃高い温度まで冷却後、約150℃に再加熱し、
テンターを用いて横方向に８倍延伸し、次いで
160℃のオーブン中を通過させて熱セツトして、
中間層の２軸延伸フイルムの肉厚が80μ、表裏
層の１軸延伸フイルム（紙状層）の肉厚が各々
35μの三層構造の合成紙を得た。
この合成紙の表面に、(株)明製作所製オフセツト
印刷試験機“RIテスター”（商品明）を用いて東
華色素(株)製オフセツトインキ“ベストSP”（商品
名、藍インキと紅インキを使用）を展色し、
セツト時間（印刷面を指で軽く触れてもイン
キが裏付けしない乾燥状態となる時間）
完全乾燥時間（印刷面上をHBの鉛筆で筆記
した場合でも、インキが裏付しない乾燥状態と
なる時間）
を調べたところ、次の通りであつた。
[Industrial Field of Application] The present invention relates to an olefin resin synthetic paper that is suitable for gravure printing and offset printing. [Prior Art] Gravure printing has been conventionally used as a means for printing even olefin resin films that do not have hydrophilic groups. In order to improve this printability, fine inorganic powder may be blended with the olefin resin, and for even better printability, a film formed from such a mixture may be stretched to give a matte surface finish. The method is also known (Tokukosho
46-4678, 46-34896, 46-40794, 46-4678, 46-34896, 46-40794,
48-3902 and 60-36173). Films containing this inorganic fine powder, especially the latter stretched products, have the advantage that they can be used not only for gravure printing but also for multicolor offset printing. This stretched product is used as synthetic paper for poster paper and sticker paper. [Object of the Invention] In performing continuous offset multicolor printing on these synthetic papers, it is desired to further shorten the ink drying time. In other words, if the printing ink is not dry, problems may occur in which the undried ink printed on the first sheet of synthetic paper transfers to the back side of the second sheet of synthetic paper (so-called backing). Additional printing,
There is a drawback that it is not possible to proceed to the next process such as bookbinding and bag making. The object of the present invention is to improve the drying properties of printing inks of conventional stretched polyolefin resins containing inorganic fine powder. [Specific means for achieving the object] In the present invention, an inorganic fine powder with a large specific surface area is used. That is, (A) component: polyolefin resin 35 to 92% by weight (B) component: inorganic fine powder with an average particle size of 10 microns or less
65 to 8% by weight A resin composition containing the above components (A) and (B) (provided that the resin composition contains at least 2% by weight of inorganic fine powder with a specific surface area of 100 m 2 /g or more) ) is stretched in at least one axial direction at a temperature lower than the melting point of the polyolefin resin. (Polyolefin resin) In the present invention, the polyolefin resin used is ethylene, propylene, butene-based resin, etc.
Examples include homopolymers of olefins such as No. 1, copolymers of these olefins, and polystyrene. Among these, when chemical resistance and strength are required, use polypropylene with a density of 0.940 to 0.970 g/cm 3
Polyethylene is preferred. These polyolefin resins may be used alone or in combination of two or more. If necessary, other thermoplastic resins other than olefin resins, such as
Polyamide, polyethylene terephthalate, vinyl chloride/vinylidene chloride copolymer, polycarbonate, etc. may be blended in an amount not exceeding 50% by weight based on the resin content. (Inorganic fine powder) Examples of the inorganic fine powder with an average particle size of 10 microns or less include heavy calcium carbonate, diatomaceous earth, calcined clay, zeolite, aluminosilicate, titanium oxide, barium oxide, synthetic silicate, and the like. This inorganic fine powder imparts pencil writing and printability to synthetic paper. Further, by stretching, a large number of fine voids are formed in the film resin matrix with these inorganic fine powders as cores, making the synthetic paper lightweight. What is important in the present invention is that the specific surface area is 100
m 2 /g or more, preferably 150 to 400 g/m 2 of inorganic fine powder is contained in the film composition in an amount of 2% by weight or more. By using such an inorganic fine powder with a large specific surface area, the ink drying properties of synthetic paper are promoted. As the inorganic fine powder with a specific surface area of 100 g/m 2 or more, synthetic silicates [for example, SiO 2 component of 75% by weight or more, a specific surface area of 300 m 2 /g, and an average particle size of 1
Those smaller than microns are sold under the trade name "Thyroid 244" by Fuji Davison Chemical Co., Ltd.]
Fine silicic acid (for example, those with a specific surface area of 240 m 2 /g and an average particle size of 1 micron or more are sold by Nippon Silica Co., Ltd. under the trade name "Nipsil VN3"),
Synthetic sodium aluminosilicate (for example, one with a specific surface area of 135 m 2 /g and an average particle size of 1 micron or less is sold by KOFRAN under the trade name "Zeolex 17S"). The content of the inorganic fine powder in the film-forming resin composition is determined so that the desired synthetic paper has transparency, translucency,
It largely depends on whether opacity is required, and generally when transparency or translucency is required (tracing paper), it is 8 to 50% by weight, preferably 8% by weight.
~42% by weight, 35-65% by weight when opacity is required (poster paper, sticker paper)
used at a rate of Since the transparency and translucency of synthetic paper depend not only on the content of the inorganic fine powder but also on the stretching temperature and stretching ratio, the blending amount should be determined by taking these factors into consideration. Specific surface area of polyolefin resin is 100g/m 2
When blending the above inorganic fine powder (a), if you use other inorganic fine powder (b) with a small specific surface area together, rather than stirring and mixing them at the same time, it is better to prepare the inorganic fine powder with a small specific surface area in advance. A more ink-friendly method is to prepare a film-forming resin composition by supporting 5 to 40 parts by weight of inorganic fine powder (a) with a large specific surface area on 100 parts by weight of powder (b) and blending this with a polyolefin resin. Effective in improving dryness. The simplest method for supporting is to introduce 100 parts by weight of an inorganic fine powder with a small specific surface area and 2.5 parts by weight of a fine powder with a large specific surface area into a spar mixer "SWV-20" (trade name) manufactured by Kawata Co., Ltd. After stirring for 1 minute, 2.5 parts by weight of (a) was further introduced and stirred for 1 minute. In order to further increase the concentration of (a), a high-speed stirring and mixing method in which the same operation is repeated can be used. As the supporting inorganic fine powder (b), it is particularly preferable to use heavy calcium carbonate having a specific surface area of 0.5 to 5 m 2 /g and containing a calcium component that improves the drying properties of the ink. (Synthetic Paper) In carrying out the present invention, in addition to the olefinic resin and the inorganic fine powder, a heat stabilizer, an ultraviolet absorber, an antioxidant, a lubricant, a dispersant, etc. may be added. The resin composition is melt-kneaded using an extruder, and a film formed by inflation molding and T-die molding is stretched in at least one direction at a temperature lower than the melting point of the olefin resin. The printable synthetic paper of the present invention is then formed. For example, in the case of homopolypropylene, the stretching temperature is
140-162°C, preferably 150-160°C, in the case of high-density polyethylene, 120-133°C, preferably 125-160°C
130℃, 90-110℃ for low density polyethylene,
Preferably 95-105℃, 120 for polystyrene
~140℃. When using two or more olefin resins together,
The stretching may be performed at a stretching temperature lower than the melting point of at least one olefin resin. Stretching is carried out uniaxially in the longitudinal and transverse directions, or biaxially in the longitudinal and transverse directions using a tenter, a mandrel, or a group of rolls. The stretching ratio is determined by the desired quality, the stretching process, and the type of material, but in general, the tenter method stretches 4 times or more, the mandrel method 1.3 times or more, and the roll method 2.5 times or more. Ru. The lower the stretching temperature and the higher the stretching ratio, the more opaque the film (synthetic paper) can be obtained. The surface of the stretched film is subjected to sizing treatment, coating treatment, and corona discharge treatment, if necessary. The synthetic paper of the present invention is capable of not only gravure printing but also offset printing and silk screen printing, and can be used for art paper, wrapping paper, label/sticker paper, tracing paper, decorative paper, back cloth, etc. Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that all parts and percentages in the royalties are based on weight. Moreover, all the calcium carbonates in the examples are heavy calcium carbonate. Example 1 (1) Mitsubishi Yuka Polypropylene “Mitsubishi Noblen”
80 parts of "MA-6" (trade name, melting point 164℃), 10 parts of high-density polyethylene "Yukalon Hard EY-40" (trade name, melting point 130℃), and calcium carbonate powder "Soton 1800" manufactured by Bihoku Funka Kogyo Co., Ltd. "(Product name,
Specific surface area 2m 2 /g, average particle size 1.5 microns) 10
After melting and kneading the composition consisting of 50% by weight using an extruder, it was extruded into a sheet from a die at a temperature of 200°C, and the sheet was cooled to about 50°C. Next, this sheet was heated to about 135° C., and then stretched 5 times in the longitudinal direction using the difference in peripheral speed between the roll groups. (2) Separately, synthetic silica “Thyroid 244” manufactured by Fuji Davison Chemical Co., Ltd. (trade name, specific surface area 300m 2 /
g) 20 parts, high density polyethylene “EY-40” 5
and 75 parts of Mitsubishi Noblen MA-3 (trade name, melting point 164℃) manufactured by Mitsubishi Yuka Co., Ltd.
Kawata mixing machine “Super Mixer SMG-”
100” (product name) for 2 minutes, after mixing, melt-knead at 240℃ using an extruder, and heat at 200℃ from a die.
Lining is applied to both sides of the longitudinally stretched sheet of (1) above at a temperature of
After cooling to a temperature 20℃ higher, reheat to approximately 150℃,
Stretched 8 times in the transverse direction using a tenter, then
Pass through the oven at 160℃ to set the heat,
The thickness of the biaxially stretched film in the middle layer is 80μ, and the thickness of the uniaxially stretched film (paper-like layer) in the front and back layers.
A synthetic paper with a three-layer structure of 35μ was obtained. The surface of this synthetic paper was coated with offset ink "Best SP" (trade name, blue ink and red ink, manufactured by Toka Shiki Co., Ltd.) using an offset printing tester "RI Tester" (product name) manufactured by Mei Seisakusho Co., Ltd. set time (the time when the printed surface is dry enough that the ink does not back up even if you lightly touch it with your finger) complete drying time (even if you write on the printed surface with an HB pencil, the ink will not show on the back side). When we investigated the time required for the dry state to occur without applying heat, the results were as follows.
【表】
比較例 １
(a) 三菱油化(株)製ポリプロピレン「三菱ノーブレ
ンMA−６」 75重量％
(b) 三菱油化(株)製高密度ポリエチレン「ユカロン
ハードEY−40」 ５重量％
(c) 富士デヴイソン化学(株)製合成シリカ「サイロ
イド244」（比表面積300m2／ｇ） 20重量％
を(株)カワタ製混合機「スーパーミキサーSMG−
100」（商品名）で３分間撹拌後、押出機（90φ・
Ｌ／Ｄ＝24）を用いて樹脂温度が約240℃でシー
ト状に押出し、ただちに冷却ロールに接して100
℃以下に冷却し、厚さ150μの白色不透明のフイ
ルムを得た。
この白色フイルムのインキ乾燥性は次の通りで
あつた。[Table] Comparative Example 1 (a) Polypropylene “Mitsubishi Noblen MA-6” manufactured by Mitsubishi Yuka Co., Ltd. 75% by weight (b) High-density polyethylene “Yukalon Hard EY-40” manufactured by Mitsubishi Yuka Co., Ltd. 5% by weight (c) 20% by weight of synthetic silica “Syroid 244” (specific surface area 300 m 2 /g) manufactured by Fuji Davison Chemical Co., Ltd. was added to a mixing machine “Super Mixer SMG-” manufactured by Kawata Co., Ltd.
100” (product name) for 3 minutes, then use an extruder (90φ・
L/D = 24) at a resin temperature of approximately 240°C, extruded into a sheet, and immediately placed in contact with a cooling roll for 100°C.
The mixture was cooled to below ℃ to obtain a white opaque film with a thickness of 150μ. The ink drying properties of this white film were as follows.
【表】
実施例 ２
実施例１において、縦延伸フイルム１に積層す
る紙状層の樹脂組成物を下記のようにする他は同
様にして三層構造（１軸／２軸／１軸）延伸フイ
ルムを得た。
(a) 三菱油化(株)製ポリプロピレン「三菱ノーブレ
ンMA−６」 57重量％
(b) 三菱油化(株)製高密度ポリエチレン「ユカロン
ハードEY−40」 ３重量％
(c) 日本シリカ(株)製微細ケイ酸「ニブシルVN3」
（商品名）（比表面積240m2／ｇ） ５重量％
(d) 備北粉化工業(株)製炭酸カルシウム「ソフトン
1800」（商品名）（比表面積２m2／ｇ）35重量％
実施例 ３
実施例１において、縦延伸フイルム１に積層す
る紙状層の樹脂組成物を下記のようにする他は同
様にして三層構造（１軸／２軸／１軸）延伸フイ
ルムを得た。
(a) 三菱油化(株)製ポリプロピレン「三菱ノーブレ
ンMA−６」 57重量％
(b) 三菱油化(株)製高密度ポリエチレン「ユカロン
ハードEY−40」 ３重量％
(c) KOFRAN製「ゼオレツクス17S」（商品名）
（比表面積135m2／ｇ） 10重量％
(d) 備北粉工業(株)製炭酸カルシウム「ソフトン
1800」（商品名）（比表面積２m2／ｇ）
30重量％。
比較例 ２
実施例１において、縦延伸フイルム１に積層す
る紙状層の樹脂組成物を下記のようにする他は同
様にして三層構造（１軸／２軸／１軸）延伸フイ
ルムを得た。
(a) ポリプロピレン「MA−６」 57重量％
(b) 高密度ポリエチレン「EY−40」 ３重量％
(c) 備北粉化工業(株)製炭酸カルシウム“ソフトン
1800”（商品名、比表面積２m2／ｇ）
40重量％。
これら合成紙のインキ乾燥性を次表に示す。[Table] Example 2 A three-layer structure (uniaxial/biaxial/uniaxial) stretching was carried out in the same manner as in Example 1, except that the resin composition of the paper-like layer laminated on the longitudinally stretched film 1 was changed as follows. I got the film. (a) Mitsubishi Yuka Co., Ltd.'s polypropylene "Mitsubishi Noblen MA-6" 57% by weight (b) Mitsubishi Yuka Co., Ltd.'s high-density polyethylene "Yukalon Hard EY-40" 3% by weight (c) Nippon Silica ( Co., Ltd.'s fine silicic acid "Nibsil VN3"
(Product name) (Specific surface area 240m 2 /g) 5% by weight (d) Calcium carbonate “Softon” manufactured by Bihoku Funka Kogyo Co., Ltd.
1800'' (trade name) (specific surface area 2 m 2 /g) 35% by weight Example 3 The same procedure as in Example 1 was carried out except that the resin composition of the paper-like layer laminated on the longitudinally stretched film 1 was changed to the following. A three-layer structured (uniaxial/biaxial/uniaxial) stretched film was obtained. (a) Mitsubishi Yuka Co., Ltd.'s polypropylene "Mitsubishi Noblen MA-6" 57% by weight (b) Mitsubishi Yuka Co., Ltd.'s high-density polyethylene "Yukalon Hard EY-40" 3% by weight (c) KOFRAN's " Zeorex 17S” (product name)
(Specific surface area 135m 2 /g) 10% by weight (d) Calcium carbonate “Softon” manufactured by Bihoku Flour Industry Co., Ltd.
1800” (product name) (specific surface area 2m 2 /g)
30% by weight. Comparative Example 2 A three-layer structure (uniaxial/biaxial/uniaxial) stretched film was obtained in the same manner as in Example 1, except that the resin composition of the paper-like layer laminated on the longitudinally stretched film 1 was changed as follows. Ta. (a) Polypropylene “MA-6” 57% by weight (b) High-density polyethylene “EY-40” 3% by weight (c) Calcium carbonate “Softon” manufactured by Bihoku Funka Kogyo Co., Ltd.
1800” (product name, specific surface area 2m 2 /g)
40% by weight. The ink drying properties of these synthetic papers are shown in the table below.
【表】
実施例 ４
(1) 三菱油化製ポリプロピレン“三菱ノーブレン
MA−６”（商品名、融点164℃）75部、高密度
ポリエチレン“ユカロンハードEY−40”（商品
名、融点130℃）10部および備北粉化工業(株)製
炭酸カルシウム粉末“ソフトン1800”（商品名、
比表面積２m2／ｇ、平均粒径1.5ミクロン）15
部よりなる組成物を押出機を用いて溶融混練し
た後、ダイスより220℃の温度でシート状に押
出し、約60℃迄、該シートを冷却した。次いで
このシートを約135℃に加熱した後、ロール群
の周速差を利用して縦方向に5.5倍延伸した。
(2) 別に比表面積が２m2／ｇの炭酸カルシウム23
部の表面に、比表面積200m2／ｇの合成シリカ
（日本アエロジル(株)製「アエロジル200」（商品
名））を炭酸カルシウムに対して５部吸着させ
て担持した無機微細粉末30重量％とポリプロピ
レン「MA−６」70重量％とを(株)カワタ製混合
機“スーパーミキサーSMG−100”（商品名）
で３分間撹拌、混合後、押出機を用いて240℃
で溶融混練し、ダイスより200℃の温度でシー
ト状に前記(1)に縦軸延伸されたシートの両側面
にラミネートし、一旦、室温より20℃高い温度
まで冷却後、約150℃に再加熱し、テンターを
用いて横方向に８倍延伸し、次いで160℃のオ
ーブン中を通過させて熱セツトして、中間層の
２軸延伸フイルムの肉厚が70μ、表裏層の１軸
延伸フイルム（紙状層）の肉厚が各々30μの三
層構造の合成紙を得た。
この合成紙を菊全判（636mm×939mm）に断裁
して三菱重工(株)製印刷機「ダイヤ」（商品名）
を用い東華色素(株)製インキ「ベストSP」にて
藍・紅の２色を印刷した。
この時、３色目と４色目（墨・黄）の追い刷
りが可能となつたのは２時間40分後であつた。
また、完全に乾燥するまでに３時間10分かかつ
た。
更に、実施例１と同様の方法で測定したイン
キ乾燥時間を表−４に示す。
実施例 ５
実施例４において、紙状層の樹脂組成物を下記
のように変更する他は同様にして合成紙を得た。
(a) ポリプロピレン「MA−６」 40重量％
(b) 比表面積２m2／ｇの炭酸カルシウムの表面
に、比表面積135m2／ｇのナトリウムオアルミ
ノシリケート（KOFRAN製「ゼオレツクス
17S」（商品名））を炭酸カルシウムに対して15
重量％の割合で吸着させ担持した無機微細粉末
60重量％。
比較例 ３
実施例４において、紙状層の樹脂組成物として
下記のものを用いる他は同様にして合成紙を得
た。
(a) ポリプロピレン「MA−６」 70重量％
(b) 比表面積が２m2／ｇの炭酸カルシウム
30重量％。[Table] Example 4 (1) Mitsubishi Yuka Polypropylene “Mitsubishi Noblen”
75 parts of "MA-6" (trade name, melting point 164℃), 10 parts of high-density polyethylene "Yukalon Hard EY-40" (trade name, melting point 130℃), and calcium carbonate powder "Softon 1800" manufactured by Bihoku Funka Kogyo Co., Ltd. "(Product name,
Specific surface area 2m 2 /g, average particle size 1.5 microns) 15
After melt-kneading the composition consisting of 1.0 parts using an extruder, it was extruded into a sheet from a die at a temperature of 220°C, and the sheet was cooled to about 60°C. Next, this sheet was heated to about 135° C., and then stretched 5.5 times in the longitudinal direction using the difference in circumferential speed between the roll groups. (2) Calcium carbonate23 with a specific surface area of 2 m 2 /g
30% by weight of an inorganic fine powder containing 5 parts of calcium carbonate adsorbed with synthetic silica ("Aerosil 200" (trade name) manufactured by Nippon Aerosil Co., Ltd.) with a specific surface area of 200 m 2 /g on the surface of the part. Polypropylene "MA-6" 70% by weight is mixed with Kawata Co., Ltd.'s mixing machine "Super Mixer SMG-100" (product name)
Stir for 3 minutes at 240℃ using an extruder after mixing.
The sheet is melt-kneaded using a die at a temperature of 200°C and laminated on both sides of the vertically stretched sheet as described in (1) above. Once cooled to a temperature 20°C higher than room temperature, it is then heated again to approximately 150°C. The film was heated and stretched 8 times in the transverse direction using a tenter, and then passed through an oven at 160°C and heat set to form a biaxially stretched film with an intermediate layer thickness of 70 μm and a uniaxially stretched film with the front and back layers. A synthetic paper having a three-layer structure with each paper-like layer having a thickness of 30 μm was obtained. This synthetic paper is cut into Kikuzen size (636mm x 939mm) and printed using a printing machine "Dia" (product name) manufactured by Mitsubishi Heavy Industries, Ltd.
Two colors, indigo and red, were printed using the ink "Best SP" manufactured by Toka Shiki Co., Ltd.. At this time, it was 2 hours and 40 minutes before additional printing of the third and fourth colors (ink and yellow) became possible.
It also took 3 hours and 10 minutes to completely dry. Furthermore, the ink drying times measured in the same manner as in Example 1 are shown in Table 4. Example 5 Synthetic paper was obtained in the same manner as in Example 4, except that the resin composition of the paper layer was changed as follows. (a) Polypropylene "MA-6" 40% by weight (b) Sodium aluminosilicate (KOFRAN's "Zeolex") with a specific surface area of 135 m 2 /g on the surface of calcium carbonate with a specific surface area of 2 m 2 /g
17S” (product name)) to calcium carbonate.
Inorganic fine powder adsorbed and supported in weight percent
60% by weight. Comparative Example 3 A synthetic paper was obtained in the same manner as in Example 4, except that the following resin composition was used as the paper-like layer resin composition. (a) Polypropylene "MA-6" 70% by weight (b) Calcium carbonate with a specific surface area of 2 m 2 /g
30% by weight.
Claims (1)
65〜８重量％ 上記(A)成分と(B)成分を含有する樹脂組成物（但
し、樹脂組成物中、比表面積が100m2／ｇ以上の
無機微細粉末が少なくとも２重量％含有されてい
る）よりなるフイルムを、ポリオレフイン系樹脂
の融点よりも低い温度で少なくとも１軸方向に延
伸した配向フイルムを紙状層とする合成紙。 ２ 比表面積が100m2／ｇ以上の無機微細粉末が、
SiO2成分を75重量％以上含有している合成シリ
ケートであることを特徴とする特許請求の範囲第
１項記載の合成紙。 ３ 比表面積が100m2／ｇ以上の無機微細粉末(a)
が、予じめ他の無機微細粉末(b)に担持されたの
ち、ポリオレフイン系樹脂に配合されることを特
徴とする特許請求の範囲第１項記載の合成紙。 ４ 比表面積が100m2／ｇ以上の無機微細粉末を
担持する他の無機微細粉末(b)が、比表面積が0.5
〜５m2／ｇの重質炭酸カルシウムであることを特
徴とする特許請求の範囲第３項記載の合成紙。 ５ 担持する無機微細粉末(b)100重量部に対し、
比表面積が100m2／ｇ以上の無機微細粉末(a)が５
〜40重量部の割合で用いられていることを特徴と
する特許請求の範囲第３項記載の合成紙。[Claims] 1 (A) Component: Polyolefin resin 35 to 92% by weight (B) Component: Inorganic fine powder with an average particle size of 10 microns or less
65 to 8% by weight A resin composition containing the above components (A) and (B) (provided that the resin composition contains at least 2% by weight of inorganic fine powder with a specific surface area of 100 m 2 /g or more) Synthetic paper whose paper-like layer is an oriented film obtained by stretching a film consisting of ) in at least one axis at a temperature lower than the melting point of a polyolefin resin. 2 Inorganic fine powder with a specific surface area of 100 m 2 /g or more,
The synthetic paper according to claim 1, which is a synthetic silicate containing 75% by weight or more of SiO 2 component. 3 Inorganic fine powder (a) with a specific surface area of 100 m 2 /g or more
The synthetic paper according to claim 1, wherein the synthetic paper is previously supported on another inorganic fine powder (b) and then blended into the polyolefin resin. 4 Other inorganic fine powder (b) supporting inorganic fine powder with a specific surface area of 100 m 2 /g or more has a specific surface area of 0.5
The synthetic paper according to claim 3, characterized in that it is heavy calcium carbonate of ~5 m 2 /g. 5 For 100 parts by weight of inorganic fine powder (b) to be supported,
Inorganic fine powder (a) with a specific surface area of 100 m 2 /g or more is 5
4. The synthetic paper according to claim 3, wherein the synthetic paper is used in an amount of 40 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7049686A JPS62227933A (en) | 1986-03-28 | 1986-03-28 | Synthetic paper of excellent printability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7049686A JPS62227933A (en) | 1986-03-28 | 1986-03-28 | Synthetic paper of excellent printability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62227933A JPS62227933A (en) | 1987-10-06 |
| JPH0474373B2 true JPH0474373B2 (en) | 1992-11-26 |
Family
ID=13433190
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7049686A Granted JPS62227933A (en) | 1986-03-28 | 1986-03-28 | Synthetic paper of excellent printability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62227933A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3299826B2 (en) * | 1993-10-05 | 2002-07-08 | 株式会社ユポ・コーポレーション | White resin film with excellent printability |
| AU1649201A (en) * | 1999-12-01 | 2001-06-12 | Oji-Yuka Synthetic Paper Co., Ltd. | Porous resin film |
| WO2001042340A1 (en) * | 1999-12-07 | 2001-06-14 | Yupo Corporation | Porous resin film |
| AU1731801A (en) | 1999-12-10 | 2001-06-18 | Oji-Yuka Synthetic Paper Co., Ltd. | Porous resin film |
| TW201418545A (en) * | 2012-11-13 | 2014-05-16 | Real Green Material Technology Corp | Stone-made environmental paper and a method for making the same |
| JP6057686B2 (en) * | 2012-12-05 | 2017-01-11 | 三菱鉛筆株式会社 | Eraser |
| US11207913B2 (en) | 2012-12-05 | 2021-12-28 | Mitsubishi Pencil Company, Limited | Erasing member and erasing tool using the same |
| JP7139130B2 (en) * | 2018-03-26 | 2022-09-20 | 株式会社ユポ・コーポレーション | printing paper |
-
1986
- 1986-03-28 JP JP7049686A patent/JPS62227933A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62227933A (en) | 1987-10-06 |
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