JPS6136019B2 - - Google Patents
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- Publication number
- JPS6136019B2 JPS6136019B2 JP52142427A JP14242777A JPS6136019B2 JP S6136019 B2 JPS6136019 B2 JP S6136019B2 JP 52142427 A JP52142427 A JP 52142427A JP 14242777 A JP14242777 A JP 14242777A JP S6136019 B2 JPS6136019 B2 JP S6136019B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- filler
- parts
- paper
- synthetic paper
- 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
- 239000000945 filler Substances 0.000 claims description 39
- 229920005672 polyolefin resin Polymers 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 16
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- 239000011342 resin composition Substances 0.000 claims description 11
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 150000002193 fatty amides Chemical class 0.000 claims description 2
- 239000000123 paper Substances 0.000 description 31
- 239000000203 mixture Substances 0.000 description 20
- -1 ethoxyl Chemical group 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000004927 clay Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 238000007639 printing Methods 0.000 description 9
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 7
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 7
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 7
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 7
- 230000003078 antioxidant effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 229910052623 talc Inorganic materials 0.000 description 5
- 239000000454 talc Substances 0.000 description 5
- 235000012222 talc Nutrition 0.000 description 5
- 239000005909 Kieselgur Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 239000000057 synthetic resin Substances 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000007645 offset printing Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052622 kaolinite Inorganic materials 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- FYHXNYLLNIKZMR-UHFFFAOYSA-N calcium;carbonic acid Chemical compound [Ca].OC(O)=O FYHXNYLLNIKZMR-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000007647 flexography Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000007644 letterpress printing Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
〔１〕発明の背景
技術分野
本発明は、白色度の低下が少ない樹脂組成物を
紙状層とする合成紙、に関する。
無機充填剤を多量にポリオレフイン樹脂に混合
することによつてポリオレフイン樹脂の剛さ、衝
撃などに対する強度、成形加工性、外観、印刷性
などの諸性質を大幅に改善しようということはよ
く知られたところである。このような充填剤含有
樹脂組成物はフイルム、シート、射出成形品その
他各種の成形品として使用されているが、このよ
うな成形品に対する要求品質は近年ますます高級
化していく傾向にある。
ところで、合成樹脂の用途の多様化の一つとし
て合成紙の製造が盛に検討されてきているが、そ
の主流となるものは充填剤含有樹脂組成物を加工
したものであつて、その代表的なものは特公昭46
−40794号公報にみることができる。この合成紙
は、従来の合成樹脂フイルムでは得られなかつた
高度の印刷効果とパルプよりの天然紙にはなかつ
たすぐれた強度とを具えた素材として新しい用途
を拡大しつつある。
このような合成紙に対する要求品質は、従来の
紙に用いられているオフセツト印刷、グラビア印
刷、フレキソ印刷、活版印刷、スクリーン印刷な
どのあらゆる印刷方式が適用可能なこと、またそ
の印刷仕上りは高級印刷紙として知られているア
ートコート紙と同等以上であること、など従来の
合成樹脂フイルムの常識からは想像できないよう
な高度なものである。
このように印刷仕上りが高級紙と同じレベルで
あることが要求されるため、合成紙そのものはで
きる限り純白に近い白さであることが必要であ
る。しかし、従来合成紙用として使用されていた
白色無機充填剤は必ずしも満足すべきものではな
かつた。すなわち、酸化チタンおよび硫酸バリウ
ムは白色度の点では問題ないが高価であり、炭酸
カルシウムは酸性溶液に溶けるため食品包装用途
などには使用できない。シリカ、クレー、タルク
などの珪酸質の充填剤は酸およびアルカリに安定
であつてしかも比較的安価であるが、珪酸質充填
剤をポリオレフイン樹脂に混合すると全体が灰色
となつて充填剤そのものに比べて白色度がかなり
低下することが多く、白色度が極めて厳しい要求
品質の一つである合成紙では実際上使用すること
ができない。
経済性および耐酸アルカリ性の点で珪酸質充填
剤は魅力のあるものであり、従つてその白色度低
下の問題が解決されたならば食品包装用途をも含
めて合成紙の使用分野の拡大ないし高品質化に資
するところが大きい。
〔〕発明の概要
本発明は合成紙の紙状層として使用する珪酸質
充填剤含有ポリオレフイン樹脂組成物の白色度の
低下を防止することを目的とし、エトキシル脂肪
アミンないしアミドを配合することによつてこの
目的を達成しようとするものである。
従つて、本発明による色相の改良された合成紙
は、充填剤含有樹脂組成物の一軸または二軸延伸
不透明フイルムを紙状層とする合成紙において、
この充填剤含有樹脂組成物が下記の成分を含むも
のであること、を特徴とするものである。
(1) ポリオレフイン樹脂 100重量部
(2) 平均粒径0.5〜10ミクロンの珪酸質充填剤
（たゞし、この珪酸質充填剤は、SiO2として全
充填剤重量の少なくとも40重量％の珪酸を含む
ものである） 少なくとも25重量部
(3) エトキシル化した脂肪アミンないし脂肪アミ
ド 充填剤の0.1〜１重量％
〔〕発明の具体的説明
1. ポリオレフイン樹脂
ポリエチレン、プロピレン含量20重量％以下
のエチレン―プロピレンランダムないしブロツ
ク共重合体、ポリプロピレン、エチレン含量20
重量％以下のプロピレン―エチレンランダムな
いしブロツク共重合体、ポリブテン―１、その
他の一種または二種以上のオレフインのみまた
はそれを主成分として構成されている重合体が
対象となる。
本発明では、このようなポリオレフイン樹脂
は単独でまたは相互の混合物として使用される
ほか、ポリオレフイン樹脂を主要成分とする他
樹脂との混合物として使用することもできる。
2. 珪酸質充填剤
珪酸質含有量がSiO2として全充填剤重量の
少なくとも40重量％のもの、が使用される。
SiO2含量が40重量％未満のものは、これをポ
リオレフイン樹脂に混合しても色相低下が少な
く、本発明による改良が不要でありかつ改良効
果が顕著に現われない。
このような珪酸質ないし珪酸塩系充填剤の具
体例を挙げれば、たとえば、珪藻土、粘土たと
えばカオリナイト、ハロイサイト、セリサイ
ト、モンモリロナイトなど、クレー、タルク、
滑石、ホワイトカーボンと呼ばれている微粒子
珪酸、珪酸塩、シリカ、その他、がある（珪酸
質充填剤は、一般に白色である）。合成紙用と
しては、珪藻土、粘土、クレー、タルクなどが
好ましい。
珪酸質充填剤の平均粒径は、0.5〜10ミクロ
ン程度であることが好ましい。0.5ミクロン未
満では凝集が起りがちで、却つて粗い粒子を混
合したことと同じになり、一方10ミクロンを越
えると生成組成物からの成形品たとえばフイル
ムの表面平滑性が低下して、たとえば合成紙と
しての用途に不適当となる。
珪酸質充填剤の使用量は、一般にポリオレフ
イン樹脂100重量部に対して少なくとも25重量
部である。25重量部未満では白色度低下の問題
は顕著には発生せず、従つて本発明による改良
が不要である。使用量の上限は、生成組成物に
期待する物性によつて決まる。一般に、ポリオ
レフイン樹脂100重量部につき150重量部を越え
ることはあまりないであろう。
合成紙としての用途を考える場合には、通常
のフイルムでは常識的に行なわれているグラビ
ア、フレキソなどの印刷の外にオフセツト印刷
性（平板印刷性）が必須要件となるため充填剤
含有量の選択は難しいが（多すぎれば紙として
の強度が低下するという欠点が生じ、少なすぎ
れば印刷性が低下する）、一般に40〜100重量
部／ポリオレフイン樹脂100重量部が適当であ
ることが多い。
3. 色相改良剤
下記の式で表わされる脂肪アミンないしアミ
ドのエトキシル化生成物である。
ここで、Ｒは炭素数８〜18のアルキル、アルケ
ニルまたはアシル（R′―CO）であり、ｍおよ
びｎはｍ＋ｎ＝２〜20の関係にある整数であ
る。アシルの場合にも、その脂肪炭素鎖
（R′）は不飽和であつてもよい。
このような化合物の具体例を挙げれば、たと
えば下記のものがある。
合成紙用としては、
が最も適している。
添加量は、珪酸質充填剤重量の0.1〜１重量
％が適当である。0.1％未満では色相改良効果
が少なく、一方１％を越えるとポリオレフイン
樹脂の臭気および粘性が大きく変化し、成形加
工性などが低下する。また、色相改良効果も１
％を越えるとほとんど変らず一定である。
4. 組成物の調整
上記必須三成分および必要に応じて混合する
所望成分から均一組成物をつくることができる
任意の方法によることができる。このような方
法は合成樹脂組成物をつくるのに一般に公知で
あつて、通常はポリオレフイン樹脂が流動可能
な温度で各成分を一時にあるいは段階的に混練
することからなる。
必要に応じて混合する所望成分としては、ポ
リオレフイン樹脂以外の樹脂質またはゴム質材
料、珪酸質充填剤以外の充填剤（これらは、そ
れぞれポリオレフイン樹脂および珪酸質充填剤
より少量であるべきである）、酸化防止剤、紫
外線吸収剤、滑材、ブロツキング防止剤、着色
料、発泡材、その他がある。
このようにして得られる本発明組成物は、充
填剤含有ポリオレフイン樹脂組成物として各種
の用途に供することができる。
5. 合成紙
合成紙の主要なものとして、充填剤含有樹脂
組成物の一軸ないし二軸延伸フイルムを紙状層
とするものがある。この紙状層はそれ自身のみ
で合成紙を構成していてもよく、あるいは基材
層の片面または両面に接合された積層構造体と
して合成紙を構成していてもよい。
強度と紙状性とを兼備するためには、積層構
造のものが好ましく、特に前記の特公昭46−
40794号公報に示されているように二軸延伸基
材フイルムの片面または両面に充填剤含有樹脂
組成物の一軸延伸フイルムを接合した紙状層と
しての構造のものが好ましい。同公報にも示さ
れているように、この好ましい積層構造の合成
紙は基材フイルムとなるべき一軸延伸樹脂シー
トの片面または両面に本発明組成物を押出ラミ
ネートし、得られた積層シートを横方向に延伸
することによつて、つくることができる。
合成紙としての性質を最大限に発揮させるた
めには、延伸工程後に20℃以上の温度（上限
は、延伸フイルムの延伸効果が維持される最高
温度）で適当時間たとえば50時間以上に保持し
てエージングを行なうことが好ましい。
紙状層が充填剤含有樹脂フイルムを延伸（使
用ポリオレフイン樹脂の二次転移点以上であり
かつ融点ないし流動点以下で引張力を印加する
ことにより行なう）されていることに相当し
て、その表面には微細な亀裂が生じていること
がふつうである。
6.実験例
実施例―１
MI＝1.0のポリプロピレン100重量部に対し、
白色度91.5％、平均粒径４ミクロンの珪藻土を25
重量部加え、更に酸化防止剤としてBHTを全体
の0.1重量部加える。この混合物に、下記の色相
改良剤(a)または(b)を加える。
ｍ，ｎは、ｍ＋ｎ＝10の整数
で表わされる化合物を0.025、0.075、0.125、
0.25、0.325重量部
または
で表わされる化合物を0.025、0.125、0.25、0.325
重量部
混合物をスーパーミキサーで十分撹拌し、押出
機で混練押出して、ペレツト状に成形した。この
ペレツトを再び適当な温度に設定された押出機で
混合、押出して、シート状に成形した。このシー
トを150℃に加熱後、縦方向に５倍延伸したのち
冷却し、更にこの延伸シートを160℃に加熱のの
ち先の延伸と直角の方向に９倍延伸した。このよ
うにして得られたフイルムは、優れた印刷性と筆
記性とを持つていた。
ペレツト及びフイルムの白色度は下表に示す値
であり、(a)または(b)の化合物を0.025重量部（す
なわち、充填剤の0.1％）以上含むものは十分な
白色度があつて、合成紙として高級紙分野に使用
することができるものであつた。また0.25重量部
（すなわち、充填剤の１％）以上の添加量では、
白色度はほとんど変らないものであつた。
[1] BACKGROUND TECHNICAL FIELD OF THE INVENTION The present invention relates to a synthetic paper whose paper-like layer is made of a resin composition with little reduction in whiteness. It is well known that by mixing large amounts of inorganic fillers with polyolefin resins, various properties such as stiffness, impact resistance, moldability, appearance, printability, etc., can be significantly improved. By the way. Such filler-containing resin compositions are used as films, sheets, injection molded products, and various other molded products, and the quality requirements for such molded products have tended to become higher and higher in recent years. Incidentally, the production of synthetic paper has been actively studied as one way to diversify the uses of synthetic resins, but the mainstream paper is processed from filler-containing resin compositions; The thing is special public service in 1977.
It can be seen in Publication No.-40794. This synthetic paper is expanding into new applications as a material that has high printing effects that cannot be obtained with conventional synthetic resin films and excellent strength that is not available with natural paper made from pulp. The required quality for such synthetic paper is that all printing methods used for conventional paper, such as offset printing, gravure printing, flexo printing, letterpress printing, and screen printing, can be applied, and that the printing finish is equivalent to high-quality printing. It is a highly advanced material that cannot be imagined from the common knowledge of conventional synthetic resin films, such as being equivalent to or better than art coated paper, which is also known as paper. Since the printing finish is required to be on the same level as high-quality paper, the synthetic paper itself needs to be as close to pure white as possible. However, the white inorganic fillers conventionally used for synthetic paper were not always satisfactory. That is, titanium oxide and barium sulfate have no problem in terms of whiteness, but are expensive, and calcium carbonate cannot be used for food packaging applications because it dissolves in acidic solutions. Silicate fillers such as silica, clay, and talc are stable against acids and alkalis and are relatively inexpensive; however, when siliceous fillers are mixed with polyolefin resin, the whole becomes gray, compared to the filler itself. In many cases, the whiteness is considerably reduced, and therefore, it cannot be practically used with synthetic paper, for which whiteness is one of the extremely strict quality requirements. Silicate fillers are attractive from the point of view of economy and acid-alkali resistance, and therefore, if the problem of reduced whiteness can be solved, the field of use of synthetic paper, including food packaging applications, could be expanded or increased. It greatly contributes to quality improvement. [] Summary of the Invention The present invention aims to prevent a decrease in whiteness of a polyolefin resin composition containing a siliceous filler used as a paper-like layer of synthetic paper by incorporating an ethoxyl fatty amine or amide. The goal is to achieve this goal. Therefore, the synthetic paper with improved hue according to the present invention is a synthetic paper in which a paper-like layer is a uniaxially or biaxially stretched opaque film of a filler-containing resin composition.
This filler-containing resin composition is characterized in that it contains the following components. (1) 100 parts by weight of a polyolefin resin (2) A silicic filler with an average particle size of 0.5 to 10 microns (the silicic filler contains at least 40% by weight of silicic acid as SiO 2 of the total filler weight). At least 25 parts by weight (3) Ethoxylated fatty amine or fatty amide 0.1 to 1% by weight of the filler [Detailed description of the invention 1. Polyolefin resin Polyethylene, ethylene-propylene random with a propylene content of 20% by weight or less or block copolymer, polypropylene, ethylene content 20
Targets include propylene-ethylene random or block copolymers, polybutene-1, and polymers composed solely or mainly of one or more other olefins in an amount of % or less by weight. In the present invention, such polyolefin resins can be used alone or as a mixture with each other, and can also be used as a mixture with other resins containing polyolefin resin as a main component. 2. Siliceous fillers Those whose siliceous content as SiO 2 is at least 40% by weight of the total filler weight are used.
If the SiO 2 content is less than 40% by weight, even when mixed with a polyolefin resin, there is little decrease in hue, and the improvement according to the present invention is unnecessary and the improvement effect is not noticeable. Specific examples of such silicic acid or silicate fillers include diatomaceous earth, clay such as kaolinite, halloysite, sericite, montmorillonite, clay, talc,
There are fine particles of silicic acid, silicates, silica, and others called talcum and white carbon (silicic acid fillers are generally white in color). For synthetic paper, diatomaceous earth, clay, clay, talc, etc. are preferable. The average particle size of the siliceous filler is preferably about 0.5 to 10 microns. If the particle size is less than 0.5 microns, agglomeration tends to occur, which is equivalent to mixing coarse particles.On the other hand, if the particle size exceeds 10 microns, the surface smoothness of molded products such as films, such as synthetic paper, will decrease. It becomes unsuitable for use as a. The amount of siliceous filler used is generally at least 25 parts by weight per 100 parts by weight of polyolefin resin. If it is less than 25 parts by weight, the problem of reduced whiteness does not occur significantly, and therefore the improvement according to the present invention is not necessary. The upper limit on the amount used depends on the desired physical properties of the resulting composition. Generally, it will not be likely to exceed 150 parts by weight per 100 parts by weight of polyolefin resin. When considering its use as a synthetic paper, in addition to printing such as gravure and flexography, which are commonly used with ordinary films, offset printability (lithographic printability) is an essential requirement, so the filler content must be adjusted accordingly. Although the selection is difficult (if the amount is too large, the strength of the paper will be reduced; if it is too small, the printability will be reduced), but in general, 40 to 100 parts by weight/100 parts by weight of the polyolefin resin is often appropriate. 3. Hue improver This is an ethoxylation product of a fatty amine or amide represented by the following formula. Here, R is alkyl, alkenyl or acyl (R'--CO) having 8 to 18 carbon atoms, and m and n are integers in the relationship m+n=2 to 20. In the case of acyl, the fatty carbon chain (R') may also be unsaturated. Specific examples of such compounds include the following. For synthetic paper, is the most suitable. The appropriate amount of addition is 0.1 to 1% by weight based on the weight of the siliceous filler. If it is less than 0.1%, the hue improvement effect will be small, while if it exceeds 1%, the odor and viscosity of the polyolefin resin will change significantly, and moldability will deteriorate. In addition, the hue improvement effect is 1
When it exceeds %, it remains constant with almost no change. 4. Preparation of the composition Any method that can produce a homogeneous composition from the above three essential components and optionally mixed desired components can be used. Such methods are generally known for making synthetic resin compositions and usually consist of kneading the components all at once or in stages at a temperature that allows the polyolefin resin to flow. Desired components to be mixed as necessary include resinous or rubbery materials other than polyolefin resins, and fillers other than silicic fillers (each of these should be in smaller amounts than the polyolefin resin and silicic filler). , antioxidants, ultraviolet absorbers, lubricants, antiblocking agents, colorants, foaming materials, and others. The composition of the present invention thus obtained can be used for various purposes as a filler-containing polyolefin resin composition. 5. Synthetic paper The main type of synthetic paper is one whose paper-like layer is a uniaxially or biaxially stretched film of a filler-containing resin composition. This paper-like layer may constitute the synthetic paper by itself, or it may constitute the synthetic paper as a laminated structure bonded to one or both sides of the base material layer. In order to have both strength and paper-like properties, it is preferable to have a laminated structure, especially the above-mentioned
As shown in Japanese Patent No. 40794, a paper-like layer structure in which a uniaxially stretched film of a filler-containing resin composition is bonded to one or both sides of a biaxially stretched base film is preferred. As shown in the same publication, this synthetic paper with a preferable laminated structure is obtained by extrusion laminating the composition of the present invention on one or both sides of a uniaxially stretched resin sheet to serve as a base film, and then laying the resulting laminated sheet on its side. It can be made by stretching in the direction. In order to maximize the properties of synthetic paper, it must be held at a temperature of 20°C or higher (the upper limit is the maximum temperature at which the stretching effect of the stretched film is maintained) for an appropriate period of time, such as 50 hours or more, after the stretching process. It is preferable to carry out aging. Corresponding to the fact that the paper-like layer is a filler-containing resin film that has been stretched (by applying a tensile force above the secondary transition point and below the melting point or pour point of the polyolefin resin used), its surface It is common for fine cracks to occur in the 6. Experimental Example-1 For 100 parts by weight of polypropylene with MI = 1.0,
25 diatomaceous earth with a whiteness of 91.5% and an average particle size of 4 microns
Add part by weight, and further add 0.1 part by weight of BHT as an antioxidant. To this mixture is added the following hue modifier (a) or (b). m, n are integers of m + n = 10, and the compounds are 0.025, 0.075, 0.125,
0.25, 0.325 parts by weight or Compounds expressed as 0.025, 0.125, 0.25, 0.325
Parts by weight The mixture was thoroughly stirred using a super mixer, and kneaded and extruded using an extruder to form pellets. The pellets were again mixed and extruded using an extruder set at an appropriate temperature to form a sheet. This sheet was heated to 150°C, stretched 5 times in the machine direction, cooled, and further heated to 160°C, and then stretched 9 times in the direction perpendicular to the previous stretching. The film thus obtained had excellent printability and writability. The whiteness of pellets and films is the value shown in the table below, and those containing 0.025 parts by weight or more of the compound (a) or (b) (i.e., 0.1% of the filler) have sufficient whiteness and cannot be synthesized. The paper could be used in the high-grade paper field. Also, if the amount added is more than 0.25 parts by weight (i.e. 1% of the filler),
The whiteness remained almost unchanged.
【表】
実施例―２
MI＝2.0のポリエチレン100重量部に対し、酸
化防止剤としてBHTを0.1重量部加え、更に
で表わされる色相改良剤化合物を0.1重量部加え
る。
この混合物に
(a) 焼成クレー
SiO2含量52％、平均粒径２μ
(b) タルク
SiO2含量62％、平均粒径３μ
(c) 珪藻土
SiO2含量92％、平均粒径５μ
(d) 炭酸カルシウム
SiO2含量０％、平均粒径５μ
(e) ろう石クレー
SiO2含量68％、平均粒径３μ
(f) カオリナイト
SiO2含量45％、平均粒径２μ
をそれぞれ30重量部混合し、ミキサーで十分混合
したのち適温に設定された押出機でシート状に押
出す。このシートを150℃に加熱し、縦横それぞ
れ５倍に延伸する。比較例として上記の色相改良
剤化合物を含まないものを作成した。得られたフ
イルムの物性は次に示す通りであり、(a)〜(c)、(e)
〜(f)の充填剤では上記色相改良剤化合物の添加に
より白色度が大巾に向上していることがわかる。[Table] Example-2 0.1 part by weight of BHT was added as an antioxidant to 100 parts by weight of polyethylene with MI = 2.0, and Add 0.1 part by weight of a hue improver compound represented by . This mixture contains (a) calcined clay with a SiO 2 content of 52% and an average particle size of 2μ (b) talc with a SiO 2 content of 62% and an average particle size of 3μ (c) diatomaceous earth with a SiO 2 content of 92% and an average particle size of 5μ (d) carbonic acid Calcium SiO 2 content 0%, average particle size 5μ (e) Roxite clay SiO 2 content 68%, average particle size 3μ (f) Kaolinite SiO 2 content 45%, average particle size 2μ 30 parts by weight each mixed, After thoroughly mixing with a mixer, extrude into a sheet using an extruder set at an appropriate temperature. This sheet is heated to 150°C and stretched 5 times in length and width. As a comparative example, one not containing the above-mentioned hue improver compound was prepared. The physical properties of the obtained film are as shown below, (a) to (c), (e)
It can be seen that the whiteness of the fillers (f) is greatly improved by the addition of the hue improver compound.
【表】
実施例 ３
ポリエチレン（MI＝２、密度0.95）100重量部
に粒径0.05ミクロンのホワイトカーボン（SiO2含
量99.8％）をそれぞれ10重量部、17重量部、25重
量部および50重量部混合したものに、酸化防止剤
としてBHTを0.1部加え、更に実施例―１で使用
したエトキシル化アミド（ｂの化合物）を充填剤
の0.2％重量混合し、ミキサーで十分予備混合し
たのち、適温に設定された押出機で混練して、シ
ート状に成形し、このシートを実施例―２と同様
に延伸して、紙状のフイルムを得た。比較例とし
てエトキシル化アミドを添加しない混合物も同様
に押出して、フイルム状に成形した。
各々のフイルムの白色度は次に示すようなもの
であり、充填剤が25重量部以上含有されている場
合にはエトキシル化アミド化合物の白色度改良効
果が顕著であることがわかる。[Table] Example 3 10 parts by weight, 17 parts by weight, 25 parts by weight and 50 parts by weight of white carbon (SiO 2 content 99.8%) with a particle size of 0.05 microns in 100 parts by weight of polyethylene (MI=2, density 0.95), respectively. To the mixture, 0.1 part of BHT was added as an antioxidant, and 0.2% of the filler weight of the ethoxylated amide (compound b) used in Example-1 was mixed. After thorough premixing with a mixer, the mixture was heated to an appropriate temperature. The mixture was kneaded in an extruder set to 1 to form a sheet, and this sheet was stretched in the same manner as in Example 2 to obtain a paper-like film. As a comparative example, a mixture to which no ethoxylated amide was added was similarly extruded and formed into a film. The whiteness of each film is as shown below, and it can be seen that the whiteness improving effect of the ethoxylated amide compound is remarkable when the filler is contained in an amount of 25 parts by weight or more.
【表】
実施例―４
MI＝1.0のポリプロピレン100重量部に対し、
平均粒径２ミクロン、白色度91％のクレーを30重
量部および酸化防止剤としてBHTを0.1重量部加
えた混合物に更に下記(a)〜(g)の化合物を0.1重量
部混合し、スーパーミキサーで十分に予備混合し
たのち、250℃に設定された押出機で混練し、約
２mm厚さのシート状に成形する。このシートを
150℃に加熱後、縦方向に５倍延伸し、次に160℃
に加熱したのち横方向に８倍延伸する。得られた
フイルムは白色で不透明であり、筆記性の優れた
ものであつた。
この白色不透明フイルムの表面をコロナ放電処
理したのち表面に高分子型帯電防止剤（CMI―
5050Z三洋化成）を塗布したのち、適当な時間熱
処理（約50℃）を行なつた。
熱処理されたフイルムの連続４色オフセツト印
刷機によるオフセツト印刷性は従来の天然紙と同
等の機械適性と印刷仕上りを示し、高級印刷向け
合成紙として極めて優れたものであつた。[Table] Example-4 For 100 parts by weight of polypropylene with MI=1.0,
A mixture of 30 parts by weight of clay with an average particle size of 2 microns and a whiteness of 91% and 0.1 parts by weight of BHT as an antioxidant was further mixed with 0.1 parts by weight of the following compounds (a) to (g), and then mixed in a super mixer. After thorough premixing, the mixture is kneaded in an extruder set at 250°C and formed into a sheet approximately 2 mm thick. this sheet
After heating to 150℃, stretching 5 times in the longitudinal direction, then stretching to 160℃
After heating, the film is stretched 8 times in the transverse direction. The obtained film was white and opaque, and had excellent writability. After corona discharge treatment was applied to the surface of this white opaque film, a polymer antistatic agent (CMI) was added to the surface.
5050Z (Sanyo Chemical) was applied, and heat treatment (approximately 50°C) was performed for an appropriate amount of time. The heat-treated film showed the same mechanical suitability and printing finish as conventional natural paper in offset printing using a continuous four-color offset printing machine, and was extremely excellent as a synthetic paper for high-grade printing.
【表】【table】
実施例―５
M.I.＝1.0のポリプロピレン100重量部に対し平
均粒径２ミクロンおよび白色度91％のクレーを20
重量部、ならびに酸化防止剤BHT（ブチル化ヒ
ドロキシトルエン）を0.1重量部加えた混合物に
C18H37N（CH2CH2OH）2で表わされる化合物を
0.1重量部添加し、十分混合撹拌したのち、250℃
に設定された押出機で厚さ1.5mmのシートに成形
する。このシートを150℃に加熱したのち縦方向
に約５倍延し冷却する。
M.I.＝3.0のポリプロピレン100重量部に対し平
均粒径２ミクロンおよび白色度91％のクレーを70
重量部ならびに酸化防止剤BHTを0.1重量部加え
た混合物にC18H37N（CH2CH2O）2で表わされる
化合物をそれぞれ０、0.02、0.07、0.2、0.5およ
び0.7重量部を加え、十分撹拌したのち、250℃に
設定された押出機で押出して、上述の縦方向延伸
シートの両面にラミネートし冷却する。
この三層積層シートを、つぎに160℃に加熱し
たのち、横方向に８倍延伸する。得られたフイル
ムは次のような性質であり、C18H37H
（CH2CH2OH）2が0.07重量部以上添加されたフイ
ルムは高級紙として用いられる白さを持つたもの
であつた。 Example-5 20 parts of clay with an average particle size of 2 microns and a whiteness of 91% was added to 100 parts by weight of polypropylene with MI = 1.0.
part by weight and 0.1 part by weight of the antioxidant BHT (butylated hydroxytoluene).
A compound represented by C 18 H 37 N(CH 2 CH 2 OH) 2
Add 0.1 part by weight, mix thoroughly, and heat to 250℃.
Form into a 1.5 mm thick sheet using an extruder set to . This sheet is heated to 150°C, stretched about 5 times in the longitudinal direction, and cooled. 70 parts by weight of clay with an average particle size of 2 microns and a whiteness of 91% for 100 parts by weight of polypropylene with MI = 3.0.
0, 0.02, 0.07, 0.2, 0.5 and 0.7 parts by weight of a compound represented by C 18 H 37 N(CH 2 CH 2 O) 2 were added to a mixture in which 0.1 parts by weight and the antioxidant BHT were added, After sufficient stirring, the mixture is extruded using an extruder set at 250°C, laminated on both sides of the above-mentioned longitudinally stretched sheet, and cooled. This three-layer laminated sheet is then heated to 160°C and then stretched 8 times in the transverse direction. The obtained film has the following properties: C 18 H 37 H
The film to which 0.07 parts by weight or more of (CH 2 CH 2 OH) 2 was added had a whiteness suitable for use as high-quality paper.
【表】
横延伸前のシートより横延伸後のフイルムは白
色度が高くなるが、これは横延伸により表面層フ
イルム内に微細な空隙が形成され（本実施例では
横延伸前表面層のシートの密度1.2が延伸後は0.8
となつている）フイルム内で光が散乱されるため
である。[Table] The whiteness of the film after transverse stretching is higher than that of the sheet before transverse stretching, but this is because fine voids are formed in the surface layer film due to transverse stretching (in this example, the whiteness of the film is higher than that of the sheet before transverse stretching). Density of 1.2 is 0.8 after stretching
This is because light is scattered within the film.
Claims (1)
不透明フイルムを紙状層とする合成紙において、
この充填剤含有樹脂組成物が下記の成分を含むも
のであることを特徴とする、色相の改良された合
成紙。 (1) ポリオレフイン樹脂 100重量部 (2) 平均粒径0.5〜10ミクロンの珪酸質充填剤
（たゞし、この珪酸質充填剤は、SiO2として全
充填剤重量の少なくとも40重量％の珪酸を含む
ものである） 少なくとも25重量部 (3) エトキシル化した脂肪アミンないし脂肪アミ
ド 充填剤の0.1〜１重量％[Claims] 1. A synthetic paper having a paper-like layer made of a uniaxially or biaxially stretched opaque film of a filler-containing resin composition,
A synthetic paper with improved hue, characterized in that the filler-containing resin composition contains the following components: (1) 100 parts by weight of a polyolefin resin (2) A silicic filler with an average particle size of 0.5 to 10 microns (the silicic filler contains at least 40% by weight of silicic acid as SiO 2 of the total filler weight). (3) Ethoxylated fatty amines or fatty amides 0.1 to 1% by weight of the filler
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14242777A JPS5474842A (en) | 1977-11-28 | 1977-11-28 | Resin composition and synthetic paper containing colorrimproved filler |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14242777A JPS5474842A (en) | 1977-11-28 | 1977-11-28 | Resin composition and synthetic paper containing colorrimproved filler |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5474842A JPS5474842A (en) | 1979-06-15 |
| JPS6136019B2 true JPS6136019B2 (en) | 1986-08-15 |
Family
ID=15315063
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14242777A Granted JPS5474842A (en) | 1977-11-28 | 1977-11-28 | Resin composition and synthetic paper containing colorrimproved filler |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5474842A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5922944A (en) * | 1982-07-30 | 1984-02-06 | Mitsubishi Petrochem Co Ltd | Resin composition for extrusion molding |
| CA1277078C (en) * | 1988-05-09 | 1990-11-27 | Yoshiharu Fukui | Inorganic filler containing polyolefin composition |
| JP4639394B2 (en) * | 2000-11-13 | 2011-02-23 | 学校法人日本大学 | Chemical recycling method for synthetic paper |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5128878A (en) * | 1974-09-05 | 1976-03-11 | Showa Yuka Kk | TOMEISEITOBUROTSUKINGUBOSHISEINOSUGURETA ENSHINHORIPUROPIRENFUIRUMU NO SEIZOHOHO |
| JPS5173077A (en) * | 1974-12-21 | 1976-06-24 | Tokuyama Soda Kk | Fukugoshiitono seizohoho |
| JPS5271546A (en) * | 1975-12-12 | 1977-06-15 | Kao Corp | Method for dispersing pigments in to synthetic resins |
-
1977
- 1977-11-28 JP JP14242777A patent/JPS5474842A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5128878A (en) * | 1974-09-05 | 1976-03-11 | Showa Yuka Kk | TOMEISEITOBUROTSUKINGUBOSHISEINOSUGURETA ENSHINHORIPUROPIRENFUIRUMU NO SEIZOHOHO |
| JPS5173077A (en) * | 1974-12-21 | 1976-06-24 | Tokuyama Soda Kk | Fukugoshiitono seizohoho |
| JPS5271546A (en) * | 1975-12-12 | 1977-06-15 | Kao Corp | Method for dispersing pigments in to synthetic resins |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5474842A (en) | 1979-06-15 |
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