JP2006117916A - Non-oriented printing paper - Google Patents
Non-oriented printing paper Download PDFInfo
- Publication number
- JP2006117916A JP2006117916A JP2005261449A JP2005261449A JP2006117916A JP 2006117916 A JP2006117916 A JP 2006117916A JP 2005261449 A JP2005261449 A JP 2005261449A JP 2005261449 A JP2005261449 A JP 2005261449A JP 2006117916 A JP2006117916 A JP 2006117916A
- Authority
- JP
- Japan
- Prior art keywords
- aliphatic
- printing paper
- acid
- range
- printing
- 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.)
- Granted
Links
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- 239000004645 polyester resin Substances 0.000 claims abstract description 42
- 229920005989 resin Polymers 0.000 claims abstract description 41
- 239000011347 resin Substances 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 23
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical group CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000007645 offset printing Methods 0.000 claims abstract description 14
- 125000001931 aliphatic group Chemical group 0.000 claims description 36
- 239000002253 acid Substances 0.000 claims description 27
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 15
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 12
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- 235000014655 lactic acid Nutrition 0.000 claims description 7
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- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 4
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- 239000002245 particle Substances 0.000 description 4
- 229920000747 poly(lactic acid) Polymers 0.000 description 4
- 239000004626 polylactic acid Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- 239000002904 solvent Substances 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- FWVNWTNCNWRCOU-UHFFFAOYSA-N 2-hydroxy-3,3-dimethylbutanoic acid Chemical compound CC(C)(C)C(O)C(O)=O FWVNWTNCNWRCOU-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
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- 239000003484 crystal nucleating agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000007646 gravure printing Methods 0.000 description 2
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- 229920001519 homopolymer Polymers 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
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- 239000000178 monomer Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
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- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
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- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
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- 230000037303 wrinkles Effects 0.000 description 2
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- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- WXYNMTGBLWPTNQ-UHFFFAOYSA-N tetrabutoxygermane Chemical compound CCCCO[Ge](OCCCC)(OCCCC)OCCCC WXYNMTGBLWPTNQ-UHFFFAOYSA-N 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- GXMNGLIMQIPFEB-UHFFFAOYSA-N tetraethoxygermane Chemical compound CCO[Ge](OCC)(OCC)OCC GXMNGLIMQIPFEB-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は印刷用紙に関する。詳しくは、脂肪族ポリエステル樹脂に無機微細粉末を配合してなる組成物を溶融させてフィルム状に成形した無延伸樹脂フィルムであって、優れた枚葉オフセット印刷性を有する印刷用紙、およびそれを用いたラベルを提供するものである。 The present invention relates to printing paper. Specifically, it is an unstretched resin film obtained by melting a composition obtained by blending an inorganic polyester powder with an aliphatic polyester resin into a film shape, and has excellent sheet-fed offset printability, and The label used is provided.
従来より、ポリオレフィン樹脂に無機微細粉末を配合し、溶融させてフィルム状に成形し、このフィルム状成形物の両面に合成紙を一体に貼り合わせて印刷可能とした、複合合成紙が提案されている（特許文献１）。この複合合成紙は、芯材層として無延伸熱可塑性樹脂層を有するものであり、トランプカード、書類ファイル、標識、台紙、花ラベル等の用紙として有用で、印刷が可能で、肉厚が２５０〜８００μｍと厚い複合積層樹脂フィルムに関するものである。
しかしながら、これら合成紙の原料となるポリオレフィン樹脂は、化石原料に由来するものであり、将来的にも安定して供給が可能であるとは言えない。また、使用後に焼却せず埋め立てて処理する場合には、長期にわたり土壌に残存するなどの廃棄上の問題もある。
そこで、従来の化石原料由来の樹脂に代わり、植物資源由来のバイオマス原料を主に利用した脂肪族ポリエステル樹脂、いわゆる「グリーンプラ（登録商標）」を用いた樹脂フィルムの登場が期待されており、既に多くの報告がされている（特許文献２、特許文献３、特許文献４、特許文献５、特許文献６、特許文献７）。
Conventionally, composite synthetic paper has been proposed, in which inorganic fine powder is blended with polyolefin resin, melted and formed into a film, and synthetic paper is integrally bonded to both sides of the film-like molded product to enable printing. (Patent Document 1). This composite synthetic paper has an unstretched thermoplastic resin layer as a core material layer, is useful as a paper for cards such as playing cards, document files, signs, mounts, flower labels, etc., can be printed, and has a wall thickness of 250. It relates to a composite laminated resin film as thick as ˜800 μm.
However, the polyolefin resin used as the raw material for these synthetic papers is derived from the fossil raw material, and cannot be said to be able to be stably supplied in the future. In addition, when landfilled without being incinerated after use, there is a problem in disposal such as remaining in the soil for a long time.
Therefore, instead of conventional fossil raw material-derived resins, the appearance of resin films using aliphatic polyester resins mainly using plant-derived biomass raw materials, so-called “Green Pla (registered trademark)”, is expected. Many reports have already been made (Patent Literature 2, Patent Literature 3, Patent Literature 4, Patent Literature 5, Patent Literature 6, Patent Literature 7).
しかしながら、枚葉オフセット印刷が可能な印刷用紙には、・紙剥けが無いこと、・耐水性があること、・寸法安定性があること、・紙くせが少ないこと、・適度な水濡れ性があること、・インキ密着性、乾燥性、インキセットが良いこと、・適正な腰（こわさ、剛度）をもつこと、・印刷機上での走行性が安定していること、・網点の再現性が良いことなど、多くの品質要求があり、これらの要求品質を満足した樹脂フィルムは未だ実現されていない。
なぜなら、上述の文献においてオキシカルボン酸の単独重合体（所謂ポリ乳酸等）を用いたものは、高い弾性率のために硬く脆く、引張破断しやすい性質があり、得られるフィルムは、用紙が走路上（ロール／ブランケット間など）でひどくしごかれる枚葉オフセット印刷や、ロール間で高張力がかかる輪転オフセット印刷やグラビア印刷等において、柔軟で可撓性のある天然紙や合成紙、ポリオレフィン系樹脂フィルムのような印刷機上での安定した走行性は得られない。
However, printing paper that can be used for sheet-fed offset printing has no paper peeling, has water resistance, has dimensional stability, has little paper shading, has moderate water wettability・ Ink adhesion, dryness, good ink set ・ Proper stiffness (stiffness, stiffness) ・ Stable running on the printing press ・ Reproduction of halftone dots There are many quality requirements such as good quality, and a resin film that satisfies these required qualities has not yet been realized.
This is because, in the above-mentioned documents, those using oxycarboxylic acid homopolymers (so-called polylactic acid or the like) are hard and brittle due to their high elastic modulus, and tend to break easily. Flexible and flexible natural paper and synthetic paper, polyolefin-based for sheet-fed offset printing that is heavily crushed on the top (between rolls / blankets, etc.), rotary offset printing and gravure printing that require high tension between rolls, etc. A stable running property on a printing machine such as a resin film cannot be obtained.
また、ポリ乳酸系以外であって脂肪族ジオールと脂肪族ジカルボン酸とを主原料とする脂肪族ポリエステル樹脂に関しては、ポリオレフィン樹脂並の優れた強度と伸び、弾性率が得られる。これを用いたフィルムや合成紙の報告もされている（特許文献８等）ものの、該特許文献における樹脂組成物は、得られたフィルムが本発明の如き印刷特性を有しているかは不明確であり、特に印刷の鮮明性を与える不透明性が得られるとは考えにくいものである。
さらに、天然紙の両面に脂肪族ポリエステル系樹脂の薄膜をラミネートした、印刷性に優れるラミネート紙が開示されている（特許文献９）が、このものは用紙の断面部から天然紙が吸水をするために樹脂薄膜の剥離やボコツキの発生が問題となり、屋外用ポスターなどの用途には十分な耐水性があるとは言えない。また中心層を構成する天然紙の繊維の凹凸（地合）が表面の粗さとして現れるため、印刷時の網点再現性は合成紙と比べて悪く、印刷イメージがぼやけたものとなり、高精細な印刷には不向きである。
In addition, with respect to aliphatic polyester resins other than polylactic acid and mainly composed of aliphatic diols and aliphatic dicarboxylic acids, excellent strength, elongation and elastic modulus comparable to polyolefin resins can be obtained. Although there have been reports of films and synthetic papers using this (Patent Document 8, etc.), it is unclear whether the obtained film has printing characteristics as in the present invention. In particular, it is difficult to think that the opacity that gives the clearness of printing is obtained.
Furthermore, a laminated paper excellent in printability in which a thin film of an aliphatic polyester resin is laminated on both sides of a natural paper is disclosed (Patent Document 9). In this paper, the natural paper absorbs water from the cross section of the paper. For this reason, peeling of the resin thin film and occurrence of unevenness become problems, and it cannot be said that there is sufficient water resistance for applications such as outdoor posters. In addition, the irregularities (texture) of the natural paper fibers that make up the center layer appear as surface roughness, so the halftone dot reproducibility during printing is worse than that of synthetic paper, and the printed image is blurred, resulting in high definition. It is not suitable for printing.
植物由来のバイオマス原料を利用できる脂肪族ポリエステル樹脂組成物を用いた無延伸樹脂フィルムであって、印刷性に優れる印刷用紙、殊に枚葉（平版）オフセット印刷用紙に関しては、上述のように印刷機上での走行安定性、不透明性、網点の再現性等の性能を有したものでなければならず、より具体的には適度な腰（こわさ、剛度）、不透明度、表面の粗さを有したものである。
適度な腰を持つ印刷用紙でなければ、印刷機上での走行安定性は悪化する。腰が低すぎる場合は、印刷機給紙部での用紙のタワミの発生や、重走等の給紙不良が問題となり、また印刷物にもシワが発生しやすい。逆に高すぎる場合は、走行部での通紙すらできないか、低速度でしか印刷できないものとなり、実用上は使用できない。
A non-stretched resin film using an aliphatic polyester resin composition that can use plant-derived biomass raw materials, and is excellent in printability, especially for sheet-fed (flat) offset printing paper, printing as described above. It must have performance such as on-machine running stability, opacity, and reproducibility of halftone dots, and more specifically, moderate waist (stiffness, stiffness), opacity, and surface roughness. It is what has.
Unless the printing paper has an appropriate waist, running stability on the printing press deteriorates. When the waist is too low, there is a problem of paper warpage in the paper feed unit of the printing press, paper feed failure such as heavy running, and wrinkles are likely to occur on the printed matter. On the other hand, if it is too high, paper cannot be passed through the running section or it can be printed only at a low speed, and cannot be used practically.
また、適度な不透明度を持つ印刷用紙でなければ、例えば、地図やカタログ、メニュー、パンフレットなど、表裏両面に異なる絵柄や情報等を印刷した場合に印刷の裏抜け（プリントスルー）が生じ、表裏面に設けた絵柄や情報が重ねて見えるために印刷の鮮明性が得られず、印刷用紙としては不適なものである。
さらに、適度な表面の粗さを持つ印刷用紙でなければ、印刷の網点再現性や、印刷機上での走行安定性が悪化する。粗さが粗すぎる場合は網点の太り（ドットゲイン）が発生しやすく、高精細な印刷には不向きである。逆に平滑すぎる場合は、印刷用紙間の離れが悪くなり、やはり重走等の給排紙不良が問題となる。
また、本発明の印刷用紙は無延伸樹脂フィルムを用いているので、表面強度等の機械強度に優れるものであり、ピッキング等の不具合が生じないといった特徴も有している。
In addition, if the printing paper does not have appropriate opacity, for example, if a different pattern or information is printed on both the front and back sides, such as maps, catalogs, menus, pamphlets, etc., print-through will occur, resulting in Since the pattern and information provided on the back surface appear to overlap each other, the clearness of printing cannot be obtained, and it is unsuitable as printing paper.
Further, unless the printing paper has an appropriate surface roughness, the halftone dot reproducibility of printing and the running stability on the printing press deteriorate. If the roughness is too rough, the halftone dots (dot gain) are likely to occur, which is not suitable for high-definition printing. On the other hand, if the surface is too smooth, the separation between the printing papers becomes worse, and a problem of paper feeding and discharging such as heavy running becomes a problem.
In addition, since the printing paper of the present invention uses an unstretched resin film, it has excellent mechanical strength such as surface strength, and has a feature that defects such as picking do not occur.
本発明者らは、上記課題を解決するために鋭意検討を重ねた結果、本発明に到達するに到った。
即ち本発明は、（ａ）下記（Ｉ）式で表される脂肪族ジオール単位と、下記（II）式で表される脂肪族ジカルボン酸単位とを少なくとも含む脂肪族ポリエステル樹脂４０〜９０重量％、及び（ｂ）無機微細粉末１０〜６０重量％を含む脂肪族ポリエステル樹脂組成物を含有する無延伸樹脂フィルムであって、該フィルムのガーレ剛度が５０〜３，０００ｍｇの範囲であり、該フィルムの不透明度が８５〜１００％の範囲であり、該フィルム表面の投影面積４，２９２μｍ2 当たりの表面積Ｓが５，０００〜５０，０００μｍ2 の範囲であり、且つ投影面積４，２９２μｍ2 当たりの凸部の体積Ｖが２，０００〜２０，０００μｍ3 の範囲であることを特徴とする印刷用紙、およびそれを用いたラベルを提供するものである。
−Ｏ−（ＣＨ2 ）m −Ｏ− ・・・（Ｉ）
（（Ｉ）式中、ｍは２〜１０の整数を表す。）
−ＯＣ−（ＣＨ2 ）n −ＣＯ− ・・・（II）
（（II）式中、ｎは１〜１２の整数を表す。）
As a result of intensive studies to solve the above problems, the present inventors have reached the present invention.
That is, the present invention relates to (a) an aliphatic polyester resin containing at least 40 to 90% by weight of an aliphatic diol unit represented by the following formula (I) and an aliphatic dicarboxylic acid unit represented by the following formula (II): And (b) an unstretched resin film containing an aliphatic polyester resin composition containing 10 to 60% by weight of inorganic fine powder, the Gurley stiffness of the film being in the range of 50 to 3,000 mg, The opacity of the film surface is in the range of 85 to 100%, the surface area S per 4,292 μm 2 of the projected area of the film surface is in the range of 5,000 to 50,000 μm 2 , and the projected area of 4,292 μm 2 The present invention provides a printing paper characterized in that the volume V of the convex portion is in the range of 2,000 to 20,000 μm 3 , and a label using the printing paper.
—O— (CH 2 ) m —O— (I)
(In the formula (I), m represents an integer of 2 to 10.)
-OC- (CH 2) n -CO- ··· (II)
(In the formula (II), n represents an integer of 1 to 12.)
また本発明の印刷用紙は、好ましくは、（ａ）脂肪族ポリエステル樹脂が、更に下記（III ）式で表される脂肪族オキシカルボン酸単位を含むことを特徴とし、
（ａ）脂肪族ポリエステル樹脂が、脂肪族ジオール単位３５〜５０モル％、脂肪族ジカルボン酸単位３５〜５０モル％、及び脂肪族オキシカルボン酸単位０〜３０モル％を含み、且つ１万〜５０万の数平均分子量を有し、脂肪族ジオールが１，４−ブタンジオールを含み、脂肪族ジカルボン酸がコハク酸およびアジピン酸のうち少なくとも一つを含み、脂肪族オキシカルボン酸が乳酸を含み、無機微細粉末が、タルク、炭酸カルシウム、酸化チタンから選ばれた少なくとも一つを含むことを特徴とするものである。
更に本発明の印刷用紙は、枚葉オフセット印刷を行なう際、印刷速度が３，０００〜１２，０００枚／時の速度範囲で安定して印刷することが可能であり、印刷物の５０％網点部分の太り率（ドットゲイン）が１５〜２５％の範囲であることを特徴とするものである。
(A) The aliphatic polyester resin contains 35-50 mol% aliphatic diol units, 35-50 mol% aliphatic dicarboxylic acid units, and 0-30 mol% aliphatic oxycarboxylic acid units, and 10,000-50 Having a number average molecular weight of 10,000, the aliphatic diol comprises 1,4-butanediol, the aliphatic dicarboxylic acid comprises at least one of succinic acid and adipic acid, the aliphatic oxycarboxylic acid comprises lactic acid, The inorganic fine powder contains at least one selected from talc, calcium carbonate, and titanium oxide.
Furthermore, when performing sheet-fed offset printing, the printing paper of the present invention can stably print at a printing speed range of 3,000 to 12,000 sheets / hour, and 50% halftone dot of printed matter. The weight ratio (dot gain) of the portion is in the range of 15 to 25%.
本発明の印刷用紙は、植物資源由来のバイオマス原料を利用できる脂肪族ポリエステル樹脂を用いたものであり、印刷機上での走行安定性、機材強度、網点の再現性、印刷の鮮明性及び耐水性等に優れるものであって、枚葉（平版）オフセット印刷を施す用途、例えば、屋外用ポスターやカタログ、メニュー、パンフレット、地図などの商業印刷用途に好適に用いられるものであり、更に同じく印刷を施すラベル用途にも好適に用いられるものである。 The printing paper of the present invention uses an aliphatic polyester resin that can use a biomass raw material derived from plant resources, running stability on a printing machine, equipment strength, reproducibility of halftone dots, sharpness of printing and It is excellent in water resistance, etc., and is suitably used for applications that perform sheet-fed (planar) offset printing, for example, commercial printing applications such as outdoor posters, catalogs, menus, brochures, maps, etc. It is also suitably used for label applications for printing.
以下に、本発明をさらに詳細に説明する。
（脂肪族ポリエステル樹脂）
本発明における脂肪族ポリエステル樹脂としては、脂肪族ジオールと脂肪族ジカルボン酸またはその誘導体を反応主成分とし、それぞれを実質的に等モルずつ重縮合反応させたものであり、好ましくは脂肪族ジカルボン酸またはその誘導体１００モルに対し脂肪族オキシカルボン酸を０．０４〜６０モル共存させ共重合させたものである。さらには、主として脂肪族または脂環式ジオール、および脂肪族または脂環式ジカルボン酸またはその誘導体を重縮合反応させる際に、乳酸に代表されるα−ヒドロキシカルボン酸タイプの脂肪族オキシカルボン酸を、脂肪族ジカルボン酸またはその誘導体１００モルに対し０．０４〜６０モル共存させ、かつ、ゲルマニウム化合物からなる触媒を使用することにより得られた数平均分子量が１万〜５０万である脂肪族ポリエステル樹脂である。
The present invention is described in further detail below.
(Aliphatic polyester resin)
As the aliphatic polyester resin in the present invention, an aliphatic diol and an aliphatic dicarboxylic acid or a derivative thereof are used as reaction main components, and each is subjected to a polycondensation reaction in substantially equimolar amounts, preferably an aliphatic dicarboxylic acid. Alternatively, an aliphatic oxycarboxylic acid is copolymerized in an amount of 0.04 to 60 mol with respect to 100 mol of the derivative. Furthermore, when an aliphatic or alicyclic diol and an aliphatic or alicyclic dicarboxylic acid or a derivative thereof are subjected to a polycondensation reaction, an α-hydroxycarboxylic acid type aliphatic oxycarboxylic acid represented by lactic acid is used. An aliphatic polyester having a number average molecular weight of 10,000 to 500,000 obtained by using a catalyst comprising a germanium compound in the presence of 0.04 to 60 mol per 100 mol of the aliphatic dicarboxylic acid or its derivative Resin.
このような脂肪族ポリエステル樹脂は、オキシカルボン酸の単独重合体（所謂ポリ乳酸など）とは異なり、用いる脂肪族ジオールや脂肪族ジカルボン酸の種類やその組み合わせ、その配合比率によって高分子鎖中のアルキレン鎖の割合なども任意に設定できる利点があり、ポリオレフィン樹脂に近い物性（弾性率や引張伸びなど）を有するものを得ることもできる。
重縮合反応させる際に、ゲルマニウム化合物からなる触媒を存在させ、乳酸などの脂肪族オキシカルボン酸を適量用いることにより、重合速度が増大し、高分子量の脂肪族ポリエステルが得られる。本発明における脂肪族ポリエステル樹脂は、脂肪族ジオールと脂肪族ジカルボン酸またはその誘導体を反応主成分とした二元系以上の多元系原料からなるものであり、所謂ポリ乳酸のように脂肪族オキシカルボン酸の重縮合及びラクトンの開環重合等により得られる一元系の脂肪族ポリエステル樹脂は含まない。この様な多元系原料からなる脂肪族ポリエステルは、分子中のアルキレン鎖によってポリオレフィン樹脂に近い物性（引張破断伸度や弾性率）を有しており、無延伸樹脂フィルムとしての成形が容易であり、得られた印刷用紙は優れた機上走行性を有する。
Such an aliphatic polyester resin is different from an oxycarboxylic acid homopolymer (so-called polylactic acid or the like) in the polymer chain depending on the type and combination of the aliphatic diol and aliphatic dicarboxylic acid used, and the blending ratio thereof. There is an advantage that the proportion of the alkylene chain can be arbitrarily set, and it is also possible to obtain a material having physical properties (such as elastic modulus and tensile elongation) close to those of the polyolefin resin.
In the polycondensation reaction, a catalyst composed of a germanium compound is present and an appropriate amount of an aliphatic oxycarboxylic acid such as lactic acid is used to increase the polymerization rate and obtain a high molecular weight aliphatic polyester. The aliphatic polyester resin in the present invention is composed of a binary or higher multi-component material having an aliphatic diol and an aliphatic dicarboxylic acid or a derivative thereof as main reaction components, and an aliphatic oxycarboxylic acid such as so-called polylactic acid. It does not include one-part aliphatic polyester resins obtained by acid polycondensation and lactone ring-opening polymerization. Aliphatic polyesters made from such multi-component materials have physical properties (tensile elongation at break and elastic modulus) similar to polyolefin resins due to the alkylene chain in the molecule, and are easy to mold as unstretched resin films. The obtained printing paper has excellent on-machine travelability.
脂肪族ジオールとしては、ＨＯ−（ＣＨ2 ）m −ＯＨ（式中、ｍは２〜１０の整数を表す。）に相当する脂肪族ジオールが好適である。
具体的には、エチレングリコール、１，３−プロパンジオール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、１，８−オクタンジオール、デカメチレングリコール、ネオペンチルグリコールなどが挙げられる。また、１，４−シクロヘキサンジメタノールなどが脂環を有する脂肪族ジオールであっても良い。これらの脂肪族ジオールは、単独でも２種以上の混合物であってもよい。得られる樹脂の性質から、好ましいのは１，４−ブタンジオールまたはエチレングリコールであり、中でも特に好ましいのは１，４−ブタンジオールである。
As the aliphatic diol, an aliphatic diol corresponding to HO— (CH 2 ) m —OH (wherein m represents an integer of 2 to 10) is preferable.
Specifically, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, decamethylene glycol, neopentyl glycol Etc. Further, 1,4-cyclohexanedimethanol or the like may be an aliphatic diol having an alicyclic ring. These aliphatic diols may be used alone or as a mixture of two or more. From the properties of the resulting resin, 1,4-butanediol or ethylene glycol is preferred, and 1,4-butanediol is particularly preferred.
脂肪族ジカルボン酸としては、ＨＯＯＣ−（ＣＨ2 ）n −ＣＯＯＨ（式中、ｎは１〜１２の整数を表す）に相当する脂肪族ジカルボン酸が好適である。
具体的には、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ウンデカジカルボン酸、ドデカジカルボン酸など、またヘキサヒドロフタル酸、ヘキサヒドロイソフタル酸、ヘキサヒドロテレフタル酸など脂環を有するもの、またはその誘導体として低級アルキルエステル類、および酸無水物、例えば、無水コハク酸、無水アジピン酸などが挙げられる。これらのジカルボン酸またはその誘導体は、単独でも２種以上の混合物であってもよい。得られるポリマーの性質から、好ましくはアルキレン鎖の炭素数ｎが１〜４程度のものであり、特に好ましいのは、コハク酸、無水コハク酸、またはコハク酸とアジピン酸の混合物である。
As the aliphatic dicarboxylic acid, an aliphatic dicarboxylic acid corresponding to HOOC— (CH 2 ) n —COOH (wherein n represents an integer of 1 to 12) is preferable.
Specifically, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecadicarboxylic acid, dodecadicarboxylic acid, hexahydrophthalic acid, hexahydro Those having an alicyclic ring such as isophthalic acid and hexahydroterephthalic acid, or derivatives thereof include lower alkyl esters and acid anhydrides such as succinic anhydride and adipic anhydride. These dicarboxylic acids or their derivatives may be used singly or as a mixture of two or more. From the properties of the obtained polymer, the alkylene chain preferably has about 1 to 4 carbon atoms, and particularly preferred is succinic acid, succinic anhydride, or a mixture of succinic acid and adipic acid.
脂肪族オキシカルボン酸としては、下記の構造式に相当する脂肪族α−ヒドロキシカルボン酸が好適である。
この脂肪族オキシカルボン酸の具体例としては、乳酸、グリコール酸、２−ヒドロキシ−ｎ−酪酸、２−ヒドロキシ−３−メチル−ｎ−酪酸、２−ヒドロキシ−３，３−ジメチル−ｎ−酪酸、３−ヒドロキシ−ｎ−酪酸、４−ヒドロキシ−ｎ−酪酸、２−ヒドロキシカプロン酸、２−ヒドロキシ３，３−ジメチル酪酸、２−ヒドロキシ−ｎ−吉草酸、３−ヒドロキシ−ｎ−吉草酸、４−ヒドロキシ−ｎ−吉草酸、５−ヒドロキシ−ｎ−吉草酸、２−ヒドロキシ−ｎ−ヘキサン酸、２−ヒドロキシ−１−ヘキサン酸、３−ヒドロキシ−ｎ−ヘキサン酸、４−ヒドロキシ−ｎ−ヘキサン酸など、またはこれらの混合物が挙げられる。これらに光学異性体が存在する場合は、Ｄ体、Ｌ体、またはラセミ体のいずれでもよく、形態としては固体、液体、または水溶液であってもよい。これらの中で特に好ましいのは、入手が容易である乳酸または乳酸水溶液である。
本発明において使用する脂肪族ジオール、脂肪族ジカルボン酸、及び脂肪族オキシカルボン酸は、糖類やデンプンなどのバイオマス原料を出発物質として調整することができるものを用いることが好ましい。
Specific examples of the aliphatic oxycarboxylic acid include lactic acid, glycolic acid, 2-hydroxy-n-butyric acid, 2-hydroxy-3-methyl-n-butyric acid, and 2-hydroxy-3,3-dimethyl-n-butyric acid. 3-hydroxy-n-butyric acid, 4-hydroxy-n-butyric acid, 2-hydroxycaproic acid, 2-hydroxy3,3-dimethylbutyric acid, 2-hydroxy-n-valeric acid, 3-hydroxy-n-valeric acid 4-hydroxy-n-valeric acid, 5-hydroxy-n-valeric acid, 2-hydroxy-n-hexanoic acid, 2-hydroxy-1-hexanoic acid, 3-hydroxy-n-hexanoic acid, 4-hydroxy- n-hexanoic acid or the like, or a mixture thereof. When optical isomers exist in these, any of D-form, L-form, and racemic form may be sufficient, and a form may be a solid, a liquid, or aqueous solution. Of these, lactic acid or a lactic acid aqueous solution, which is easily available, is particularly preferable.
As the aliphatic diol, aliphatic dicarboxylic acid, and aliphatic oxycarboxylic acid used in the present invention, it is preferable to use those that can be prepared using biomass raw materials such as sugars and starch as starting materials.
本発明に係る無延伸樹脂フィルムの原料となる脂肪族ポリエステル樹脂は、従来から知られている方法によって製造することができ、特に限定されるものではない。例えば、特開平０８−２３９４６１号公報に開示されているような溶融重縮合法、または有機溶媒中で脱水重縮合する方法などが挙げられる。この脂肪族ポリエステル樹脂を製造する際の重縮合反応条件は、従来から採用されている適切な条件を設定することができ、特に制限されない。脂肪族ジオールの使用量は、脂肪族ジカルボン酸またはその誘導体１００モルに対し実質的に等モルであるが、一般には、エステル化中の留出があることから、１〜２０モル％過剰に用いられる。
添加することができる脂肪族オキシカルボン酸の量は、多すぎると耐熱性、機械的特性などが不十分となる傾向があり、少ないと重縮合反応生成物の分子量が低い傾向がある。脂肪族オキシカルボン酸の量は、脂肪族ジカルボン酸またはその誘導体１００モルに対し、０〜６０モル、好ましくは０．０４〜６０モル、より好ましくは１〜４０モル、特に好ましくは２〜２０モルである。
The aliphatic polyester resin used as the raw material of the unstretched resin film according to the present invention can be produced by a conventionally known method and is not particularly limited. For example, a melt polycondensation method as disclosed in JP-A-08-239461 or a dehydration polycondensation method in an organic solvent can be used. The polycondensation reaction conditions for producing the aliphatic polyester resin can be set to appropriate conditions that have been conventionally employed, and are not particularly limited. The amount of the aliphatic diol used is substantially equimolar with respect to 100 mol of the aliphatic dicarboxylic acid or derivative thereof, but in general, since there is distillation during esterification, it is used in an excess of 1 to 20 mol%. It is done.
When the amount of the aliphatic oxycarboxylic acid that can be added is too large, the heat resistance and mechanical properties tend to be insufficient, and when the amount is small, the molecular weight of the polycondensation reaction product tends to be low. The amount of the aliphatic oxycarboxylic acid is 0 to 60 mol, preferably 0.04 to 60 mol, more preferably 1 to 40 mol, particularly preferably 2 to 20 mol, per 100 mol of the aliphatic dicarboxylic acid or derivative thereof. It is.
脂肪族オキシカルボン酸の添加時期や添加方法は、重縮合開始以前であれば特に限定されず、例えば、（１）あらかじめ触媒を脂肪族オキシカルボン酸溶液に溶解させた状態で添加する方法、（２）原料仕込み時に触媒を添加すると同時に添加する方法、などが挙げられる。
脂肪族ポリエステル樹脂は、上記原料をゲルマニウム化合物からなる重合触媒の存在下に重縮合させることによって得ることが好ましい。ゲルマニウム化合物としては、例えば、テトラアルコキシゲルマニウムなどの有機ゲルマニウム化合物、または酸化ゲルマニウムおよび塩化ゲルマニウムなどの無機ゲルマニウム化合物などが挙げられる。価格や入手の容易さなどから、酸化ゲルマニウム、テトラエトキシゲルマニウム、またはテトラブトキシゲルマニウムなどが特に好ましい。ゲルマニウム化合物は、１種でも２種以上の混合物でもよい。
ゲルマニウム化合物には、ポリエステル樹脂の製造に使用できる他の触媒と併用することもできる。併用できる触媒は、反応系に可溶の金属触媒であり、例えば、チタン、アンチモン、スズ、マグネシウム、カルシウム、亜鉛などの化合物が挙げられる。
The addition timing and addition method of the aliphatic oxycarboxylic acid are not particularly limited as long as they are before the start of polycondensation. For example, (1) a method in which the catalyst is previously dissolved in an aliphatic oxycarboxylic acid solution, 2) A method of adding the catalyst at the same time as adding the catalyst at the time of charging the raw materials.
The aliphatic polyester resin is preferably obtained by polycondensation of the above raw materials in the presence of a polymerization catalyst comprising a germanium compound. Examples of the germanium compound include organic germanium compounds such as tetraalkoxygermanium, and inorganic germanium compounds such as germanium oxide and germanium chloride. In view of price and availability, germanium oxide, tetraethoxygermanium, tetrabutoxygermanium, and the like are particularly preferable. The germanium compound may be a single type or a mixture of two or more types.
The germanium compound can be used in combination with other catalysts that can be used in the production of polyester resins. The catalyst that can be used in combination is a metal catalyst that is soluble in the reaction system, and examples thereof include compounds such as titanium, antimony, tin, magnesium, calcium, and zinc.
これら触媒の使用量は、重縮合反応で使用されるモノマー量に対して０．００１〜３重量％、より好ましくは０．００５〜１．５重量％である。触媒の添加時期は、重縮合開始以前であれば得に限定されないが、原料仕込み時に添加するか、または脂肪族オキシカルボン酸水溶液に触媒を溶解して添加する方法が好ましい。中でも、触媒の保存性の観点から、脂肪族オキシカルボン酸に溶解して添加する方法が好ましい。
脂肪族ポリエステル樹脂を製造する際の温度、時間、圧力などの条件は、原料モノマーの組合せ、組成比、触媒の種類、量などの組合せにより変化するが、温度は１５０〜２６０℃、好ましくは１８０〜２３０℃の範囲で選ぶのがよく、重合時間は２時間以上、好ましくは４〜１５時間の範囲で選ぶのがよい。反応圧力は１０ｍｍＨｇ以下の減圧、好ましくは２ｍｍＨｇ以下の減圧とするのがよい。
The amount of these catalysts used is 0.001 to 3% by weight, more preferably 0.005 to 1.5% by weight, based on the amount of monomer used in the polycondensation reaction. The catalyst addition time is not particularly limited as long as it is before the start of polycondensation, but a method of adding the catalyst at the time of charging the raw materials or dissolving the catalyst in an aliphatic oxycarboxylic acid aqueous solution is preferable. Among these, from the viewpoint of storage stability of the catalyst, a method of adding it by dissolving in an aliphatic oxycarboxylic acid is preferable.
Conditions such as temperature, time, and pressure when producing the aliphatic polyester resin vary depending on combinations of raw material monomers, composition ratio, catalyst type, amount, etc., but the temperature is 150 to 260 ° C., preferably 180 ° C. The temperature is preferably selected in the range of ˜230 ° C., and the polymerization time is selected in the range of 2 hours or more, preferably in the range of 4 to 15 hours. The reaction pressure is reduced to 10 mmHg or less, preferably 2 mmHg or less.
脂肪族ポリエステル樹脂の原料組成比は、前記（Ｉ）式で表される脂肪族ジオール単位と、前記（II）式で表される脂肪族カルボン酸単位のモル比が、実質的に等しいことが必要である。（Ｉ）式で表される脂肪族ジオール単位と（II）式で表される脂肪族ジカルボン酸単位は、各々３８．５〜５０モル％の範囲、好ましくは３８．５〜４９．９９モル％、より好ましくは４１．５〜４９．７５モル％の範囲、特に好ましくは４５．５〜４９．５モル％の範囲で選ぶのがよい。また前記（III ）式で表される脂肪族オキシカルボン酸単位は、０〜２３モル％の範囲で選ぶのがよい。好ましいのは０．０２〜２３モル％の範囲、より好ましくは０．５〜１７モル％の範囲、特に好ましくは１〜９モル％の範囲である。脂肪族オキシカルボン酸が３０モル％を超えると、耐熱性、機械的特性が不十分である。 The raw material composition ratio of the aliphatic polyester resin is such that the molar ratio of the aliphatic diol unit represented by the formula (I) and the aliphatic carboxylic acid unit represented by the formula (II) is substantially equal. is necessary. The aliphatic diol unit represented by the formula (I) and the aliphatic dicarboxylic acid unit represented by the formula (II) are each in the range of 38.5 to 50 mol%, preferably 38.5 to 49.99 mol%. More preferably, it should be selected in the range of 41.5 to 49.75 mol%, particularly preferably in the range of 45.5 to 49.5 mol%. The aliphatic oxycarboxylic acid unit represented by the formula (III) is preferably selected in the range of 0 to 23 mol%. The range of 0.02 to 23 mol% is preferable, the range of 0.5 to 17 mol% is more preferable, and the range of 1 to 9 mol% is particularly preferable. When aliphatic oxycarboxylic acid exceeds 30 mol%, heat resistance and mechanical properties are insufficient.
脂肪族ポリエステル樹脂には、本発明の目的・効果を損なわない限り、他の共重合成分を導入することができる。他の共重合成分としては、３官能以上の多価オキシカルボン酸、多価カルボン酸、多価アルコールなどが挙げられる。これらの他の共重合成分を導入した場合には、脂肪族ポリエステル樹脂の溶融粘度を高めることができ、好ましい。他の共重合成分の具体例としては、リンゴ酸、酒石酸、クエン酸、トリメチロールプロパン、グリセリン、ペンタエリスリトール、トリメリット酸、ピロメリット酸などが挙げられる。得られる脂肪族ポリエステル樹脂の物性の観点から、リンゴ酸、トリメチロールプロパン、グリセリンなどが特に好ましい。
脂肪族ポリエステル樹脂の分子量は、数平均分子量（ＧＰＣ法により測定しポリスチレン換算した値）で１万〜５０万の範囲であり、好ましくは３万〜２０万の範囲である。数平均分子量が１万未満であると、印刷用紙としての機械的強度が不足し、逆に５０万を越えると成形が困難となり、いずれも好ましくない。
Other copolymer components can be introduced into the aliphatic polyester resin as long as the objects and effects of the present invention are not impaired. Examples of other copolymerization components include tri- or higher functional polyoxycarboxylic acids, polyhydric carboxylic acids, polyhydric alcohols, and the like. When these other copolymerization components are introduced, the melt viscosity of the aliphatic polyester resin can be increased, which is preferable. Specific examples of other copolymer components include malic acid, tartaric acid, citric acid, trimethylolpropane, glycerin, pentaerythritol, trimellitic acid, pyromellitic acid, and the like. From the viewpoint of physical properties of the resulting aliphatic polyester resin, malic acid, trimethylolpropane, glycerin and the like are particularly preferable.
The molecular weight of the aliphatic polyester resin is in the range of 10,000 to 500,000, preferably in the range of 30,000 to 200,000 in terms of number average molecular weight (measured by GPC method and converted to polystyrene). When the number average molecular weight is less than 10,000, the mechanical strength as a printing paper is insufficient. On the other hand, when the number average molecular weight exceeds 500,000, molding becomes difficult.
また、その融点は７０〜１８０℃の範囲である。融点が７０℃未満であると耐熱性が不十分であり、１８０℃を超えるものは製造が難しい。中でも好ましい融点の範囲は７０〜１５０℃、さらに好ましくは８０〜１３５℃である。さらに、ＭＦＲ（ＪＩＳ−Ｋ−７２１０に準拠して測定した値である温度１９０℃における）は、０．０１〜５０ｇ／１０分の範囲が好ましい。
樹脂フィルムを成形するにあたり、成形性を改善する目的から脂肪族ポリエステル樹脂組成物を構成する樹脂分は、脂肪族ポリエステル樹脂以外の熱可塑性樹脂、例えばポリオレフィン樹脂を混合した混合物であっても良い。ただし、化石原料由来の樹脂を混合する場合は、本発明の目的に沿わせるためにこれらは樹脂分中５０重量％未満とするのが好ましい。２種類以上の樹脂を配合し混合物とする場合であってこれらの相溶性に乏しい場合は、相溶化剤を配合することもできる。
Moreover, the melting | fusing point is the range of 70-180 degreeC. When the melting point is less than 70 ° C., the heat resistance is insufficient, and those exceeding 180 ° C. are difficult to produce. Among these, the preferable melting point range is 70 to 150 ° C, more preferably 80 to 135 ° C. Further, the MFR (at a temperature of 190 ° C., which is a value measured according to JIS-K-7210) is preferably in the range of 0.01 to 50 g / 10 minutes.
In molding the resin film, the resin component constituting the aliphatic polyester resin composition for the purpose of improving moldability may be a mixture in which a thermoplastic resin other than the aliphatic polyester resin, for example, a polyolefin resin is mixed. However, when mixing the resin derived from a fossil raw material, it is preferable to make these less than 50 weight% in a resin part in order to meet the objective of this invention. When two or more kinds of resins are blended to form a mixture and the compatibility is poor, a compatibilizer can be blended.
（無機微細粉末）
本発明において原料として配合される無機微細粉末としては、充填材または顔料、場合によっては結晶核剤として機能するものであり、樹脂フィルムに印刷用紙としての白色度や不透明度を付与するものであり、例えば、炭酸カルシウム、タルク、焼成クレー、カオリン、シリカ、珪藻土、炭酸マグネシウム、炭酸バリウム、硫酸マグネシウム、硫酸バリウム、硫酸カルシウム、水酸化アルミニウム、酸化亜鉛、水酸化マグネシウム、酸化カルシウム、酸化マグネシウム、酸化チタン、アルミナ、マイカ、アスベスト粉、シラスバルーン、ゼオライト、珪酸白土などが挙げられ、特に炭酸カルシウム、タルク、クレー、硫酸バリウム、酸化チタンなどが好適である。これらは単独でも、２種以上の混合物であってもよい。
無機微細粉末の平均粒径は、３０μｍ以下のものが好ましく、１０μｍ以下のものが更に好ましく、０．２〜５μｍのものが最も好ましい。粒径が大きすぎると表面に粗大な凹凸が生じやすく印刷の鮮明性が得られにくい点、好ましくない。また粒径が小さすぎると、樹脂組成物への分散性が悪く、成形性に劣り好ましくない。
無機微細粉末は樹脂組成物への分散性の観点から、その表面が表面処理されているものが好ましい。この際の表面処理は、脂肪酸またはその金属塩などの物質によって処理されているのが好ましい。
(Inorganic fine powder)
The inorganic fine powder blended as a raw material in the present invention functions as a filler or pigment, and in some cases as a crystal nucleating agent, and imparts whiteness and opacity as printing paper to a resin film. , For example, calcium carbonate, talc, calcined clay, kaolin, silica, diatomaceous earth, magnesium carbonate, barium carbonate, magnesium sulfate, barium sulfate, calcium sulfate, aluminum hydroxide, zinc oxide, magnesium hydroxide, calcium oxide, magnesium oxide, oxidation Examples thereof include titanium, alumina, mica, asbestos powder, shirasu balloon, zeolite, silicate clay, and calcium carbonate, talc, clay, barium sulfate, titanium oxide and the like are particularly preferable. These may be used alone or as a mixture of two or more.
The average particle size of the inorganic fine powder is preferably 30 μm or less, more preferably 10 μm or less, and most preferably 0.2 to 5 μm. If the particle size is too large, coarse unevenness is likely to occur on the surface, and printing sharpness is difficult to obtain. On the other hand, if the particle size is too small, the dispersibility in the resin composition is poor and the moldability is inferior.
From the viewpoint of dispersibility in the resin composition, the inorganic fine powder preferably has a surface-treated surface. The surface treatment at this time is preferably treated with a substance such as a fatty acid or a metal salt thereof.
（組成）
原料の樹脂組成物に配合される無機微細粉末の配合割合は、樹脂組成物１００重量％に対して無機微細粉末１０〜６０重量％の範囲で選ばれる。無機微細粉末の割合が１０重量％に満たないと、不透明度の低いフィルムとなり印刷用紙として好ましくない。また６０重量％を超えると樹脂組成物の混練性、分散性やフィルム成形性が劣り好ましくない。より好ましい無機微細粉末の配合割合は１２〜５５重量％の範囲であり、特に好ましくは１５〜５０重量％の範囲である。
(composition)
The blending ratio of the inorganic fine powder to be blended in the raw material resin composition is selected in the range of 10 to 60% by weight of the inorganic fine powder with respect to 100% by weight of the resin composition. If the ratio of the inorganic fine powder is less than 10% by weight, the film becomes low in opacity, which is not preferable as printing paper. On the other hand, if it exceeds 60% by weight, the kneadability, dispersibility and film moldability of the resin composition are inferior. The blending ratio of the inorganic fine powder is more preferably in the range of 12 to 55% by weight, particularly preferably in the range of 15 to 50% by weight.
（任意成分）
なお、本発明に係る樹脂組成物には、本発明の目的、効果を損なわない範囲で他の樹脂添加剤を添加できる。他の樹脂添加剤としては、可塑剤、熱安定剤、酸化防止剤、紫外線吸収剤、染料、顔料、帯電防止剤、蛍光剤、滑剤、難燃剤、結晶核剤などが挙げられる。上記樹脂組成物に配合される可塑剤としては、ジペンタエリスリトールのエステル化物、ポリブタジェン水添加物、エポキシ化大豆油などが挙げられる。これらは単独でも、２種以上の混合物であってもよい。また可塑剤の配合割合は、樹脂組成物１００重量部に対して０〜５０重量部の範囲で選ばれ、中でも３〜２０重量部の範囲が好ましい。
(Optional component)
In addition, other resin additives can be added to the resin composition which concerns on this invention in the range which does not impair the objective and effect of this invention. Examples of other resin additives include plasticizers, heat stabilizers, antioxidants, ultraviolet absorbers, dyes, pigments, antistatic agents, fluorescent agents, lubricants, flame retardants, and crystal nucleating agents. Examples of the plasticizer blended in the resin composition include esterified dipentaerythritol, polybutadiene water additive, epoxidized soybean oil, and the like. These may be used alone or as a mixture of two or more. The blending ratio of the plasticizer is selected in the range of 0 to 50 parts by weight with respect to 100 parts by weight of the resin composition, and the range of 3 to 20 parts by weight is particularly preferable.
原料樹脂に無機微細粉末やその他の樹脂添加剤を配合して均一な樹脂組成物を得るには、各成分を所定量秤量して混合機に入れ、十分に撹拌・混合し、均一に分散させれば良い。この際に使用できる混合機としては、ドラム、タンブラー型混合機、リボンブレンダー、ヘンシェルミキサー、スーパーミキサーなどが挙げられ、ヘンシェルミキサーやスーパーミキサーなどの高速撹拌型の混合機が好ましい。
上記方法で調製された樹脂組成物は、次に溶融混練して一旦ペレット化した後、樹脂フィルムの成形に供するか、またはこの樹脂組成物を溶融混練して直接フィルムの成形に供することができる。樹脂組成物を溶融混練するには、従来から知られている溶融混練装置、例えば、スクリュー押出機、二軸スクリュー押出機、ミキシングロール、バンバリーミキサー、二軸型混練機などを使用すればよい。
In order to obtain a uniform resin composition by mixing inorganic fine powder and other resin additives with the raw material resin, weigh each component into a mixer, stir and mix thoroughly, and disperse uniformly. Just do it. Examples of the mixer that can be used in this case include a drum, a tumbler mixer, a ribbon blender, a Henschel mixer, and a super mixer, and a high-speed stirring mixer such as a Henschel mixer and a super mixer is preferable.
The resin composition prepared by the above method can then be melt-kneaded and pelletized once, and then subjected to molding of a resin film, or the resin composition can be melt-kneaded and directly subjected to film molding. . In order to melt-knead the resin composition, a conventionally known melt-kneading apparatus such as a screw extruder, a twin screw extruder, a mixing roll, a Banbury mixer, a twin screw kneader or the like may be used.
（印刷用紙の製造）
本発明の印刷用紙を製造するには、上記の方法で調製した樹脂組成物を溶融させて、フィルム状に成形する方法による。樹脂組成物をフィルム状に成形するには、通常の熱可塑性樹脂をフィルム状に成形する成形方法に準じて行えばよい。例えば、円形ダイによるインフレーション成形法、Ｔ−ダイによるＴ−ダイ成形法、カレンダー成形法などが挙げられる。本発明に係わる無延伸とは未延伸と同義である。特に本発明では、Ｔ−ダイによるＴ−ダイ成形法を用いるのが好ましい。
本発明の印刷用紙は、単層構造であっても良いし、二層以上に積層された複層構造であっても良い。積層フィルムとする際には、複数の原料樹脂を複数の押出機で溶融し、共押出ダイ内で複数層に積層する方法や、原料樹脂の一つを先にフィルム状に成形し、これに他の押出機で溶融させた他の原料樹脂をダイからフィルム状に押出して溶融ラミネートする方法、またはこれらを組み合わせる方法などが挙げられ、いずれの方法によっても良い。この場合、複数の原料樹脂には、これまで例示した種々の脂肪族ポリエステル樹脂以外に、異なる熱可塑性樹脂、無機微細粉末、任意成分、配合比率等を採用し得るが、少なくとも最外層を構成する樹脂組成物は本発明に係る脂肪族ポリエステル樹脂組成物を用いることが好ましく、全層とも本発明のものを用いるのがより好ましい。
(Manufacture of printing paper)
In order to produce the printing paper of the present invention, the resin composition prepared by the above method is melted and formed into a film. In order to mold the resin composition into a film, it may be performed according to a molding method in which a normal thermoplastic resin is molded into a film. Examples thereof include an inflation molding method using a circular die, a T-die molding method using a T-die, and a calendar molding method. Unstretched according to the present invention is synonymous with unstretched. In particular, in the present invention, it is preferable to use a T-die molding method using a T-die.
The printing paper of the present invention may have a single layer structure or a multilayer structure in which two or more layers are laminated. When making a laminated film, melt multiple raw resins with multiple extruders and laminate them in multiple layers in a coextrusion die, or form one of the raw resin first into a film, Examples include a method of extruding other raw resin melted by another extruder into a film shape from a die and melt laminating, or a method of combining them, and any method may be used. In this case, in addition to the various aliphatic polyester resins exemplified so far, different thermoplastic resins, inorganic fine powders, optional components, blending ratios, and the like can be adopted as the plurality of raw material resins, but at least the outermost layer is constituted. It is preferable to use the aliphatic polyester resin composition according to the present invention as the resin composition, and it is more preferable to use the present invention for all layers.
成形した後のフィルムには、通常の熱可塑性樹脂フィルムと同様に、熱処理、コロナ処理、フレーム処理などの後処理を施すこともできる。
上述するように、本発明の無延伸樹脂フィルムは、脂肪族ポリエステル樹脂に無機微細粉末を配合することにより不透明化させることができる。これにより得られる無延伸樹脂フィルムの密度は１．３〜２．２ｇ／ｃｍ3 であり、１．３５〜２．１ｇ／ｃｍ3 であることが好ましく、１．４〜１．９ｇ／ｃｍ3 であることが特に好ましい。密度が１．３ｇ／ｃｍ3 未満のものは原料配合面から得にくく、２．２ｇ／ｃｍ3 を越えては非常に重くて取扱いにくいものとなる。
The film after molding can be subjected to post-treatment such as heat treatment, corona treatment, and frame treatment, as in the case of ordinary thermoplastic resin films.
As described above, the unstretched resin film of the present invention can be made opaque by blending an inorganic fine powder with an aliphatic polyester resin. Thus the density of unstretched resin film obtained was 1.3~2.2g / cm 3, is preferably 1.35~2.1g / cm 3, 1.4~1.9g / cm 3 It is particularly preferred that When the density is less than 1.3 g / cm 3 , it is difficult to obtain from the raw material blending surface, and when it exceeds 2.2 g / cm 3 , it is very heavy and difficult to handle.
（印刷用紙の物性）
得られた無延伸樹脂フィルムは、本発明の印刷用紙として、以下の諸物性を満たす必要がある。
〔腰（ガーレ剛度）〕
本発明の印刷用紙の腰は、ガーレ剛度として、ＭＤ（流れ方向）、ＴＤ（幅方向）の両目方向で５０〜３０００ｍｇの範囲である。好ましくはＭＤ、ＴＤの両目方向で１００〜２８００ｍｇの範囲であり、特に好ましくはＭＤ、ＴＤの両目方向で２００〜２６００ｍｇの範囲である。一般に剛度は基材の厚み因子に依存する特性であるが、これらの範囲規定は、印刷機上での制約に依るものであって、厚み因子も加味した上で上記範囲である必要がある。印刷用紙としての厚みは、例えば８０〜５００μｍであり、好ましくは１００〜４８０μｍであり、特に好ましくは２００〜４００μｍである。印刷用紙のガーレ剛度がＭＤ、ＴＤの両目方向で５０〜３０００ｍｇの範囲であれば、トラブルの発生することがない安定した機上走行性が得られる。
(Physical properties of printing paper)
The obtained unstretched resin film needs to satisfy the following physical properties as the printing paper of the present invention.
[Waist (Gurley stiffness)]
The waist of the printing paper of the present invention is in the range of 50 to 3000 mg as the Gurley stiffness in both eye directions of MD (flow direction) and TD (width direction). The range is preferably 100 to 2800 mg in both directions of MD and TD, and particularly preferably in the range of 200 to 2600 mg in both directions of MD and TD. Generally, the rigidity is a characteristic that depends on the thickness factor of the base material. However, these range specifications depend on restrictions on the printing press and need to be within the above range in consideration of the thickness factor. The thickness of the printing paper is, for example, 80 to 500 μm, preferably 100 to 480 μm, and particularly preferably 200 to 400 μm. If the Gurley stiffness of the printing paper is in the range of 50 to 3000 mg in both the MD and TD directions, a stable on-machine running property without causing trouble can be obtained.
ガーレ剛度がＭＤ、ＴＤ何れかの目方向でも５０ｍｇに満たない場合は、印刷機給紙部での用紙のタワミ発生や重走等の給紙不良が問題となる。また、印刷物にもシワが発生しやすい。逆に３０００ｍｇを越える場合は印刷機走行部で用紙が追随せずに暴れ、通紙すらできないか、低速度でしか印刷できないものとなり、更に紙詰まりを起こすとブランケットを痛めてしまうために実用上は使用できない。
腰（ガーレ剛度）は一般に厚みや充填剤種類、充填剤含量に依存する特性であるが、本発明ではこのような因子を含み、印刷機上での制約として、ガーレ剛度がＭＤ，ＴＤの両目方向で５０〜３０００ｍｇの範囲である。
印刷用紙の目方向に依らず、ガーレ剛度がＭＤ，ＴＤ方向ともに上記範囲内であれば、印刷の面付けの自由度が向上し、印刷加工時の実務上より好ましいものとなる。
When the Gurley stiffness is less than 50 mg in either the MD or TD eye direction, there is a problem of paper feeding failure or heavy paper feed in the printing press paper feed unit. Also, wrinkles are likely to occur on the printed matter. On the other hand, if it exceeds 3000 mg, the paper will run unsuccessfully in the running section of the printing machine, and even the paper will not pass or it can only be printed at a low speed, and if a paper jam occurs, the blanket will be damaged. Cannot be used.
Waist (Gurley stiffness) is generally a property that depends on thickness, type of filler, and filler content. In the present invention, such factors are included, and Gurley stiffness has both MD and TD as constraints on the printing press. The range is 50 to 3000 mg in the direction.
Regardless of the eye direction of the printing paper, if the Gurley stiffness is in the above range in both the MD and TD directions, the degree of freedom of imposition of printing is improved, which is more preferable in practice during printing.
〔不透明度〕
本発明の印刷用紙の不透明度は、８５〜１００％の範囲である。好ましくは９０〜１００％の範囲であり、特に好ましくは９５〜１００％の範囲である。不透明度が８５％に満たない場合は印刷の裏抜けが生じ、印刷の鮮明性に欠ける。
〔表面の粗さ〕
本発明の無延伸樹脂フィルムは、印刷用紙としては投影面積４，２９２μｍ2 当たりの表面積Ｓが５，０００〜５０，０００μｍ2 の範囲であり、且つ投影面積４，２９２μｍ2 当たりの凸部の体積Ｖが２，０００〜２０，０００μｍ3 の範囲である。
本発明において、無延伸樹脂フィルムの表面の粗さを観察するために、従来の探針を用いた接触型の三次元粗さ計ではなく、レーザー光を用いた非接触型の超深度形状測定顕微鏡を用いている。
[Opacity]
The opacity of the printing paper of the present invention is in the range of 85-100%. Preferably it is 90 to 100% of range, Most preferably, it is 95 to 100% of range. When the opacity is less than 85%, print back-through occurs and the print clarity is poor.
[Surface roughness]
The unstretched resin film of the present invention has a surface area S per projected area of 4,292 μm 2 in the range of 5,000 to 50,000 μm 2 as a printing paper, and the volume of projections per projected area of 4,292 μm 2. V is in the range of 2,000 to 20,000 μm 3 .
In the present invention, in order to observe the roughness of the surface of the unstretched resin film, not a contact type three-dimensional roughness meter using a conventional probe, but a non-contact type ultra-deep shape measurement using a laser beam. A microscope is used.
従来、印刷用紙の印刷品質を、探針を用いた接触型の三次元粗さ計にて求めた算術平均粗さ（Ｒａ）、最大高さ（Ｒｖ）、ピークカウント（Ｐｃ）などのパラメータにて説明しようとする試みがなされている。しかしこれらは充分な相関が得られるものではなかった。
このことは従来の探針を用いた接触型の三次元粗さ計では、解像度は探針の先端径（２μｍ程度）に依存し、用いる無機微細粉末が２μｍより細かく、生じる凹凸が非常に微細な場合はこれを観測できず緩和した結果になってしまうためであると推定される。レーザー光を用いた非接触型の超深度形状測定顕微鏡は、用いるレーザー光の波長、レンズの絞りにも依るが、０．３μｍ程度の解像度でサンプルを破壊せずに表面の粗さを観察できるため、配合する無機微細粉末の粒径のオーダーにも合致しており、測定結果と印刷用紙の印刷品質とに高い相関を得ることができた。
Conventionally, the print quality of printing paper is set to parameters such as arithmetic average roughness (Ra), maximum height (Rv), and peak count (Pc) obtained with a contact-type three-dimensional roughness meter using a probe. Attempts have been made to explain. However, these did not provide sufficient correlation.
This is because, in a contact type three-dimensional roughness meter using a conventional probe, the resolution depends on the tip diameter (about 2 μm) of the probe, the inorganic fine powder used is finer than 2 μm, and the resulting irregularities are very fine. In this case, it is presumed that this is because it cannot be observed and the result is relaxed. A non-contact type ultra-deep shape measurement microscope using laser light can observe the surface roughness without breaking the sample with a resolution of about 0.3 μm, depending on the wavelength of the laser light used and the aperture of the lens. Therefore, it matched the order of the particle size of the inorganic fine powder to be blended, and a high correlation could be obtained between the measurement result and the printing quality of the printing paper.
すなわち本発明の印刷用紙としては、投影面積４，２９２μｍ2 当たりの表面積Ｓが５，０００〜５０，０００μｍ2 の範囲であり、且つ投影面積４，２９２μｍ2 当たりの凸部の体積Ｖが２，０００〜２０，０００μｍ3 の範囲のものである。表面積Ｓが８，０００〜４０，０００μｍ2 の範囲であり、且つ凸部の体積Ｖが４，０００〜１５，０００μｍ3 の範囲であることがより好ましく、表面積Ｓが１０，０００〜３０，０００μｍ2 の範囲であり、且つ凸部の体積Ｖが５，０００〜１０，０００μｍ3 の範囲であることが特に好ましい。
無延伸樹脂フィルムの投影面積４，２９２μｍ2 当たりの表面積Ｓが５，０００μｍ2 に満たない場合は、全体に凹凸の少ない高平滑な表面となり、無延伸樹脂フィルム間の滑りが悪くなり重走等の給紙トラブルを起こす可能性が高く、またインキのタックが充分に得られずインキ密着性も悪い。表面積Ｓが５０，０００μｍ2 を超えて大きい場合は全体に凹凸が多く粗い表面となり、表面強度が低下する傾向がある。
That is, as the printing paper of the present invention, the projected area 4,292Myuemu surface area S per 2 ranges from 5,000～50,000Myuemu 2, and the volume V of the convex portion of the per projected area 4,292Myuemu 2 2, The range is from 000 to 20,000 μm 3 . More preferably, the surface area S is in the range of 8,000 to 40,000 μm 2 , and the volume V of the convex portion is in the range of 4,000 to 15,000 μm 3 , and the surface area S is 10,000 to 30,000 μm. 2 and the volume V of the convex portion is particularly preferably in the range of 5,000 to 10,000 μm 3 .
When the surface area S per projected area 4,292 μm 2 of the unstretched resin film is less than 5,000 μm 2 , the entire surface becomes a highly smooth surface with little unevenness, and the slip between the unstretched resin films becomes worse and heavy running, etc. Ink sticking is poor and ink adhesion is poor. When the surface area S is larger than 50,000 μm 2 , the entire surface is rough and has a rough surface, and the surface strength tends to decrease.
無延伸樹脂フィルムの投影面積４，２９２μｍ2 当たりの凸部の体積Ｖが２，０００μｍ3 に満たない場合は、凹凸が有っても高さや深さが小さく結果的に高平滑な表面となり、無延伸樹脂フィルム間の離れが悪くなり、やはり重走等の給排紙不良が問題となる。凸部の体積Ｖが２０，０００μｍ3 を超えて大きい場合は、凹凸が大きすぎる粗い表面となり、網点の太り（ドットゲイン）が発生しやすく印刷の網点再現性は悪化するために高精細な印刷には不向きである。またインキの色沈みも起こりやすく、鮮明な画像を得るために更にインキ量を増加させ、網点の太り（ドットゲイン）がより悪化する悪循環に陥りやすい。 When the volume V of the projection per projected area 4,292 μm 2 of the unstretched resin film is less than 2,000 μm 3 , the height and depth are small even if there are irregularities, resulting in a highly smooth surface. The separation between the non-stretched resin films is deteriorated, and there is still a problem of poor paper supply / discharge such as heavy running. When the volume V of the convex portion is larger than 20,000 μm 3 , the irregularity becomes too rough and the dot is thickened (dot gain) and the dot reproducibility of printing deteriorates. It is not suitable for printing. Ink color sinking is also likely to occur, and the amount of ink is further increased in order to obtain a clear image, and a vicious circle in which the thickening of dot (dot gain) is further deteriorated is likely to occur.
（印刷）
このようにして得られる印刷用紙は、種々の印刷に適しており、酸化重合型（溶剤型）オフセット印刷は勿論、紫外線硬化型オフセット印刷、凸版印刷、グラビア印刷、フレキソ印刷、レータープレス印刷、シルクスクリーン印刷などにより、シートの形態（枚葉）やロールの形態（巻取）で印刷、印字した印刷製品を作成できる。
(printing)
The printing paper thus obtained is suitable for various types of printing, as well as oxidation polymerization (solvent type) offset printing, UV curable offset printing, letterpress printing, gravure printing, flexographic printing, lator press printing, silk printing. Printing products can be created by printing in the form of sheets (sheets) or rolls (winding) by screen printing.
（粘着ラベルへの適用）
本発明の印刷用紙は、少なくとも片面に粘着剤層を設けることによりラベルとしても使用できる。設けられる粘着剤層の種類や厚さ（塗工量）は、被着体の種類や使用される環境、接着の強度等により種々選択が可能である。
一般に用いられる水系もしくは溶剤系の粘着剤としては、ゴム系粘着剤、アクリル系粘着剤、シリコーン系粘着剤が代表的であり、ゴム系粘着剤の具体例には、ポリイソブチレンゴム、ブチルゴムとこれらの混合物、或いはこれらゴム系粘着剤にアビエチン酸ロジンエステル、テルペン・フェノール共重合体、テルペン・インデン共重合体などの粘着付与剤を配合したものが挙げられる。アクリル系粘着剤の具体例としては、２−エチルヘキシルアクリレート・アクリル酸ｎ−ブチル共重合体、２−エチルヘキシルアクリレート・アクリル酸エチル・メタクリル酸メチル共重合体などのガラス転移点が−２０℃以下のものが挙げられる。
(Application to adhesive labels)
The printing paper of the present invention can also be used as a label by providing an adhesive layer on at least one side. The type and thickness (coating amount) of the pressure-sensitive adhesive layer to be provided can be variously selected depending on the type of adherend, the environment in which it is used, the strength of adhesion, and the like.
Typical water-based or solvent-based pressure-sensitive adhesives include rubber-based pressure-sensitive adhesives, acrylic pressure-sensitive pressure-sensitive adhesives, and silicone-based pressure-sensitive adhesives. Specific examples of rubber-based pressure-sensitive adhesives include polyisobutylene rubber and butyl rubber. Or a mixture of these rubber adhesives with a tackifier such as abietic rosin ester, terpene / phenol copolymer, terpene / indene copolymer, and the like. As specific examples of the acrylic pressure-sensitive adhesive, the glass transition point of 2-ethylhexyl acrylate / n-butyl acrylate copolymer, 2-ethylhexyl acrylate / ethyl acrylate / methyl methacrylate copolymer, or the like is −20 ° C. or lower. Things.
これらの合成高分子粘着剤は、有機溶媒溶液や、ディスパージョンやエマルジョンといった水に分散された状態で使用可能である。ラベルの不透明度向上のため、粘着剤はチタンホワイト等の顔料を含有したものを使用することも可能である。
粘着剤層は、溶液状態で印刷用紙と離型紙との貼合面上に塗工して形成できる。塗工は、ダイコーター、バーコーター、コンマコーター、リップコーター、ロールコーター、グラビアコーター、スプレーコーター、ブレードコーター、リバースコーター、エアーナイフコーター等により行ない、必要によりスムージングを行ない、乾燥工程を経て粘着剤層は形成される。
粘着剤層の形成は、用いる離型紙へ粘着剤を塗工し、必要により乾燥を行ない、粘着剤層を形成したものに印刷用紙を積層する方法が一般的であるが、場合によっては印刷用紙に直接に粘着剤を塗工して形成することもできる。
該粘着剤の塗工量は特に限定されないが、通常は固形分量で３〜６０ｇ／ｍ2 、好ましくは１０〜４０ｇ／ｍ2 の範囲である。
These synthetic polymer pressure-sensitive adhesives can be used in a state of being dispersed in water such as an organic solvent solution, a dispersion or an emulsion. In order to improve the opacity of the label, it is possible to use a pressure-sensitive adhesive containing a pigment such as titanium white.
The pressure-sensitive adhesive layer can be formed by coating on the bonding surface between the printing paper and the release paper in a solution state. Coating is done with a die coater, bar coater, comma coater, lip coater, roll coater, gravure coater, spray coater, blade coater, reverse coater, air knife coater, etc., smoothing if necessary, and after going through a drying process, an adhesive. A layer is formed.
For the formation of the pressure-sensitive adhesive layer, it is common to apply a pressure-sensitive adhesive to the release paper to be used, dry it if necessary, and laminate the printing paper on the one with the pressure-sensitive adhesive layer formed. It can also be formed by directly applying an adhesive.
The coating amount of the pressure-sensitive adhesive is not particularly limited, but is usually in the range of 3 to 60 g / m 2 , preferably 10 to 40 g / m 2 in terms of solid content.
以下、製造例、実施例、比較例及び評価例により、本発明をさらに具体的に説明する。以下に示す原料、使用量、割合、操作等は、本発明の趣旨を逸脱しない限り適宜変更することができる。従って、本発明の範囲は以下に示す具体例により何ら制限されるものではない。なお、各実施例、比較例で使用した原料を表１に示す。 Hereinafter, the present invention will be described more specifically with reference to production examples, examples, comparative examples, and evaluation examples. The following raw materials, amounts used, ratios, operations, and the like can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited by the specific examples shown below. The raw materials used in each example and comparative example are shown in Table 1.
（脂肪族ポリエステル樹脂の製造）
〔製造例１〕
撹拌装置、窒素ガス導入管、加熱装置、温度計、助剤添加口を備えた容量６００リットルの反応容器に、コハク酸を１３７ｋｇ、１，４−ブタンジオールを１１６リットル、酸化ゲルマニウム１重量％を予め溶解させた９０重量％ＤＬ−乳酸水溶液７．４３ｋｇ、結晶核剤としてスーパータルクＳＧ９５（日本タルク社製）０．２ｋｇをそれぞれ仕込み、窒素ガス雰囲気中、１２０〜２２０℃で２時間重縮合反応させた。引き続いて容器内温を昇温させ、窒素ガスの導入を停止し、０．５ｍｍＨｇの減圧下で５時間脱グリコール反応を行った。この反応生成物を水中にストランド状に押し出し、カッターで裁断した。得られた脂肪族ポリエステル樹脂（脂肪族ポリエステル１）は白色であり、収量は１８０ｋｇであった。
(Manufacture of aliphatic polyester resin)
[Production Example 1]
In a 600 liter reaction vessel equipped with a stirrer, nitrogen gas inlet tube, heating device, thermometer, and auxiliary agent addition port, 137 kg of succinic acid, 116 liters of 1,4-butanediol, and 1% by weight of germanium oxide A pre-dissolved 90 wt% DL-lactic acid aqueous solution (7.43 kg) and super talc SG95 (manufactured by Nippon Talc Co., Ltd.) 0.2 kg as a nucleating agent were charged, respectively, and a polycondensation reaction at 120 to 220 ° C. for 2 hours in a nitrogen gas atmosphere. I let you. Subsequently, the internal temperature of the container was raised, the introduction of nitrogen gas was stopped, and a deglycolization reaction was performed for 5 hours under a reduced pressure of 0.5 mmHg. This reaction product was extruded in strands into water and cut with a cutter. The obtained aliphatic polyester resin (aliphatic polyester 1) was white and the yield was 180 kg.
得られた脂肪族ポリエステル樹脂は、融点が１１０℃（ＤＳＣ法により得られたピーク温度、昇温速度１６℃／ｍｉｎ、窒素ガス雰囲気下で測定）、数平均分子量（Ｍｎ）が６５，０００、重量平均分子量が１５０，０００であった。ここで、平均分子量はゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法によって測定したものである（東ソー社製のＨＬＣ−８０２０型ＧＰＣ装置を使用。カラムはＰＬｇｅｌ−５μ−ＭＩＸ。ポリスチレン換算。クロロホルム溶媒。）。また、 1Ｈ−ＮＭＲによるポリマー組成は、乳酸単位３．１モル％、コハク酸単位４８．０モル％、１，４−ブタンジオール単位４８．９モル％であった。さらに、ＪＩＳ−Ｋ−７２１０に準拠して測定したＭＦＲは、９．６ｇ／１０分であった。 The resulting aliphatic polyester resin has a melting point of 110 ° C. (peak temperature obtained by DSC method, temperature increase rate of 16 ° C./min, measured in a nitrogen gas atmosphere), number average molecular weight (Mn) of 65,000, The weight average molecular weight was 150,000. Here, the average molecular weight is measured by a gel permeation chromatography (GPC) method (using an HLC-8020 GPC apparatus manufactured by Tosoh Corporation. The column is PLgel-5μ-MIX. Polystyrene conversion. Chloroform solvent. .) The polymer composition by 1 H-NMR was 3.1 mol% lactic acid units, 48.0 mol% succinic acid units, and 48.9 mol% 1,4-butanediol units. Furthermore, MFR measured based on JIS-K-7210 was 9.6 g / 10min.
〔製造例２〕
製造例１で使用したのと同じ反応容器に、コハク酸を１２３ｋｇ、アジピン酸を１７ｋｇ、１，４−ブタンジオールを１２１リットル、酸化ゲルマニウム１重量％をあらかじめ溶解させた９０％ＤＬ−乳酸水溶液７．４３ｋｇ、トリメチロールプロパン０．２３ｋｇ、スーパータルクＳＧ９５（日本タルク社製）０．２ｋｇをそれぞれ仕込み、窒素ガス雰囲気中、１２０〜２２０℃で２時間重縮合反応させた。
引き続いて容器内温を昇温させ、窒素ガスの導入を停止し、０．５ｍｍＨｇの減圧下で５時間脱グリコール反応を行った。この反応生成物を水中にストランド状に押し出し、カッターで裁断した。得られた脂肪族ポリエステル樹脂（脂肪族ポリエステル２）は白色であり、収量は１８０ｋｇであった。
この脂肪族ポリエステル樹脂は、融点が９０℃、数平均分子量（Ｍｎ）が６８，０００、重量平均分子量が１７３，０００であった。また、 1Ｈ−ＮＭＲによるポリマー組成は、乳酸単位３．３モル％、コハク酸単位４３．３モル％、アジピン酸４．８モル％、１，４−ブタンジオール単位４８．６モル％であった。さらに、ＭＦＲは８．２ｇ／１０分であった。
[Production Example 2]
90% DL-lactic acid aqueous solution 7 in which 123 kg of succinic acid, 17 kg of adipic acid, 121 liters of 1,4-butanediol, and 1% by weight of germanium oxide were previously dissolved in the same reaction vessel used in Production Example 1. .43 kg, 0.23 kg of trimethylolpropane, and 0.2 kg of super talc SG95 (manufactured by Nippon Talc Co., Ltd.) were charged, respectively, and subjected to a polycondensation reaction at 120 to 220 ° C. for 2 hours in a nitrogen gas atmosphere.
Subsequently, the internal temperature of the container was raised, the introduction of nitrogen gas was stopped, and a deglycolization reaction was performed for 5 hours under a reduced pressure of 0.5 mmHg. This reaction product was extruded in strands into water and cut with a cutter. The obtained aliphatic polyester resin (aliphatic polyester 2) was white and the yield was 180 kg.
This aliphatic polyester resin had a melting point of 90 ° C., a number average molecular weight (Mn) of 68,000, and a weight average molecular weight of 173,000. The polymer composition by 1 H-NMR was 3.3 mol% lactic acid units, 43.3 mol% succinic acid units, 4.8 mol% adipic acid, and 48.6 mol% 1,4-butanediol units. It was. Furthermore, MFR was 8.2 g / 10min.
〔実施例１〕
製造例１で得た脂肪族ポリエステル１の８５重量％、表１に記載のタルク１４重量％、および酸化チタン１重量％とからなる樹脂組成物を、ヘンシェルミキサーで撹拌混合した後に、二軸混練機（（株）神戸製鋼所製、ＮＥＸＴ−Ｔ６０）によって溶融混練し、ペレットとした。
得られたペレットはシリンダー温度を１８０℃に設定した押出機（三鈴エリー社製、ＭＫ−４０）によって溶融した後、押出機先端に装着したＴダイからフィルム状に押出し、冷却ロールにより冷却して本発明の印刷用紙を得た。
この印刷用紙の厚みは２５０μｍ、密度は１．３５ｇ／ｃｍ3 、不透明度は８９％、表面積Ｓは１２，９００μｍ2 、凸部の体積Ｖは５，４００μｍ3 、ガーレ剛度は流れ方向で５８０ｍｇ、幅方向で５８０ｍｇであった。また、この印刷用紙は耐水性を有するものであった。得られた印刷用紙の印刷適性評価と併せ、結果を表２にまとめて示す。
[Example 1]
A resin composition comprising 85% by weight of aliphatic polyester 1 obtained in Production Example 1, 14% by weight of talc listed in Table 1, and 1% by weight of titanium oxide was stirred and mixed with a Henschel mixer, and then biaxially kneaded. It was melt-kneaded by a machine (manufactured by Kobe Steel, NEXT-T60) to obtain pellets.
The obtained pellets were melted by an extruder (manufactured by Misuzu Erie Co., Ltd., MK-40) set at a cylinder temperature of 180 ° C., then extruded into a film from a T die attached to the tip of the extruder, and cooled by a cooling roll. A printing paper of the present invention was obtained.
This printing paper has a thickness of 250 μm, a density of 1.35 g / cm 3 , an opacity of 89%, a surface area S of 12,900 μm 2 , a convex volume V of 5,400 μm 3 , a Gurley stiffness of 580 mg in the flow direction, It was 580 mg in the width direction. Further, this printing paper has water resistance. The results are summarized in Table 2 together with the printability evaluation of the obtained printing paper.
〔実施例２〜８、比較例１〜８〕
製造例１の脂肪族ポリエステル、表１に記載の無機微細粉末を表２に示す比率で混合した樹脂組成物を用いて、実施例１と同様の方法により印刷用紙を得た。厚み、密度、不透明度、表面積Ｓ、体積Ｖ、ガーレ剛度等の物性測定の結果を表２にまとめて示す。
〔実施例９〕
製造例２で得た脂肪族ポリエステル２を用いる以外は、実施例７と同様の方法により印刷用紙を得た。物性測定の結果を表２に示す。
[Examples 2-8, Comparative Examples 1-8]
Printing paper was obtained by the same method as in Example 1 using the resin composition obtained by mixing the aliphatic polyester of Production Example 1 and the inorganic fine powder described in Table 1 in the ratio shown in Table 2. Table 2 summarizes the results of measuring physical properties such as thickness, density, opacity, surface area S, volume V, and Gurley stiffness.
Example 9
A printing paper was obtained in the same manner as in Example 7 except that the aliphatic polyester 2 obtained in Production Example 2 was used. The results of physical property measurement are shown in Table 2.
〔実施例１０〕
上質紙の両面にポリエチレンフィルムをラミネートし、その片面にシリコーン処理を施した厚み１５０μｍ、密度０．９ｇ／ｃｍ3 の剥離紙のシリコーン処理面に、アクリル系粘着剤（東洋インキ製造（株）製、商品名：オリバインＢＰＳ−１１０９）を固形分量で２５ｇ／ｍ2 となるように塗工した後、乾燥させて粘着剤層を形成した。この剥離紙上の粘着剤層を、実施例１で得られた印刷用紙上に積層させて、粘着剤層及び剥離物を有する粘着ラベルを得た。
得られたものの厚みは４２５μｍ、ガーレ剛度は流れ方向２７５０ｍｇ、幅方向２７６０ｍｇであり、後述する印刷機の走行性、印刷網点再現性、ピッキングは良好なものであった。
Example 10
Acrylic adhesive (made by Toyo Ink Co., Ltd.) is applied to the silicone-treated surface of a release paper with a thickness of 150 μm and a density of 0.9 g / cm 3 , which is obtained by laminating polyethylene film on both sides of high-quality paper and applying silicone treatment on one side. , Trade name: olivine BPS-1109) was applied to a solid content of 25 g / m 2 and then dried to form an adhesive layer. The pressure-sensitive adhesive layer on the release paper was laminated on the printing paper obtained in Example 1 to obtain a pressure-sensitive adhesive label having a pressure-sensitive adhesive layer and a peeled material.
The obtained product had a thickness of 425 μm, a Gurley stiffness of 2750 mg in the flow direction and 2760 mg in the width direction, and the running property, printing dot reproducibility, and picking described later were good.
（評価例）
〔厚み〕
ＪＩＳ−Ｐ−８１１８に従って測定した。
〔密度〕
ＪＩＳ−Ｐ−８１１８に従って測定した。
〔不透明度〕
ＪＩＳ−Ｐ−８１３８に準拠し、測定試料背面に、黒色および白色標準板を当て、光の反射率の比（黒色板／白色板）を百分率で示した値で示す。一般に不透明度が低いほど光の裏抜けが多くなり、印刷物の鮮明性に欠ける。
(Evaluation example)
[Thickness]
It measured according to JIS-P-8118.
〔density〕
It measured according to JIS-P-8118.
[Opacity]
Based on JIS-P-8138, a black and white standard plate is applied to the back of the measurement sample, and the light reflectance ratio (black plate / white plate) is shown as a percentage value. In general, the lower the opacity, the more light penetration occurs and the printed material lacks clarity.
〔ガーレ剛度〕
ＪＡＰＡＮ ＴＡＰＰＩ 規格Ｎｏ．４０に従って測定した。
〔表面積Ｓ及び凸部の体積Ｖ〕
（株）キーエンス製の超深度形状測定顕微鏡（商品名：ＶＫ−８５５０）を用いて、本発明の印刷用紙の投影面積４，２９２μｍ2 当たりの表面積Ｓ、及び投影面積４，２９２μｍ2 当たりのフィルム表面の凸部の体積Ｖを、解像度０．３μｍ、倍率２０００倍にて測定した。凸部の体積Ｖは中心面と平行な、最大谷深さ部を基準面とした時の山部の体積である。
[Gurley stiffness]
JAPAN TAPPI Standard No. Measured according to 40.
[Surface area S and convex volume V]
KEYENCE manufactured ultradeep shape measuring microscope (trade name: VK-8550) using a surface area S, and the projected area 4,292Myuemu 2 per projected area 4,292Myuemu 2 per the printing paper of the present invention the film The volume V of the convex portion on the surface was measured at a resolution of 0.3 μm and a magnification of 2000 times. The volume V of the convex part is the volume of the peak part when the maximum valley depth part is parallel to the center plane and the reference plane is used.
（印刷適性評価）
〔オフセット印刷機走行性〕
（株）Ｔ＆Ｋ ＴＯＫＡ製の合成紙用油性オフセット印刷インキ（商品名：ベストＳＰ墨、藍、紅、黄）及び給紙部がバキュームベルト方式のローランド製オフセット４色印刷機（商品名：ローランド７００）を用い、本発明の印刷用紙の表面側に、５０％網点を含むテストパターンの４色枚葉オフセット印刷を行なう際、印刷用紙の印刷機走行性を次の基準で評価した。
・良好（○）：３，０００〜１２，０００枚／時の速度で安定して印刷ができる。
・やや不良（△）：安定して印刷するために３，０００枚／時よりも速度を落とす必要がある。
・不良（×）：重走トラブルや用紙の暴れにより機器が自動停止し、全く印刷ができない。
(Printability evaluation)
[Offset printing machine runnability]
Oil-based offset printing ink for synthetic paper (trade name: Best SP ink, indigo, red, yellow) manufactured by T & K TOKA Co., Ltd. and Roland's offset 4-color printing machine with a vacuum feeding system (trade name: Roland 700) ), The printing machine running performance of the printing paper was evaluated according to the following criteria when performing a four-color sheet offset printing of a test pattern including 50% halftone dots on the surface side of the printing paper of the present invention.
-Good (O): Stable printing can be performed at a speed of 3,000 to 12,000 sheets / hour.
Slightly poor (Δ): It is necessary to reduce the speed from 3,000 sheets / hour in order to print stably.
-Defective (X): The device automatically stops due to heavy running trouble or paper runaway, and printing cannot be performed at all.
〔オフセット印刷網点再現性〕
上記で得た印刷物の５０％網点部分を、実体顕微鏡に接続した画像解析装置（ニレコ（株）製、商品名：型式ルーゼックスＩＤ）で画像処理を行い、網点の実面積率から網点の太り率（ドットゲイン）を計算により求め、次の基準で良否を評価した。一般には表面の粗度、特に凸部の体積Ｖが大きいほど網点部のインキは周囲に流れて網点の太り率は増加し、不鮮明でぼやけたイメージの印刷物となる傾向がある。
・良好（○）：ドットゲインが１５〜２５％の範囲である。
・やや不良（△）：ドットゲインが２５％を越えて３０％以下の範囲である。
・不良（×）：ドットゲインが３０％を越えて大きい。
[Offset printing halftone dot reproducibility]
The 50% halftone dot portion of the printed matter obtained above is subjected to image processing with an image analysis apparatus (manufactured by Nireco Corporation, product name: model Luzex ID) connected to a stereomicroscope, and the halftone dot is determined from the actual area ratio of the halftone dot. The weight ratio (dot gain) was calculated and the quality was evaluated according to the following criteria. In general, as the surface roughness, particularly the volume V of the convex portion, increases, the ink at the halftone dots flows to the surroundings, and the thickness ratio of the halftone dots increases, and the printed matter tends to be blurred and blurred.
Good (O): The dot gain is in the range of 15 to 25%.
Slightly poor (Δ): The dot gain is in the range of more than 25% and 30% or less.
-Defect (x): The dot gain exceeds 30% and is large.
〔印刷鮮明性〕
上記で得た印刷物の反対面側に、更に画像や文字情報を含むテストパターンを印刷し、インキ乾燥後、室内照明下で表面側より印刷物の透けを目視により観察し、次の基準で良否を評価した。
・非常に良好（◎）：反対面側の画像は判別できず、文字情報は読み取れない。
・良好（○）：反対面側の画像、文字情報は判別できないが、色濃度変化は見える。
・不良（×）：反対面側の画像が重ねて見え、文字情報が読みとれる。
[Print sharpness]
On the opposite side of the printed matter obtained above, a test pattern including images and character information is further printed.After drying the ink, the transparency of the printed matter is visually observed from the surface side under room lighting. evaluated.
-Very good (◎): The image on the opposite side cannot be distinguished, and the character information cannot be read.
-Good (O): The image and character information on the opposite side cannot be distinguished, but the color density change is visible.
-Defect (x): The image on the opposite side is seen superimposed, and the character information can be read.
本発明による印刷用紙は、脂肪族ポリエステル樹脂に無機微細粉末を配合してなる組成物を溶融させてフィルム状に成形した無延伸樹脂フィルムからなる印刷用紙であり、優れた枚葉オフセット印刷性を有する印刷用紙として用いられる。 The printing paper according to the present invention is a printing paper composed of an unstretched resin film formed by melting a composition obtained by blending an inorganic fine powder into an aliphatic polyester resin and molding it into a film, and has excellent sheet-fed offset printability. Used as printing paper.
Claims (10)
−Ｏ−（ＣＨ2 ）m −Ｏ− ・・・（Ｉ）
（（Ｉ）式中、ｍは２〜１０の整数を表す。）
−ＯＣ−（ＣＨ2 ）n −ＣＯ− ・・・（II）
（（II）式中、ｎは１〜１２の整数を表す。） (A) 40 to 90% by weight of an aliphatic polyester resin containing at least an aliphatic diol unit represented by the following formula (I) and an aliphatic dicarboxylic acid unit represented by the following formula (II); and (b) An unstretched resin film containing an aliphatic polyester resin composition containing 10 to 60% by weight of inorganic fine powder, wherein the Gurley stiffness of the film is in the range of 50 to 3,000 mg, and the opacity of the film is 85 The surface area S per projected area of 4,292 μm 2 on the film surface is in the range of 5,000 to 50,000 μm 2 and the volume V of the projections per projected area of 4,292 μm 2 Is in the range of 2,000 to 20,000 μm 3 .
—O— (CH 2 ) m —O— (I)
(In the formula (I), m represents an integer of 2 to 10.)
-OC- (CH 2) n -CO- ··· (II)
(In the formula (II), n represents an integer of 1 to 12.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2005261449A JP4911935B2 (en) | 2004-09-10 | 2005-09-09 | Unstretched printing paper |
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| JP2004263332 | 2004-09-10 | ||
| JP2004263332 | 2004-09-10 | ||
| JP2005261449A JP4911935B2 (en) | 2004-09-10 | 2005-09-09 | Unstretched printing paper |
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| JP2006117916A true JP2006117916A (en) | 2006-05-11 |
| JP4911935B2 JP4911935B2 (en) | 2012-04-04 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20130078431A1 (en) * | 2011-09-28 | 2013-03-28 | Casio Computer Co., Ltd. | Composition for label base, method for producing label base, and label |
| JP2014056121A (en) * | 2012-09-12 | 2014-03-27 | Casio Electronics Co Ltd | Composition for label base material, label base material, label, and manufacturing methods therefor |
| JP2014077061A (en) * | 2012-10-10 | 2014-05-01 | Mitsubishi Chemicals Corp | Resin composition and molded product obtained by molding the resin composition |
| WO2014156744A1 (en) * | 2013-03-28 | 2014-10-02 | リンテック株式会社 | Adhesive sheet for tire, method of producing adhesive sheet for tire and method of use of adhesive sheet for tire |
| WO2015045656A1 (en) * | 2013-09-24 | 2015-04-02 | カシオ計算機株式会社 | Toner for film |
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| JPH08333444A (en) * | 1995-06-08 | 1996-12-17 | Toppan Printing Co Ltd | Thermally recording card |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20130078431A1 (en) * | 2011-09-28 | 2013-03-28 | Casio Computer Co., Ltd. | Composition for label base, method for producing label base, and label |
| JP2013083923A (en) * | 2011-09-28 | 2013-05-09 | Casio Electronics Co Ltd | Method for producing label |
| JP2014056121A (en) * | 2012-09-12 | 2014-03-27 | Casio Electronics Co Ltd | Composition for label base material, label base material, label, and manufacturing methods therefor |
| JP2014077061A (en) * | 2012-10-10 | 2014-05-01 | Mitsubishi Chemicals Corp | Resin composition and molded product obtained by molding the resin composition |
| WO2014156744A1 (en) * | 2013-03-28 | 2014-10-02 | リンテック株式会社 | Adhesive sheet for tire, method of producing adhesive sheet for tire and method of use of adhesive sheet for tire |
| WO2015045656A1 (en) * | 2013-09-24 | 2015-04-02 | カシオ計算機株式会社 | Toner for film |
| JP2015064427A (en) * | 2013-09-24 | 2015-04-09 | カシオ計算機株式会社 | Toner for film |
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