JP5944661B2 - Heat sensitive stencil printing base paper - Google Patents
Heat sensitive stencil printing base paper Download PDFInfo
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- JP5944661B2 JP5944661B2 JP2011285631A JP2011285631A JP5944661B2 JP 5944661 B2 JP5944661 B2 JP 5944661B2 JP 2011285631 A JP2011285631 A JP 2011285631A JP 2011285631 A JP2011285631 A JP 2011285631A JP 5944661 B2 JP5944661 B2 JP 5944661B2
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- polyol
- base paper
- heat
- sensitive stencil
- lithium
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- 229920005862 polyol Polymers 0.000 claims description 41
- 150000003077 polyols Chemical class 0.000 claims description 40
- 150000002642 lithium compounds Chemical class 0.000 claims description 33
- 239000000853 adhesive Substances 0.000 claims description 25
- 230000001070 adhesive effect Effects 0.000 claims description 25
- -1 imide lithium derivative Chemical class 0.000 claims description 24
- 229920005992 thermoplastic resin Polymers 0.000 claims description 23
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000654 additive Substances 0.000 claims description 17
- 230000000996 additive effect Effects 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 9
- 239000000839 emulsion Substances 0.000 claims description 9
- 229920000570 polyether Polymers 0.000 claims description 9
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229920001610 polycaprolactone Polymers 0.000 claims description 6
- 239000004632 polycaprolactone Substances 0.000 claims description 6
- 229920005906 polyester polyol Polymers 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 238000010030 laminating Methods 0.000 claims description 5
- 150000003949 imides Chemical class 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical class 0.000 claims 2
- 239000002216 antistatic agent Substances 0.000 description 24
- 239000000835 fiber Substances 0.000 description 23
- 229920000728 polyester Polymers 0.000 description 22
- 230000000694 effects Effects 0.000 description 12
- 239000000306 component Substances 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 229920002994 synthetic fiber Polymers 0.000 description 8
- 239000012209 synthetic fiber Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003623 enhancer Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
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- 229920000642 polymer Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- XFDQYYUJIBWHQS-UHFFFAOYSA-N 3,10-dioxabicyclo[10.2.2]hexadeca-1(14),12,15-triene-2,11-dione Chemical compound O=C1OCCCCCCOC(=O)C2=CC=C1C=C2 XFDQYYUJIBWHQS-UHFFFAOYSA-N 0.000 description 2
- LZFNKJKBRGFWDU-UHFFFAOYSA-N 3,6-dioxabicyclo[6.3.1]dodeca-1(12),8,10-triene-2,7-dione Chemical compound O=C1OCCOC(=O)C2=CC=CC1=C2 LZFNKJKBRGFWDU-UHFFFAOYSA-N 0.000 description 2
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
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- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 238000009413 insulation Methods 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
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- DADKKHHMGSWSPH-UHFFFAOYSA-N 1-butyl-3-methylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC(C)=C1 DADKKHHMGSWSPH-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000007696 Kjeldahl method Methods 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
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- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
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- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 235000012907 honey Nutrition 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
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- 235000019426 modified starch Nutrition 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
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- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
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Landscapes
- Printing Plates And Materials Therefor (AREA)
- Manufacture Or Reproduction Of Printing Formes (AREA)
- Laminated Bodies (AREA)
Description
感熱孔版印刷用の原紙は、一般的に、多孔性支持体（以下、「支持体」という場合がある）と、該支持体上に積層された熱可塑性樹脂フィルムからなる。このうちデジタル印刷機に用いられるものは、通常、長尺の帯状形状を有し、ロール状に巻き取られた状態で印刷機に装着され、印刷の際に、当該ロールから繰り出して使用される。 A base paper for heat-sensitive stencil printing is generally composed of a porous support (hereinafter sometimes referred to as “support”) and a thermoplastic resin film laminated on the support. Of these, those used for digital printing machines usually have a long belt-like shape, are mounted on the printing machine in a state of being wound up in a roll shape, and are used by being unwound from the roll during printing. .
多孔性支持体としては、薄葉紙、紗、不織布等が用いられている。薄葉紙（以下、「和紙」という場合がある）を使用する場合、低コスト化を目的として天然繊維を配合することが多いが、天然繊維は合成繊維に比べて極細のものが少なく、また夾雑物が混入しているため、支持体中のインク通過を阻害し、画像性が低下する原因となる。そこで、近年は高品質画像を目的に、支持体に天然繊維を使用していない原紙が使用されるようになっている。 As the porous support, thin paper, cocoons, nonwoven fabrics, and the like are used. When thin paper (hereinafter sometimes referred to as “Japanese paper”) is used, natural fibers are often blended for the purpose of cost reduction, but natural fibers are less fine than synthetic fibers and are not contaminated. Is mixed in, the ink passing through the support is obstructed and the image quality is lowered. Therefore, in recent years, a base paper that does not use natural fibers as a support has been used for the purpose of high-quality images.
しかし、支持体に天然繊維を配合していない和紙を用いた原紙は、天然繊維を配合したものに比べて静電気を帯びやすく、搬送性が低いという問題がある。この帯電現象は低温低湿環境下で顕著に現れる。 However, base paper using Japanese paper that does not contain natural fibers in the support has a problem that it is more easily charged and less transportable than those containing natural fibers. This charging phenomenon appears remarkably in a low temperature and low humidity environment.
上記問題の解決策として、原紙に帯電防止剤を添加することが知られている。例えば、原紙に導電性カーボンを添加する方法（特許文献１）、イオン性高分子化合物を配合する方法（特許文献２、３）が挙げられる。さらに、添加した帯電防止剤の裏抜けを防止するために、カチオン性重合体を配合する方法（特許文献４）、低分子界面活性剤をマイクロカプセルに包んで添加する方法（特許文献５）などがある。 As a solution to the above problem, it is known to add an antistatic agent to the base paper. Examples thereof include a method of adding conductive carbon to the base paper (Patent Document 1) and a method of adding an ionic polymer compound (Patent Documents 2 and 3). Furthermore, in order to prevent the added antistatic agent from falling through, a method of blending a cationic polymer (Patent Document 4), a method of adding a low molecular surfactant in a microcapsule (Patent Document 5), etc. There is.
しかし、帯電防止剤を添加した原紙で製版を重ねると、感熱孔版印刷機のサーマルヘッド素子部に帯電防止剤の堆積物が形成され、該堆積物にさらに異物が付着して、穿孔を阻害することがある。この現象が発生すると、印刷画像の主走査方向に白い線が入る。特に、リン酸系の帯電防止剤は、サーマルヘッドに付着して、熱によりリン酸塩に変じやすい。該塩は、通常の使用や手入れでは除去することができず、使用するにつれて増加し続ける。また、リン酸系の帯電防止剤も含め、界面活性剤タイプの帯電防止剤は、空気中の水分を捕捉することで帯電防止効果を発生するものが多く、湿度の高いところでは大きな効果を発揮するが、低湿度環境では効果が薄れるという問題もある。また、高分子帯電防止剤は添加量当たりの帯電防止能が低く、添加量が多くなりがちであるため、穿孔性の低下等の弊害を生じやすい。 However, when the plate making is repeated with the base paper to which the antistatic agent is added, a deposit of the antistatic agent is formed on the thermal head element portion of the thermal stencil printing machine, and further foreign matter adheres to the deposit and inhibits perforation. Sometimes. When this phenomenon occurs, a white line enters the main scanning direction of the printed image. In particular, the phosphoric acid-based antistatic agent adheres to the thermal head and is easily converted into a phosphate by heat. The salt cannot be removed by normal use or care and continues to increase as it is used. In addition, many surfactant-type antistatic agents, including phosphoric acid-based antistatic agents, generate antistatic effects by trapping moisture in the air, and are highly effective at high humidity. However, there is also a problem that the effect is reduced in a low humidity environment. In addition, since the polymer antistatic agent has a low antistatic ability per addition amount and tends to increase the addition amount, it tends to cause adverse effects such as a decrease in perforation property.
そこで、本発明は、感熱孔版印刷機のサーマルヘッド素子部に堆積物を生じることなく、少量の添加で、低湿度下でも帯電防止性に優れる、感熱孔版印刷用原紙を提供することを目的とする。 Accordingly, the present invention has an object to provide a heat-sensitive stencil sheet that is excellent in antistatic property even at low humidity with a small amount of addition, without causing deposits in the thermal head element portion of the heat-sensitive stencil printing machine. To do.
即ち、本発明は多孔性支持体の少なくとも一の面上に熱可塑性樹脂フィルムを設けた感熱孔版印刷用原紙であって、該感熱孔版印刷用原紙がリチウム元素換算で５〜５０ｐｐｍのリチウム化合物を含有することを特徴とする、感熱孔版印刷用原紙である。
また、本発明は、多孔性支持体の少なくとも一の面上に熱可塑性樹脂フィルムを設けた感熱孔版印刷用原紙の製造方法であって、
（１）ポリオール中に分散されたリチウム化合物と、ウレタン系接着剤および／またはウレタン系エマルジョンとの混合物を、該熱可塑性樹脂フィルムおよび／または該多孔性支持体に施与する工程、及び
（２）該多孔性支持体の少なくとも一の面上に、該熱可塑性樹脂フィルムを積層する工程、
を含むことを特徴とする方法である。
That is, the present invention is a heat-sensitive stencil printing paper provided with a thermoplastic resin film on at least one surface of a porous support, and the heat-sensitive stencil printing paper contains 5 to 50 ppm of a lithium compound in terms of lithium element. A base paper for heat-sensitive stencil printing, characterized by containing.
Further, the present invention is a method for producing a heat-sensitive stencil printing base paper provided with a thermoplastic resin film on at least one surface of a porous support,
(1) applying a mixture of a lithium compound dispersed in a polyol and a urethane-based adhesive and / or a urethane-based emulsion to the thermoplastic resin film and / or the porous support; and (2 ) Laminating the thermoplastic resin film on at least one surface of the porous support;
It is the method characterized by including.
上記本発明の感熱孔版印刷用原紙は、所定量のリチウム化合物を含むことによって、一般的な導電性フィラーや界面活性剤型の帯電防止剤を用いた場合の、上記各問題がなく、低湿度下でも、優れた帯電防止効果を示す。さらに、該リチウム系帯電防止剤を、ウレタン外添剤もしくは接着剤と組合わせて使用することによって、帯電防止能をより向上することができる。 The heat-sensitive stencil sheet of the present invention contains a predetermined amount of a lithium compound, thereby eliminating the above-described problems when using a general conductive filler or a surfactant-type antistatic agent, and having low humidity. Even under, it shows an excellent antistatic effect. Furthermore, the antistatic ability can be further improved by using the lithium antistatic agent in combination with a urethane external additive or an adhesive.
本発明の感熱孔版印刷用原紙（以下、「原紙」という場合がある）において、熱可塑性樹脂フィルムに用いられる熱可塑性樹脂としては、ポリエステル、ポリアミド、ポリプロピレン、ポリエチレン、ポリ塩化ビニル、ポリ塩化ビニリデンまたはその共重合体等を用いることができ、これらのうち穿孔性の点で、ポリエステル、ポリ塩化ビニリデンが好ましく、より好ましくはポリエステルである。該ポリエステルとしては、ポリエチレンテレフタレート、エチレンテレフタレートとエチレンイソフタレートとの共重合体、ポリエチレンナフタレート、ポリヘキサメチレンテレフタレート、ヘキサメチレンテレフタレートと１，４−シクロヘキサンジメチレンテレフタレートとの共重合体等が挙げられる。 In the heat-sensitive stencil printing base paper of the present invention (hereinafter sometimes referred to as “base paper”), the thermoplastic resin used for the thermoplastic resin film is polyester, polyamide, polypropylene, polyethylene, polyvinyl chloride, polyvinylidene chloride or The copolymer can be used, and among these, polyester and polyvinylidene chloride are preferable, and polyester is more preferable from the viewpoint of perforation. Examples of the polyester include polyethylene terephthalate, a copolymer of ethylene terephthalate and ethylene isophthalate, polyethylene naphthalate, polyhexamethylene terephthalate, a copolymer of hexamethylene terephthalate and 1,4-cyclohexanedimethylene terephthalate, and the like. .
該熱可塑性樹脂フィルムは、本発明の効果を阻害しない量で、難燃剤、熱安定剤、酸化防止剤、紫外線吸収剤、顔料、染料、脂肪酸エステル、ワックス等の有機滑材あるいはポリシロキサン等の消泡剤等を含んでよい。また、該熱可塑性樹脂フィルムの厚さは、原紙に要求される感度等によって適宜決定されるが、通常０．１〜１０μｍとされ、好ましくは０．１〜５μｍ、より好ましくは０．１〜３μｍである。該厚さが１０μｍを越えると穿孔性が低下する傾向があり、０．１μｍ未満ではフィルムの製膜安定性が悪い。 The thermoplastic resin film is an amount such as a flame retardant, a heat stabilizer, an antioxidant, an ultraviolet absorber, a pigment, a dye, a fatty acid ester, an organic lubricant such as a wax, or a polysiloxane in an amount that does not inhibit the effect of the present invention. An antifoaming agent etc. may be included. The thickness of the thermoplastic resin film is appropriately determined depending on the sensitivity required for the base paper, but is usually 0.1 to 10 μm, preferably 0.1 to 5 μm, more preferably 0.1 to 0.1 μm. 3 μm. When the thickness exceeds 10 μm, the piercing property tends to decrease, and when it is less than 0.1 μm, the film formation stability is poor.
多孔性支持体（以下「支持体」という場合がある）としては、合成繊維を主体とする短繊維を抄紙した薄葉紙、不織布、織物またはスクリーン紗などが好ましく用いられる。合成繊維としては、例えばポリエステル、ポリアミド、ポリフェニレンサルファイド、ポリアクリロニトリル、ポリプロピレン、ポリエチレンまたはそれらの共重合体などが用いられる。これらの合成繊維は、単体で用いても、２種以上を併用してもよい。 As the porous support (hereinafter sometimes referred to as “support”), a thin paper, a nonwoven fabric, a woven fabric, a screen wrinkle or the like made from a short fiber mainly composed of synthetic fibers is preferably used. As the synthetic fiber, for example, polyester, polyamide, polyphenylene sulfide, polyacrylonitrile, polypropylene, polyethylene, or a copolymer thereof is used. These synthetic fibers may be used alone or in combination of two or more.
これらの中では、強度およびもしくは耐水性の点で、ポリエステル、ポリアクリロニトリルが好ましく、より好ましくはポリエステル製の和紙が使用される。該ポリエステルとしては、ポリエチレンテレフタレート、エチレンテレフタレートとエチレンイソフタレートとの共重合体、ポリエチレンナフタレート、ポリヘキサメチレンテレフタレート、ヘキサメチレンテレフタレートと１，４−シクロヘキサンジメチレンテレフタレートとの共重合体等が挙げられる。該ポリエステル製の和紙に用いられるポリエステル繊維としては、一般にポリエチレンテレフタレート系延伸ポリエステル繊維や未延伸ポリエステル繊維、ポリエチレンテレフタレート系ポリエステルを芯成分とし、テレフタル酸、イソフタル酸、エチレングリコール、ジエチレングリコールなどから構成させる非晶性共重合ポリエステルを鞘成分とするポリエステル系複合繊維などが挙げられる。 Among these, polyester and polyacrylonitrile are preferable in terms of strength and / or water resistance, and polyester paper is more preferably used. Examples of the polyester include polyethylene terephthalate, a copolymer of ethylene terephthalate and ethylene isophthalate, polyethylene naphthalate, polyhexamethylene terephthalate, a copolymer of hexamethylene terephthalate and 1,4-cyclohexanedimethylene terephthalate, and the like. . As the polyester fiber used for the Japanese paper made of polyester, generally, a polyethylene terephthalate-based stretched polyester fiber, an unstretched polyester fiber, or a polyethylene terephthalate-based polyester is used as a core component, and the non-stretched polyester fiber is composed of terephthalic acid, isophthalic acid, ethylene glycol, diethylene glycol, or the like. Examples thereof include polyester-based composite fibers having a crystalline copolymer polyester as a sheath component.
多孔性支持体に用いられる合成繊維としては、原紙に求められる品質に応じて各種の繊維径のものを適宜使用することができ、単一の繊維径の合成繊維を用いてもよいが、２種以上の繊維径の合成繊維を併用することができる。たとえば、太繊維を配合して剛性や耐刷性能を向上させ、また、細繊維を配合して画像性を向上させてもよい。該支持体に用いる繊維の平均繊維径は、２０μｍ以下であることが好ましく、より好ましくは０．１μｍ〜１５μｍである。
また、こうぞ、みつまた、麻、ケナフ等の天然繊維、レーヨン、キュプラ、リヨセル等の再生セルロース繊維、ビニロン、ポリエステル、ポリアクリロニトリル等の合成繊維またはこれらの混合物を添加してもよい。
As the synthetic fiber used for the porous support, those having various fiber diameters can be appropriately used according to the quality required for the base paper, and synthetic fibers having a single fiber diameter may be used. Synthetic fibers having a fiber diameter of more than one species can be used in combination. For example, thick fibers may be blended to improve rigidity and printing durability, and fine fibers may be blended to improve image quality. The average fiber diameter of the fibers used for the support is preferably 20 μm or less, more preferably 0.1 μm to 15 μm.
In addition, natural fibers such as koji, honey or hemp and kenaf, regenerated cellulose fibers such as rayon, cupra and lyocell, synthetic fibers such as vinylon, polyester and polyacrylonitrile, or a mixture thereof may be added.
また、該支持体には、本発明の効果を阻害しない量で、難燃剤、熱安定剤、酸化防止剤、紫外線吸収剤、顔料、染料、脂肪酸エステル、ワックス等の有機滑材あるいはポリシロキサン等の消泡剤等を配合することができる。 In addition, the support may be an organic lubricant such as a flame retardant, a heat stabilizer, an antioxidant, an ultraviolet absorber, a pigment, a dye, a fatty acid ester, a wax, or a polysiloxane in an amount that does not impair the effects of the present invention. An antifoaming agent or the like can be blended.
該支持体は湿式抄紙法により作ることができ、繊維を分散およびフィルタリングした後にワイヤ上にすくい取り、脱水、及び乾燥させて製造することができる。 The support can be made by a wet papermaking process and can be produced by dispersing and filtering the fibers, then scooping them on the wire, dewatering and drying.
該支持体の繊維の坪量は２０ｇ／ｍ２以下が好ましく、より好ましくは５ｇ／ｍ２〜２０ｇ／ｍ２、さらに好ましくは５ｇ／ｍ２〜１５ｇ／ｍ２である。坪量が前記上限値を超えると、インキの通過性が低下して画像鮮明性が低下しやすく、坪量が前記下限値より少ないと、支持体として十分な強度を得られない場合がある。さらに、引張り強さ（湿潤状態、抄紙流れ方向）が０．１ｋＮ／ｍ以上であることが好ましく、より好ましくは０．４ｋＮ／ｍ以上である。 The basis weight of the fibers of the support is preferably from 20 g / m 2 or less, more preferably 5g / m 2 ~20g / m 2 , more preferably from 5g / m 2 ~15g / m 2 . If the basis weight exceeds the upper limit, ink permeability is likely to deteriorate and image sharpness tends to be reduced. If the basis weight is less than the lower limit, sufficient strength as a support may not be obtained. Furthermore, the tensile strength (wet state, papermaking flow direction) is preferably 0.1 kN / m or more, more preferably 0.4 kN / m or more.
本発明の原紙は、リチウム元素換算で５〜５０ｐｐｍ、好ましくは１５〜３５ｐｐｍのリチウム化合物を含む。該リチウム量は、例えば、原紙をケルダール法によって処理した後、ＩＣＰ発光分析を行なうことによって、測定することができる。リチウムは、全元素中で酸化還元電位が最も低いことから、特許文献２、３においてもリチウム塩が挙げられている。しかし、これらはアニオン性高分子のリチウム塩であるために、単位質量あたりのリチウム含有量が少ない。このため、所望の帯電防止能を達成しようとすると、自ずと配合量が多くなり、原紙の強度や穿孔性を低下するという問題がある。 The base paper of the present invention contains 5 to 50 ppm, preferably 15 to 35 ppm of lithium compound in terms of lithium element. The amount of lithium can be measured, for example, by treating the base paper by the Kjeldahl method and performing ICP emission analysis. Since lithium has the lowest oxidation-reduction potential among all the elements, Patent Documents 2 and 3 also mention lithium salts. However, since these are lithium salts of anionic polymers, the lithium content per unit mass is small. For this reason, when it is going to achieve desired antistatic ability, there exists a problem that the compounding quantity will naturally increase and the intensity | strength and punchability of a base paper will fall.
本発明の原紙中に含有されるリチウム化合物の分子量は、約２０００以下であることが好ましく、より好ましくは８００以下の低分子リチウム化合物の形態で含まれる。該リチウム化合物としては、イミドリチウム誘導体が好ましく、より好ましくは下記式（１）で表されるビス（パーフロロアルキルスルホニル）イミドリチウム化合物である。
上式において、Ｒ１及びＲ２は、夫々、独立に炭素数１〜１２のフッ素化炭化水素基、好ましくは炭素数１〜８のフッ素化炭化水素基、例えば、ＣＦ３−、Ｃ２Ｆ５−、ＣＨＦ２−等である。該スルホンイミドリチウム化合物自体は公知であるが（例えば特開2008-266155号公報）、感熱孔版印刷用原紙に使用された例は無い。該化合物は、その導電性効果が湿度の影響を受け難く、低湿度でも高い帯電防止効果を示す。
The molecular weight of the lithium compound contained in the base paper of the present invention is preferably about 2000 or less, more preferably 800 or less in the form of a low molecular lithium compound. The lithium compound is preferably an imidolithium derivative, more preferably a bis (perfluoroalkylsulfonyl) imidelithium compound represented by the following formula (1).
In the above formula, R 1 and R 2 are each independently a fluorinated hydrocarbon group having 1 to 12 carbon atoms, preferably a fluorinated hydrocarbon group having 1 to 8 carbon atoms, such as CF 3 —, C 2 F 5 -, CHF 2 -, and the like. Although the sulfonimide lithium compound itself is known (for example, Japanese Patent Application Laid-Open No. 2008-266155), there is no example used for a heat-sensitive stencil printing base paper. The compound is less susceptible to humidity due to its conductive effect, and exhibits a high antistatic effect even at low humidity.
好ましくは、リチウム化合物は、該化合物を分散もしくは溶解する担体もしくは媒体中に含まれる。該担体を変えることで水系・非水系の各種用途に使用でき、さらに、原紙中において、リチウム化合物が該担体および／又は該担体から誘導される構造、例えば高分子網目構造、中に担持されて、原紙中に強固に保持される。該担体としては、ポリオールもしくはその誘導体が好ましく、例えば、ポリエーテルポリオール、ポリエステル系ポリオール、ポリカプロラクトン系ポリオール、シリコーンポリオール等、およびそれらの誘導体が挙げられる。該リチウム化合物を接着剤に添加する場合には、グリコールのエーテル誘導体が、外添剤に添加する場合には、ポリエーテルポリオールが、夫々、担体として好ましい。 Preferably, the lithium compound is contained in a carrier or medium in which the compound is dispersed or dissolved. By changing the carrier, it can be used for various aqueous and non-aqueous applications. Further, in the base paper, the lithium compound is supported in the carrier and / or a structure derived from the carrier, for example, a polymer network structure. , Firmly held in the base paper. The carrier is preferably a polyol or a derivative thereof, and examples thereof include polyether polyols, polyester-based polyols, polycaprolactone-based polyols, silicone polyols, and derivatives thereof. When the lithium compound is added to the adhesive, an ether derivative of glycol is preferable as the carrier, and when it is added to the external additive, a polyether polyol is preferable as the carrier.
本発明の原紙は、リチウム化合物に加え、フッ素元素量換算で１００〜７００ｐｐｍ、好ましくは２００〜５００ｐｐｍのフッ素化炭化水素基をさらに含むことが好ましい。該フッ素量は、燃焼法および／もしくはイオンクロマトグラフ法により測定できる。また該フッ素量は、上記式（１）の化合物の添加により、達成することができる。 The base paper of the present invention preferably further contains a fluorinated hydrocarbon group of 100 to 700 ppm, preferably 200 to 500 ppm, in terms of the amount of fluorine element, in addition to the lithium compound. The amount of fluorine can be measured by a combustion method and / or an ion chromatography method. The amount of fluorine can be achieved by adding the compound of the above formula (1).
本発明の原紙は、下記工程を含む方法で作ることができる。
（１）ポリオール中に分散されたリチウム化合物と、ウレタン系接着剤および／またはウレタン系エマルジョンとの混合物を、該熱可塑性樹脂フィルムおよび／または該多孔性支持体に施与する工程、及び
（２）該多孔性支持体の少なくとも一の面上に、該熱可塑性樹脂フィルムを積層する工程。
The base paper of the present invention can be produced by a method including the following steps.
(1) applying a mixture of a lithium compound dispersed in a polyol and a urethane-based adhesive and / or a urethane-based emulsion to the thermoplastic resin film and / or the porous support; and (2 ) A step of laminating the thermoplastic resin film on at least one surface of the porous support.
工程（１）には、三種類の態様がある。第一の態様は、リチウム化合物を、熱可塑性樹脂フィルムと支持体の貼り合わせに用いる接着剤に添加して、熱可塑性樹脂フィルム及び／又は支持体上に施与する方法である。第二の態様はリチウム化合物を、支持体の外添剤、例えば紙力増強剤、撥水剤に添加して、支持体に施与した後、硬化する方法である。第三の態様は、これら双方を行なう方法であり、接着剤と外添剤の双方にリチウム化合物を添加する。第一の態様は、静電気の原因であるフィルムに帯電防止剤を含む接着剤が直接接触することから、効果的である。ただし、リチウム化合物の添加量が多くなると接着力が低下し、また、原紙の穿孔性を阻害する場合がある。そこで、帯電防止剤とその担体を合計した量での添加量の目安は、接着剤の固形分に対し５質量％〜３０質量％、好ましくは５質量％〜１５質量％である。該帯電防止剤を含む接着剤を、原紙に対して固形分で０．０５ｇ／ｍ２〜１．０ｇ／ｍ２になるように塗布することで、上記リチウムの量を達成できる。 There are three types of steps in the step (1). The first aspect is a method in which a lithium compound is added to an adhesive used for laminating a thermoplastic resin film and a support, and applied to the thermoplastic resin film and / or the support. The second embodiment is a method in which a lithium compound is added to an external additive such as a paper strength enhancer or a water repellent, applied to the support, and then cured. The third aspect is a method of performing both of these, and a lithium compound is added to both the adhesive and the external additive. The first aspect is effective because an adhesive containing an antistatic agent is in direct contact with the film that causes static electricity. However, when the addition amount of the lithium compound is increased, the adhesive strength is lowered, and the punchability of the base paper may be hindered. Therefore, the standard of the amount added in the total amount of the antistatic agent and its carrier is 5% by mass to 30% by mass, preferably 5% by mass to 15% by mass with respect to the solid content of the adhesive. The adhesives comprising antistatic agents, by applying to be 0.05g / m 2 ~1.0g / m 2 on a solids relative to the base paper can be achieved the amount of the lithium.
熱可塑性樹脂フィルムと支持体の貼り合わせに用いる接着剤としては、酢酸ビニル系、アクリル系、塩化ビニル酢酸ビニル共重合系、ポリエステル系、ウレタン系などの加熱型接着剤、アクリレート系、ポリエステルアクリレート系、ウレタンアクリレート系、エポキシアクリレート系、ポリオールアクリレート系等の光硬化型の接着剤が挙げられ、これらのうちウレタンアクリレート系、ウレタン系が好ましく、これらを上記ポリオール系担体中の帯電防止剤と組み合わせて使用することが好ましい。工程（２）の積層工程中もしくは後の硬化過程において、ポリオールがウレタン高分子網目構造に固定されることによって、原紙中での帯電防止剤がより固定化される。 Adhesives used for bonding the thermoplastic resin film to the support include vinyl acetate, acrylic, vinyl chloride vinyl acetate copolymer, polyester, urethane and other heating adhesives, acrylate, polyester acrylate , Urethane acrylate-based, epoxy acrylate-based, polyol acrylate-based and other photo-curable adhesives. Among these, urethane acrylate-based and urethane-based adhesives are preferable, and these are combined with the antistatic agent in the polyol-based carrier. It is preferable to use it. The antistatic agent in the base paper is further fixed by fixing the polyol to the urethane polymer network structure in the laminating step of the step (2) or in the subsequent curing process.
該ウレタン系接着剤としては、一液型、二液型のいずれであってもよい。該ウレタンにおけるポリオール成分としては、ポリエーテルポリオール、ポリエステルポリオールが、イソシアネート成分としては、炭素数６〜１６の、アルキレン基等の脂肪族基、シクロアルキレン基等の脂環式基、又はアリレーン基等の芳香族基を有するジイソシアネート、例えば、１，６−ジイソシアナートへキサン、１，３−ビス（イソシアナートメチル）ベンゼン、１，３−ビス（イソシアナートメチル）シクロヘキサン、１，５−ナフタレンジイソシアネート、及びこれらの混合物が挙げられる。 The urethane adhesive may be either a one-component type or a two-component type. As the polyol component in the urethane, polyether polyol and polyester polyol are used, and as the isocyanate component, an aliphatic group such as an alkylene group having 6 to 16 carbon atoms, an alicyclic group such as a cycloalkylene group, an arylene group, and the like. Diisocyanates having an aromatic group such as 1,6-diisocyanatohexane, 1,3-bis (isocyanatomethyl) benzene, 1,3-bis (isocyanatomethyl) cyclohexane, 1,5-naphthalene diisocyanate , And mixtures thereof.
第二の態様では、帯電防止剤を含む外添剤、例えば紙力増強剤、撥水剤を支持体に塗布もしくは含浸させる。帯電防止剤の量としては、外添剤本来の機能である和紙の強度・剛性付与を妨げないように、帯電防止剤とその担体を合計した量での添加量の目安は、外添剤の固形分に対して１．０質量％〜３０．０質量％であり、帯電防止剤を含む該外添剤を、原紙に対して固形分で０．０１ｇ／ｍ２〜１．０ｇ／ｍ２の量になるように施与する。塗布後、加熱して外添剤を固化もしくは硬化する。 In the second embodiment, an external additive containing an antistatic agent such as a paper strength enhancer or a water repellent is applied or impregnated on the support. As the amount of antistatic agent, in order not to impede the strength and rigidity of Japanese paper, which is the original function of the external additive, the total amount of antistatic agent and its carrier is a guideline for the amount of external additive. 1.0 wt% to 30.0 wt% based on the solids content, 0.01 g / m 2 by solid content external additive, relative to the base paper containing the antistatic agent to 1.0 g / m 2 Apply to the amount of After coating, the external additive is solidified or cured by heating.
外添剤、特に紙力増強剤としては、一般の紙基材に用いられる、ポリビニルアルコール、カルボキシ変性ポリビニルアルコール等のポリビニルアルコール類、カルボキシメチルセルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、セルロースサルフェート等のセルロース誘導体、デンプンおよびカチオン化デンプン等の変性デンプン、ゼラチン、カゼイン等のたんぱく質、アニオン化ポリアクリルアミド樹脂、ポリアミドポリアミンエピクロルヒドリン樹脂等のアミド系樹脂、アクリレート系樹脂、ウレタン系樹脂、ウレタンアクリレート系樹脂、スチレン−無水マレイン酸共重合体ナトリウム、ポリスチレンスルフォン酸ナトリウム等のスチレン系樹脂、等を挙げることができ、これらの水溶液もしくはエマルジョンが用いられる。さらにこれらは単独もしくは併用することができる。これらのうち、ウレタン系樹脂のエマルジョン、ウレタンアクリレート系樹脂のエマルジョンが好ましく、上記ポリオール系担体中の帯電防止剤と組み合わせて使用することが好ましい。外添剤は、工程（２）の前に加熱硬化する。得られた支持体上に、工程（２）において、熱可塑性樹脂フィルムを、熱融着、もしくは接着剤を用いて、積層する。 As an external additive, particularly a paper strength enhancer, polyvinyl alcohols such as polyvinyl alcohol and carboxy-modified polyvinyl alcohol, cellulose derivatives such as carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, and cellulose sulfate, which are used for general paper base materials, Modified starches such as starch and cationized starch, proteins such as gelatin and casein, amide resins such as anionized polyacrylamide resins, polyamide polyamine epichlorohydrin resins, acrylate resins, urethane resins, urethane acrylate resins, styrene-anhydrous maleic resins Examples thereof include styrene resins such as acid copolymer sodium and sodium polystyrene sulfonate, and their aqueous solutions or emulsions. Used. Furthermore, these can be used alone or in combination. Among these, an emulsion of urethane resin and an emulsion of urethane acrylate resin are preferable, and it is preferable to use in combination with the antistatic agent in the polyol carrier. The external additive is cured by heating before the step (2). In step (2), the thermoplastic resin film is laminated on the obtained support using heat fusion or an adhesive.
上記三種類の態様のうち、第二または第三の態様が好ましく、第ニの態様が最も好ましい。これは、原紙における重量構成比で支持体が原紙の大部分を占めることから、接着剤に添加する場合よりも多くの帯電防止剤を添加しやすい事、また、原紙は巻き重ねられた状態でフィルム表面に接触しているため、外添剤として添加した方が搬送性の向上に寄与し易い事などが理由である。 Of the above three types of embodiments, the second or third embodiment is preferred, and the second embodiment is most preferred. This is because the support occupies most of the base paper by the weight composition ratio of the base paper, so it is easier to add more antistatic agent than when it is added to the adhesive, and the base paper is in a state of being rolled up. This is because, since it is in contact with the film surface, the addition as an external additive tends to contribute to the improvement of transportability.
以下、本発明を実施例により説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.
ウレタン系エマルジョン（商品名スーパーフレックス８００、固形分３５％、第一工業製薬製）９７．５ｇ中に、ポリエーテルポリオールを担体とするイミドリチウム型の帯電防止剤（サンコノールＰＥＯ−２０Ｒ、式（１）のＲ１、Ｒ２がともにＣＦ３ＳＯ２−、分子量２８７、イミドリチウム成分２０％、三光化学製）を２．５ｇ添加し、得られた混合物を、ポリエステル繊維のみで抄紙された支持体（厚み４０ミクロン、坪量１２ｇ／ｍ２）に２．８ｇ／ｍ２の量で塗布し、加熱硬化した。次いで、ポリエステルフィルム（二軸延伸ポリエチレンテレフタレートフィルム、厚み２ミクロン）の片面にＵＶ硬化型接着剤（ウレタン（メタ）アクリレート系）を、０．４５ｇ／ｍ２の量で塗布し、上記支持体を積層した後、ポリエステルフィルム側から紫外線（オーク製作所製ＯＨＤ−３２０Ｍ）を照射して硬化させ、原紙を作製した。該原紙中のリチウム含有量は２４ｐｐｍであった。 Imide lithium type antistatic agent (Sanconol PEO-20R, formula (1) using polyether polyol as a carrier in 97.5 g of urethane emulsion (trade name Superflex 800, solid content 35%, manufactured by Daiichi Kogyo Seiyaku) ) In which R 1 and R 2 are both CF 3 SO 2 —, molecular weight 287, imidolithium component 20%, manufactured by Sanko Chemical Co., Ltd.), and 2.5 g of the resulting mixture is made from a polyester fiber alone. It was applied in an amount of 2.8 g / m 2 on (thickness 40 microns, basis weight 12 g / m 2 ) and cured by heating. Next, a UV curable adhesive (urethane (meth) acrylate)) was applied to one side of a polyester film (biaxially stretched polyethylene terephthalate film, thickness 2 microns) in an amount of 0.45 g / m 2 , and the support was then applied. After the lamination, ultraviolet rays (OHD-320M manufactured by Oak Manufacturing Co., Ltd.) were irradiated and cured from the polyester film side to prepare a base paper. The lithium content in the base paper was 24 ppm.
テトラエチレングリコールジメチルエーテルを担体とするイミドリチウム型の帯電防止剤（サンコノールＴＧＲ、式（１）のＲ１、Ｒ２ともにＣＦ３ＳＯ２−、分子量２８７、イミドリチウム成分５６％、三光化学製）１０ｇを、ＵＶ硬化型接着剤（ウレタン（メタ）アクリレート系）９０ｇに添加して、撹拌し、接着液を得た。これを実施例１で使用したものと同様のポリエステルフィルムに０．４５ｇ／ｍ２の量で塗布した。別途、ポリウレタン水系ラテックスに、リチウム化合物を配合しなかったことを除き、実施例１と同様に処理したポリエステル繊維製和紙を処理した。これを、接着剤層の上に積層した後、実施例１と同様にして、紫外線で硬化させて原紙を作製した。該原紙中のリチウム含有量は３４ｐｐｍであった。 10 g of imidolithium type antistatic agent using tetraethylene glycol dimethyl ether as a carrier (Sanconol TGR, R 1 and R 2 of formula (1) are both CF 3 SO 2 —, molecular weight 287, imidolithium component 56%, Sanko Chemical) Was added to 90 g of a UV curable adhesive (urethane (meth) acrylate) and stirred to obtain an adhesive solution. This was applied to the same polyester film used in Example 1 in an amount of 0.45 g / m 2 . Separately, a polyester fiber Japanese paper treated in the same manner as in Example 1 was treated except that the lithium compound was not blended with the polyurethane water-based latex. This was laminated on the adhesive layer and then cured with ultraviolet rays in the same manner as in Example 1 to produce a base paper. The lithium content in the base paper was 34 ppm.
＜比較例１＞
接着剤にリチウム化合物を添加しなかったことを除き、実施例２と同様に原紙を作製した。
<Comparative Example 1>
A base paper was prepared in the same manner as in Example 2 except that no lithium compound was added to the adhesive.
＜比較例２＞
リチウム化合物に代えて、リン酸エステル型の帯電防止剤（デートロンＮ−２０、固形分２２％、日華化学製）１．９９ｇをウレタン系エマルジョンに添加したことを除き、実施例１と同様にして、原紙を作成した。和紙への実塗布量と原紙全体の総重量から算出したリン酸エステルの含有量は約３４７ｐｐｍであった。
<Comparative Example 2>
In the same manner as in Example 1, except that 1.99 g of a phosphoric acid ester type antistatic agent (Daytron N-20, solid content 22%, manufactured by Nikka Chemical) was added to the urethane emulsion instead of the lithium compound. A base paper was created. The phosphate ester content calculated from the actual amount applied to Japanese paper and the total weight of the base paper was about 347 ppm.
＜比較例３＞
リチウム化合物に代えて、帯電防止効果を持つN-ブチル-3-メチルピリジニウム・ビストリフルオロメタンスルホニルイミド（ＣＩＬ３１２、主成分量９９％以上、日本カーリット製）１０ｇをＵＶ硬化型接着剤に添加したことを除き、実施例２と同様にして原紙を作成した。フィルムへの実塗布量と原紙全体の総重量から算出したイオン性液体の含有量は約４９７ｐｐｍであった。
<Comparative Example 3>
In place of the lithium compound, 10 g of N-butyl-3-methylpyridinium bistrifluoromethanesulfonylimide (CIL312, main component amount 99% or more, manufactured by Nippon Carlit) with antistatic effect was added to the UV curable adhesive. A base paper was prepared in the same manner as in Example 2 except for. The content of the ionic liquid calculated from the actual coating amount on the film and the total weight of the whole base paper was about 497 ppm.
各原紙を以下の方法で評価した。結果を表１に示す。
＜表面固有抵抗＞
温度／湿度が２３℃／５０％および５℃／３０％の条件下で、極超絶縁計ＳＭ−８２２０（日置電機製）を用いて、原紙の表面固有抵抗を測定した。結果を表１に示す。表１中、「＞１．０×１０１６［Ω／□］」は、該極超絶縁計の測定上限を超えたことを意味する。
Each base paper was evaluated by the following method. The results are shown in Table 1.
<Surface specific resistance>
Under the conditions of temperature / humidity of 23 ° C./50% and 5 ° C./30%, the surface resistivity of the base paper was measured using a super insulation meter SM-8220 (manufactured by Hioki Electric). The results are shown in Table 1. In Table 1, “> 1.0 × 10 16 [Ω / □]” means that the measurement upper limit of the ultra-insulation meter was exceeded.
＜サーマルヘッド表面への異物の堆積状態＞
作製した原紙をリソグラフＭＤ６６５０Ｗ（理想科学工業製）に装着して、網点原稿を２，０００版連続製版した後に、サーマルヘッド表面への異物の堆積状態をサーフテスト（ミツトヨ製）にて観察した。
<Foreign matter accumulation on the thermal head surface>
The prepared base paper was mounted on a lithograph MD6650W (made by Riso Kagaku Kogyo Co., Ltd.), and a halftone dot original was continuously made up to 2,000 plates, and then the accumulation state of foreign matters on the surface of the thermal head was observed by a surf test (made by Mitutoyo). .
表１に示すように、リチウム化合物は、リチウム量として数十ｐｐｍ程度のわずかな添加量で、リン酸エステルと同等以上の帯電防止効果を発揮し、低温・低湿度でも安定した効果を示すのに加え、サーマルヘッド上の堆積物も顕著に少ない。また、リチウム化合物を和紙の外添剤に添加することで（実施例１）、より高い効果が得られることが分かった。 As shown in Table 1, the lithium compound exhibits an antistatic effect equivalent to or better than that of a phosphate ester with a slight addition amount of several tens of ppm as a lithium amount, and exhibits a stable effect even at low temperature and low humidity. In addition, deposits on the thermal head are significantly less. It was also found that a higher effect can be obtained by adding a lithium compound to the external additive of Japanese paper (Example 1).
本発明の感熱孔版印刷用原紙は、サーマルヘッドの素子部に堆積物を形成することなく、低温・低湿度下でも帯電防止性に優れる。 The base paper for heat-sensitive stencil printing of the present invention is excellent in antistatic property even at low temperature and low humidity without forming deposits on the element portion of the thermal head.
Claims (13)
（１）ポリオール中に分散されたリチウム化合物と、ウレタン系接着剤および／またはウレタン系エマルジョンとの混合物を、前記熱可塑性樹脂フィルムおよび／または前記多孔性支持体に施与する工程、及び
（２）前記多孔性支持体の少なくとも一の面上に、前記熱可塑性樹脂フィルムを積層する工程、
を含むことを特徴とする方法。 A method for producing a heat-sensitive stencil sheet having a thermoplastic resin film provided on at least one surface of a porous support,
(1) a lithium compound dispersed in the polyol, a mixture of a urethane adhesive and / or urethane emulsion and applied to the thermoplastic resin film and / or the porous support step, and (2 ) on at least one surface of the porous support, the step of laminating the thermoplastic resin film,
A method comprising the steps of:
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