JPS6228830B2 - - Google Patents
Info
- Publication number
- JPS6228830B2 JPS6228830B2 JP8823780A JP8823780A JPS6228830B2 JP S6228830 B2 JPS6228830 B2 JP S6228830B2 JP 8823780 A JP8823780 A JP 8823780A JP 8823780 A JP8823780 A JP 8823780A JP S6228830 B2 JPS6228830 B2 JP S6228830B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- alcohol
- methacrylic acid
- ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 28
- 229920001577 copolymer Polymers 0.000 claims description 28
- 238000007639 printing Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 150000002148 esters Chemical class 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- -1 vinyl aromatic hydrocarbons Chemical class 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 6
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 6
- 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 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 239000000976 ink Substances 0.000 description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 20
- 239000002904 solvent Substances 0.000 description 20
- 238000001035 drying Methods 0.000 description 15
- 238000009835 boiling Methods 0.000 description 12
- 239000002966 varnish Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- 235000019198 oils Nutrition 0.000 description 11
- KBAYQFWFCOOCIC-GNVSMLMZSA-N [(1s,4ar,4bs,7s,8ar,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,7,8,8a,9,10,10a-dodecahydrophenanthren-1-yl]methanol Chemical compound OC[C@@]1(C)CCC[C@]2(C)[C@H]3CC[C@H](C(C)C)C[C@H]3CC[C@H]21 KBAYQFWFCOOCIC-GNVSMLMZSA-N 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 125000001931 aliphatic group Chemical group 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000007645 offset printing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 235000019169 all-trans-retinol Nutrition 0.000 description 2
- 239000011717 all-trans-retinol Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- NPSJHQMIVNJLNN-UHFFFAOYSA-N 2-ethylhexyl 4-nitrobenzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=C([N+]([O-])=O)C=C1 NPSJHQMIVNJLNN-UHFFFAOYSA-N 0.000 description 1
- 239000004808 2-ethylhexylester Substances 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001753 carvones Chemical class 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は新規な印刷インキ用バインダーに関す
る。さらに詳しくは、脂肪族高沸点溶剤に対する
溶解性のすぐれた印刷インキ用バインダーに関す
る。
印刷インキ、とくにオフセツト印刷インキに要
求される基本的性質としては、つぎのごときもの
があげられる。すなわち
(1) 粘度および降伏値などの流動特性を示す値が
適当であること、
(2) 水とインキが相接して平面上に画線を形成す
るために画線部と非画線部との間に界面的なバ
ランスが保たれること、
(3) 顔料の分散性がよいこと、
(4) セツトおよび乾燥が早く、印刷物のブロツキ
ングがないこと、
(5) 印刷面の光沢が良好で、かつ均一な印刷物が
えられること、
(6) 印刷面の耐摩耗性がよいこと、
などがあげられる。
従来より使用されている印刷インキワニスは、
ロジン変性フエノール樹脂、アルキツド樹脂、エ
ステルガムなどの樹脂をアマニ油などの乾性油に
溶解し、さらに脂肪族系高沸点溶剤を添加して調
整されている。このようなワニスを使用した印刷
インキのセツトおよび乾燥は溶剤の紙への浸透ま
たは加熱による蒸発と、引き続く乾性油の酸化重
合による皮膜形成により支配され、とくに後者が
律速段階である。乾性油は印刷面の光沢を向上さ
せる目的で使用されるものであり、これの使用量
を減少すれば、それに応じてセツト、乾燥が早く
なるが、当然の結果として光沢の低下をきたす。
さらに乾性油の使用量を減ずれば、前記の樹脂は
溶剤への溶解性が乏しいためにワニスの調製すら
困難となる。逆に溶剤を減少すれば光沢は良好と
なるがセツト、乾燥がきわめて遅くなる。したが
つて乾性油と溶剤とを併用し、目的に応じて適宜
その割合を変更しているのが現状である。
乾性油を含む印刷インキにはいまひとつの問題
点がある。すなわち印刷機のロールに付着したイ
ンキは、そのまま放置すれば乾性油の酸化重合に
より硬化して不溶性の皮膜を形成するために、印
刷を中断するばあいにはその都度ロール上のイン
キを拭取らなければならない。このような問題を
解決するためには、乾性油を含む印刷インキにポ
リシクロペンタジエンを添加する方法や乾性油の
一部を特定のリン酸エステルで置換する方法が提
案されているが、いずれもインキ処方上の解決策
である。
特開昭53−98385号には、メタクリル酸イソブ
チル、メタクリル酸イソボルニルおよびメタクリ
ル酸の共重合体が脂肪族系高沸点溶剤に溶解する
ことおよびこれらを主成分とし乾性油を含まない
印刷インキワニスが開示されているが、印刷紙の
光沢はなお不充分である。
しかるに本発明者らは叙上の欠点を克服するべ
く鋭意研究を重ねた結果、たとえば「マギー
535」（米国、マギー社製）、「日石５号ソルベン
ト」（日本石油(株)製）などの脂肪族系高沸点溶剤
に溶解し、乾性油を含まずとも印刷インキとくに
オフセツト印刷インキに適合しうるバインダーを
見出し、本発明を完成するにいたつた。
すなわち本発明の印刷インキ用バインダーは、
10〜60重量％のビニル芳香族炭化水素、30〜90重
量％のロジンアルコールとアクリル酸またはメタ
クリル酸とのエステル、0.5〜10重量％のα・β
−不飽和カルボンおよび０〜10重量％の共重合し
うる他の単量体を共重合せしめてえられる樹脂状
共重合体を有効成分とする印刷インキ用バインダ
ーに関するものである。
本発明に用いるビニル芳香族炭化水素として
は、たとえばスチレン、α−メチルスチレン、ビ
ニルトルエン、ビニルキシレンなどがあげられ、
このうちとくに好ましいものはスチレンである。
使用量は全モノマーに対して10〜60％（重量％、
以下同様）であり、好ましくは20〜50％である。
該成分は共重合体をインキバインダーとして使用
するばあい、顔料に対する濡れが良好で顔料分散
性を向上させ、結局印刷面の光沢を良好にする。
該成分が多くなるほどインキのセツトが速くなる
が、多すぎると高沸点溶剤への溶解性が劣り好ま
しくない。また少なすぎるとインキのセツトが遅
くなり好ましくない。
本発明において用いるロジンアルコールとして
は、たとえばアビエチルアルコール、ジヒドロア
ビエチルアルコール、テトラヒドロアビエチルア
ルコール、デヒドロアビエチルアルコールなどが
あげられ、商業的にはハーキユレス・インコポレ
ーテツド社製「アビトール（Abitol）」として
入手でき、これは14〜23％のデヒドロアビエチル
アルコール、36〜39％のジヒドロアビエチルアル
コール、38〜50％のテトラヒドロアビエチルアル
コール、３〜８％のエステルおよび７〜12％の炭
化水素からなるものである。使用量は30〜90％、
好ましくは40〜80％であり、該成分は共重合体を
脂肪族系高沸点溶剤に可溶性とする。30％より少
ないと可溶性ならしめるのに不充分であり、90％
より多いとセツトが遅くなりミスチングも顕著と
なり好ましくなる。
本発明に用いるα・β−不飽和カルボン酸とし
ては、たとえばアクリル酸、メタクリル酸、マレ
イン酸、フマル酸、イタコン酸、無水マレイン酸
など、または前記ジカルボン酸と炭素数１〜12個
の１価アルコールとの半エステルがあげられる。
使用量は0.5〜10％、好ましくは１〜６％であ
り、10％を超えるとミスチングがいちじるしくな
り、かつ界面的バランスがくずれ非画線部を形成
しないので好ましくなく、該成分は共重合体に適
度の極性を付与し、顔料分散性を良好にし、イン
キ光沢を向上させる。
本発明にはそのほかに共重合しうるモノマーと
して、たとえばアクリル酸またはメタクリル酸の
メチルエステル、エチルエステル、イソブチルエ
ステル、２−エチルヘキシルエステル、２−ヒド
ロキシエチルエステル、グリシジルエステルな
ど、酢酸ビニル、プロピオン酸ビニル、メチルビ
ニルエーテル、アクリロニトリルなどがあげられ
る。使用量は10％以下である。該成分は生成共重
合体の脂肪族系高沸点溶剤への溶解性を損なわな
い範囲で共重合体へ組込まれるものである。
本発明のバインダーの製造に関しては、重合反
応は公知の方法で行なうことができ、モノマーに
対し、溶媒50〜90％、重合開始剤0.5〜10％を前
記組成のモノマー混合物とともに反応器に仕込
み、反応温度50〜200℃で１〜８時間反応せしめ
る。あるいは反応器にまず溶媒を仕込み、ついで
モノマー混合物および重合開始剤を別々にまたは
混合して分割添加もしくは連続添加して前記反応
条件で重合せしめてもよい。重合に用いる溶媒と
しては、たとえばトルエン、キシレンなどの芳香
族炭化水素類、イソプロピルアルコール、tert−
ブチルアルコール、エチルセロソルブ、ブチルセ
ロソルブなどのアルコール類またはメチルエチル
ケトン、メチルブチルケトンなどのケトン類があ
げられ、重合開始剤としては、たとえばアゾビス
イソブチロニトリルなどの油溶性アゾ化合物また
はベンゾイルパーオキサイド、クメンハイドロパ
ーオキサイド、ジタ−シヤリ−ブチルパーオキサ
イド、過酸化２−エチルヘキサン酸ターシヤリ−
ブチルなどの過酸化物があげられる。
つぎに共重合体の採取については、共重合体溶
液を蒸留に付し、溶媒およびもし存在すれば低分
子量重合体を留去し、共重合体を蒸留残渣として
採取する。
共重合体の軟化点については、環球法（JIS Ｋ
−2531）に基づいて行ない、90℃以上、好適には
110〜150℃であることが望ましい。
トレランスについては、共重合体５ｇを脂肪族
系高沸点溶剤（アニリン点73℃、初留点278℃、
終留点312℃）10ｇに溶解させ、20℃においてさ
らに前記溶剤を添加し、溶液中に白濁が生じた時
点の共重合体に対する溶剤の重量割合で表わし、
２倍以上、好適には５倍以上であることが望まし
い。
重量平均分子量については好適には、1000〜
10000程度であることが望ましい。
つぎにメタクリル酸のロジンアルコールエステ
ルの合成例を述べる。
撹拌機、温度計、還流冷却器を付けた四ツ口コ
ルベンに「アビトール」816部（重量部、以下同
様）およびトルエン1057部を仕込み、80℃に加熱
混合したのち、メタクリル酸241部、フエノチア
ジン5.3部およびパラトルエンスルホン酸21.1部
を仕込んだ。ついでトルエンの還流温度で生成す
る水を除去しながら８時間撹拌し、冷却、中和、
水洗および脱水したのちトルエンを留去した。
かくしてメタクリル酸の「アビトール」エステ
ル87.5％および「アビトール」中の水酸基を含有
しない中性物質12.5％を含有する生成物をえた。
つぎに実施例および応用例をあげて本発明を詳
細に説明する。
実施例 １
撹拌機、温度計、還流冷却器および滴下ロート
を付けた四ツ口コルベンにトルエン174部を仕込
み、加熱してトルエンの還流温度に保持した。つ
いでモノマーとしてメタクリル酸３部、スチレン
25部、メタクリル酸の「アビトール」エステル72
部と重合開始剤として過酸化２−エチルヘキサン
酸tert−ブチル５部の混合物を滴下ロートから沸
騰トルエン中に３時間を要して滴下し、その後３
時間同温度に保持した。その間実験はチツ素雰囲
気下で行なつた。
ついでトルエンを留去し、さらに加熱してコル
ベン内温200℃まで昇温し、最後に80mmHgまで減
圧して低分子量物質を留去したのち、内容物を取
り出した。
えられた共重合体の酸価は19.2、軟化点は117
℃およびトレランスは20倍以上であり、該共重合
体は赤褐色の樹脂であつた。
実施例 ２
モノマーとしてメタクリル酸３部、スチレン45
部およびメタクリル酸の「アビトール」エステル
52部を用いたほかは実施例１と同様の条件で実験
を行なつた結果、酸価19.3、軟化点135℃および
トレランス12倍以上の褐色の樹脂状共重合体をえ
た。
実施例 ３
モノマーとしてアクリル酸３部、スチレン50部
およびアクリル酸の「アビトール」エステル47部
を用いたほかは、実施例１と同様の条件で実験を
行なつた結果、酸価19.0、軟化点137℃およびト
レランス３倍の褐色樹脂状共重合体をえた。
実施例 ４
モノマーとしてメタクリル酸５部、スチレン25
部およびメタクリル酸の「アビトール」エステル
70部を用いたほかは実施例１と同様の条件で実験
を行なつた結果、酸価38.6、軟化点118℃および
トレランス20倍以上の褐色の樹脂状共重合体をえ
た。
実施例 ５
モノマーとしてメタクリル酸３部、スチレン35
部およびメタクリル酸の「アビトール」エステル
62部を用いたほかは実施例１と同様の条件で実験
を行なつた結果、酸価18.7、軟化点135℃および
トレランス20倍以上の褐色の樹脂状共重合体をえ
た。
実施例 ６
モノマーとしてメタクリル酸1.5部、スチレン
35部およびメタクリル酸の「アビトール」エステ
ル63.5部を用いたほかは実施例１と同様の条件で
実験を行なつた結果、酸価9.8、軟化点134.5℃お
よびトレランス20倍以上の黄褐色の樹脂状共重合
体をえた。
比較例 １
モノマーとしてスチレン35部およびメタクリル
酸の「アビトール」エステル65部を用いたほかは
実施例１と同様の条件で実験を行なつた結果、酸
価0.5以下、軟化点128℃およびトレランス20倍以
上の褐色の樹脂状共重合体をえた。
比較例 ２
モノマーとしてメタクリル酸３倍およびメタク
リル酸の「アビトール」エステル97部を用いたほ
かは実施例１と同様の条件で実験を行なつた結
果、酸価19.3、軟化点93℃およびトレランス20倍
以上の褐色の樹脂状共重合体をえた。
比較例 ３
モノマーとしてメタクリル酸３部、スチレン70
部およびメタクリル酸の「アビトール」エステル
27部を用いたほかは実施例１と同様の条件で実験
を行なつた結果、酸価19.0、軟化点162℃および
トレランス２倍未満の黄褐色の樹脂状共重合体を
えた。
比較例 ４
メタクリル酸／メタクリル酸イソブチル／メタ
クリル酸イソボルニル共重合体と称されるロー
ム・アンド・ハース社製「アクリロイドQS−
47」（「マギー535」の60％ワニス）を使用した。
このものは酸価11.7部およびトレランス2.7倍の
淡黄色ワニスであつた。
本発明の種々の実施例のバインダーおよび比較
例についてオフセツト印刷インキへの応用試験を
行なつた。
（インキの調整）
実施例１〜６および比較例１〜２の共重合体40
部を前記脂肪族系高沸点溶剤60部に溶解させてワ
ニスをえた。比較例３の共重合体は溶解性が劣る
のでワニスがえられなかつた。比較例４のワニス
はそのまゝ使用した。
これらのワニスを用いて後述の配合割合で３本
ロールにより練肉して印刷インキをえた。なおゲ
ルワニスは各ワニス98部とアルミソープ２部を
200℃で１時間加熱して調製した。
The present invention relates to a novel binder for printing inks. More specifically, the present invention relates to a printing ink binder with excellent solubility in aliphatic high-boiling point solvents. The basic properties required of printing inks, especially offset printing inks, are as follows. In other words, (1) values that indicate flow characteristics such as viscosity and yield value must be appropriate; (2) water and ink should come into contact with each other to form streaks on a flat surface; (3) Good pigment dispersibility; (4) Fast setting and drying, no blocking of printed matter; (5) Good gloss of printed surface. (6) The printing surface has good abrasion resistance. Traditionally used printing ink varnishes are
It is prepared by dissolving resins such as rosin-modified phenolic resins, alkyd resins, and ester gums in drying oils such as linseed oil, and then adding an aliphatic high-boiling solvent. The setting and drying of printing inks using such varnishes is dominated by penetration of the solvent into the paper or evaporation by heating and subsequent film formation by oxidative polymerization of the drying oil, the latter being the rate-limiting step in particular. Drying oil is used for the purpose of improving the gloss of the printed surface, and if the amount used is reduced, the setting and drying will be faster, but as a natural result, the gloss will decrease.
Furthermore, if the amount of drying oil used is reduced, it becomes difficult to prepare a varnish because the resin has poor solubility in solvents. On the other hand, if the amount of solvent is reduced, the gloss will be better, but the setting and drying will be extremely slow. Therefore, the current situation is to use a drying oil and a solvent in combination, and to change their ratios as appropriate depending on the purpose. Printing inks containing drying oil have another problem. In other words, if ink adhering to the roll of a printing press is left as it is, it will harden through oxidative polymerization of the drying oil and form an insoluble film, so it is necessary to wipe off the ink on the roll each time printing is interrupted. There must be. In order to solve these problems, methods have been proposed such as adding polycyclopentadiene to printing ink containing drying oil and replacing part of the drying oil with a specific phosphoric acid ester, but none of these methods work. This is a solution for ink formulation. JP-A No. 53-98385 discloses that a copolymer of isobutyl methacrylate, isobornyl methacrylate, and methacrylic acid is soluble in an aliphatic high-boiling solvent, and a printing ink varnish containing these as main components and containing no drying oil. However, the gloss of printed paper is still insufficient. However, as a result of intensive research to overcome the above-mentioned drawbacks, the inventors of the present invention have discovered, for example, "Maggie".
535 (manufactured by Magee Corporation, USA) and "Nisseki No. 5 Solvent" (manufactured by Nippon Oil Co., Ltd.), it can be dissolved in aliphatic high boiling point solvents, and can be used in printing inks, especially offset printing inks, even without drying oil. A compatible binder was found and the present invention was completed. That is, the printing ink binder of the present invention is
10-60% by weight of vinyl aromatic hydrocarbons, 30-90% by weight of esters of rosin alcohol and acrylic acid or methacrylic acid, 0.5-10% by weight of α and β
This invention relates to a binder for printing ink containing as an active ingredient a resinous copolymer obtained by copolymerizing unsaturated carvone and 0 to 10% by weight of other copolymerizable monomers. Examples of vinyl aromatic hydrocarbons used in the present invention include styrene, α-methylstyrene, vinyltoluene, vinylxylene, etc.
Among these, styrene is particularly preferred.
The amount used is 10 to 60% (weight%,
The same applies below), and preferably 20 to 50%.
When the copolymer is used as an ink binder, this component provides good wetting to pigments, improves pigment dispersibility, and ultimately improves the gloss of the printed surface.
The larger the amount of this component, the faster the ink will set, but if it is too large, the solubility in high-boiling solvents will be poor, which is not preferable. On the other hand, if the amount is too small, the setting of the ink becomes slow, which is not preferable. Examples of the rosin alcohol used in the present invention include abiethyl alcohol, dihydroabiethyl alcohol, tetrahydroabiethyl alcohol, and dehydroabiethyl alcohol. Commercially available products include "Abitol" manufactured by Hercules Inc. '', which contains 14-23% dehydroabiethyl alcohol, 36-39% dihydroabiethyl alcohol, 38-50% tetrahydroabiethyl alcohol, 3-8% ester and 7-12% char. It consists of hydrogen. Usage amount is 30-90%,
It is preferably 40 to 80%, and this component makes the copolymer soluble in aliphatic high-boiling solvents. Less than 30% is insufficient to make it soluble, and 90%
If the number is larger, setting becomes slower and misting becomes more noticeable, which is preferable. Examples of the α/β-unsaturated carboxylic acid used in the present invention include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, or the above-mentioned dicarboxylic acid and a monohydric acid having 1 to 12 carbon atoms. Examples include half esters with alcohol.
The amount used is 0.5 to 10%, preferably 1 to 6%; if it exceeds 10%, misting becomes noticeable and the interfacial balance is disrupted, resulting in no non-printing area, which is undesirable. It imparts appropriate polarity to the ink, improves pigment dispersibility, and improves ink gloss. In addition, the present invention includes copolymerizable monomers such as methyl ester, ethyl ester, isobutyl ester, 2-ethylhexyl ester, 2-hydroxyethyl ester, glycidyl ester of acrylic acid or methacrylic acid, vinyl acetate, vinyl propionate, etc. , methyl vinyl ether, acrylonitrile, etc. The amount used is less than 10%. This component is incorporated into the copolymer to the extent that it does not impair the solubility of the resulting copolymer in an aliphatic high-boiling solvent. Regarding the production of the binder of the present invention, the polymerization reaction can be carried out by a known method, in which 50 to 90% of a solvent and 0.5 to 10% of a polymerization initiator are charged to a reactor together with a monomer mixture having the above composition, based on the monomers. The reaction is carried out at a reaction temperature of 50 to 200°C for 1 to 8 hours. Alternatively, the reactor may be first charged with a solvent, and then the monomer mixture and the polymerization initiator may be added separately or in a mixed manner in portions or continuously to be polymerized under the above reaction conditions. Examples of solvents used in polymerization include aromatic hydrocarbons such as toluene and xylene, isopropyl alcohol, and tert-
Examples include alcohols such as butyl alcohol, ethyl cellosolve, and butyl cellosolve, and ketones such as methyl ethyl ketone and methyl butyl ketone. Examples of polymerization initiators include oil-soluble azo compounds such as azobisisobutyronitrile, benzoyl peroxide, and cumene. Hydroperoxide, di-tert-butyl peroxide, tertiary-2-ethylhexanoate peroxide
Examples include peroxides such as butyl. Next, for collection of the copolymer, the copolymer solution is subjected to distillation to remove the solvent and the low molecular weight polymer, if present, and the copolymer is collected as a distillation residue. Regarding the softening point of copolymers, the ring and ball method (JIS K
−2531), preferably at 90°C or above.
The temperature is preferably 110-150°C. For tolerance, 5g of the copolymer was mixed with an aliphatic high boiling point solvent (aniline point: 73°C, initial boiling point: 278°C,
Dissolved in 10g of copolymer (final boiling point 312°C), further added the above solvent at 20°C, and expressed as the weight ratio of the solvent to the copolymer at the time when cloudiness occurred in the solution,
It is desirable that it is 2 times or more, preferably 5 times or more. The weight average molecular weight is preferably from 1000 to
It is desirable that it be around 10,000. Next, an example of synthesis of rosin alcohol ester of methacrylic acid will be described. In a four-necked Kolben equipped with a stirrer, a thermometer, and a reflux condenser, 816 parts of "Avitol" (parts by weight, the same applies hereinafter) and 1057 parts of toluene were charged, and after heating and mixing at 80°C, 241 parts of methacrylic acid and phenothiazine were added. 5.3 parts and 21.1 parts of para-toluenesulfonic acid were charged. Next, the mixture was stirred for 8 hours while removing water generated at the reflux temperature of toluene, cooled, neutralized,
After washing with water and dehydration, toluene was distilled off. A product was thus obtained containing 87.5% of ``Avitol'' ester of methacrylic acid and 12.5% of neutral substances containing no hydroxyl groups in ``Avitol''. Next, the present invention will be explained in detail by giving examples and application examples. Example 1 174 parts of toluene was charged into a four-necked colben equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, and the mixture was heated and maintained at the reflux temperature of toluene. Then, 3 parts of methacrylic acid and styrene were added as monomers.
25 parts, “Abitol” ester of methacrylic acid 72
A mixture of 5 parts of tert-butyl 2-ethylhexanoate peroxide as a polymerization initiator was added dropwise from a dropping funnel into boiling toluene over 3 hours, and then
The temperature was maintained at the same time. During that time, experiments were conducted under a nitrogen atmosphere. Then, toluene was distilled off, and the mixture was further heated to raise the internal temperature of the colben to 200°C.Finally, the pressure was reduced to 80 mmHg to distill off low molecular weight substances, and then the contents were taken out. The acid value of the obtained copolymer was 19.2 and the softening point was 117.
C and tolerance were 20 times or more, and the copolymer was a reddish brown resin. Example 2 3 parts of methacrylic acid and 45 parts of styrene as monomers
"Abitol" ester of methacrylic acid and methacrylic acid
As a result of conducting an experiment under the same conditions as in Example 1 except that 52 parts of the copolymer was used, a brown resinous copolymer having an acid value of 19.3, a softening point of 135° C., and a tolerance of 12 times or more was obtained. Example 3 An experiment was conducted under the same conditions as in Example 1, except that 3 parts of acrylic acid, 50 parts of styrene, and 47 parts of acrylic acid "Avitol" ester were used as monomers. As a result, the acid value was 19.0, the softening point was A brown resinous copolymer with a temperature of 137°C and a tolerance of 3 times was obtained. Example 4 5 parts of methacrylic acid and 25 parts of styrene as monomers
"Abitol" ester of methacrylic acid and methacrylic acid
As a result of conducting an experiment under the same conditions as in Example 1 except that 70 parts of the copolymer was used, a brown resinous copolymer having an acid value of 38.6, a softening point of 118° C., and a tolerance of 20 times or more was obtained. Example 5 3 parts of methacrylic acid and 35 parts of styrene as monomers
"Abitol" ester of methacrylic acid and methacrylic acid
As a result of conducting an experiment under the same conditions as in Example 1 except that 62 parts were used, a brown resinous copolymer having an acid value of 18.7, a softening point of 135° C., and a tolerance of 20 times or more was obtained. Example 6 1.5 parts of methacrylic acid, styrene as monomers
An experiment was conducted under the same conditions as in Example 1 except that 35 parts and 63.5 parts of "Abitol" ester of methacrylic acid were used. As a result, a yellowish brown resin with an acid value of 9.8, a softening point of 134.5°C, and a tolerance of 20 times more was obtained. A copolymer was obtained. Comparative Example 1 An experiment was conducted under the same conditions as in Example 1 except that 35 parts of styrene and 65 parts of methacrylic acid "Abitol" ester were used as monomers. As a result, the acid value was 0.5 or less, the softening point was 128°C, and the tolerance was 20. More than twice as much brown resinous copolymer was obtained. Comparative Example 2 An experiment was conducted under the same conditions as in Example 1, except that 3 times as much methacrylic acid and 97 parts of "Abitol" ester of methacrylic acid were used as monomers. As a result, the acid value was 19.3, the softening point was 93°C, and the tolerance was 20. More than twice as much brown resinous copolymer was obtained. Comparative example 3 3 parts of methacrylic acid and 70 parts of styrene as monomers
"Abitol" ester of methacrylic acid and methacrylic acid
An experiment was conducted under the same conditions as in Example 1 except that 27 parts was used, and as a result, a yellowish brown resinous copolymer having an acid value of 19.0, a softening point of 162° C., and a tolerance of less than twice was obtained. Comparative Example 4 “Acryloid QS-
47" (60% varnish of "Maggie 535") was used.
This was a pale yellow varnish with an acid value of 11.7 parts and a tolerance of 2.7 times. Various binders of the present invention and comparative examples were tested for application to offset printing inks. (Adjustment of ink) Copolymers 40 of Examples 1 to 6 and Comparative Examples 1 to 2
A varnish was obtained by dissolving one part in 60 parts of the aliphatic high-boiling solvent. Since the copolymer of Comparative Example 3 had poor solubility, a varnish could not be obtained. The varnish of Comparative Example 4 was used as is. Using these varnishes, printing inks were obtained by kneading with three rolls at the mixing ratios described below. For gel varnish, use 98 parts of each varnish and 2 parts of aluminum soap.
It was prepared by heating at 200°C for 1 hour.
【表】
※：インキのフロー値およびタツク値を
それぞれ17.5±0.5および12.5±0.5
に調製した。
（性能試験および結果）
光沢：インキ0.4c.c.をR.I.テスター（(株)明製作所
製）にてアート紙に展色したのち、20℃、65％
RHにて24時間調湿した。目視によりつぎの基
準で判定した。
◎：優、〇：良、△：可、×：不可
セツト時間：インキ0.4c.c.を前記R.I.テスターに
てアート紙に展色したのち展色物を時間ごとに
分割し、R.I.テスターローラーを用いて展色物
から別のアート紙上へのインキの付着度を観察
し、インキが付着しなくなるまでの時間（分）
を測定した。
ミスチング：インキ４c.c.をインコメーターにチヤ
ージし、400rpmで１分間、さらに1200rpmに
て３分間回転し、ロール直下に置いた白色紙上
へのインキの飛散度合を観察した。
試験結果を第１表に示す。[Table] *: Ink flow value and tack value are 17.5±0.5 and 12.5±0.5, respectively.
It was prepared as follows.
(Performance test and results) Gloss: After applying 0.4 cc of ink on art paper using an RI tester (manufactured by Mei Seisakusho Co., Ltd.), at 20℃, 65%
Humidity was controlled at RH for 24 hours. Judgment was made by visual inspection according to the following criteria. ◎: Excellent, 〇: Good, △: Fair, ×: Not possible Setting time: After applying 0.4cc of ink on art paper using the RI tester, divide the applied color by time and use the RI tester roller. Observe the degree of ink adhesion from the exhibited color to another art paper, and measure the time (minutes) until the ink stops adhering.
was measured. Misting: Charge 4 c.c. of ink into an incometer, rotate at 400 rpm for 1 minute, and then at 1200 rpm for 3 minutes, and observe the degree of ink scattering onto white paper placed directly below the roll. The test results are shown in Table 1.
【表】【table】
Claims (1)
90重量％のロジンアルコールとアクリル酸または
メタクリル酸とのエステル、0.5〜10重量％の
α・β−不飽和カルボン酸および０〜10重量％の
共重合しうる他の単量体を共重合せしめてえられ
る樹脂状共重合体を有効成分とする印刷インキ用
バインダー。 ２ 20〜50重量％のビニル芳香族炭化水素、40〜
80重量％のロジンアルコールとアクリル酸または
メタクリル酸とのエステル、１〜６重量％のα・
β−不飽和カルボン酸および０〜10重量％の共重
合しうる他の単量体を共重合させてなる特許請求
の範囲第１項記載のバインダー。 ３ ロジンアルコールがデヒドロアビエチルアル
コール、ジヒドロアビエチルアルコールおよびテ
トラヒドロアビエチルアルコールの混合物である
特許請求の範囲第１項または第２項記載のバイン
ダー。[Claims] 1 10 to 60% by weight of vinyl aromatic hydrocarbons, 30 to 60% by weight
Copolymerized with 90% by weight of ester of rosin alcohol and acrylic acid or methacrylic acid, 0.5 to 10% by weight of α/β-unsaturated carboxylic acid, and 0 to 10% by weight of other copolymerizable monomers. A printing ink binder containing a resinous copolymer as an active ingredient. 2 20-50% by weight vinyl aromatic hydrocarbons, 40-50% by weight
80% by weight ester of rosin alcohol and acrylic acid or methacrylic acid, 1-6% by weight α・
The binder according to claim 1, which is obtained by copolymerizing a β-unsaturated carboxylic acid and 0 to 10% by weight of other copolymerizable monomers. 3. The binder according to claim 1 or 2, wherein the rosin alcohol is a mixture of dehydroabiethyl alcohol, dihydroabiethyl alcohol, and tetrahydroabiethyl alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8823780A JPS5714662A (en) | 1980-06-27 | 1980-06-27 | Binder for printing ink |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8823780A JPS5714662A (en) | 1980-06-27 | 1980-06-27 | Binder for printing ink |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5714662A JPS5714662A (en) | 1982-01-25 |
| JPS6228830B2 true JPS6228830B2 (en) | 1987-06-23 |
Family
ID=13937247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8823780A Granted JPS5714662A (en) | 1980-06-27 | 1980-06-27 | Binder for printing ink |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5714662A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02102424U (en) * | 1989-01-27 | 1990-08-15 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1274526A (en) * | 1985-03-14 | 1990-09-25 | Thomas Frier Steckel | High molecular weight nitrogen-containing condensates and fuels and lubricants containing same |
| US4971881A (en) * | 1989-01-05 | 1990-11-20 | Monsanto Company | Toner composition comprising rosin modified styrene acrylic resin |
| US8952191B2 (en) * | 2012-11-19 | 2015-02-10 | Xerox Corporation | Ester resin compositions |
-
1980
- 1980-06-27 JP JP8823780A patent/JPS5714662A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02102424U (en) * | 1989-01-27 | 1990-08-15 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5714662A (en) | 1982-01-25 |
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