JP3835950B2 - Hydrocarbon resin - Google Patents
Hydrocarbon resin Download PDFInfo
- Publication number
- JP3835950B2 JP3835950B2 JP18985899A JP18985899A JP3835950B2 JP 3835950 B2 JP3835950 B2 JP 3835950B2 JP 18985899 A JP18985899 A JP 18985899A JP 18985899 A JP18985899 A JP 18985899A JP 3835950 B2 JP3835950 B2 JP 3835950B2
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- hydrocarbon resin
- catalyst
- polymerization
- general formula
- 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 - Lifetime
Links
- 239000013032 Hydrocarbon resin Substances 0.000 title claims description 19
- 229920006270 hydrocarbon resin Polymers 0.000 title claims description 19
- 239000000178 monomer Substances 0.000 claims description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 8
- WUQYBSRMWWRFQH-UHFFFAOYSA-N 2-prop-1-en-2-ylphenol Chemical compound CC(=C)C1=CC=CC=C1O WUQYBSRMWWRFQH-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 description 22
- 239000003054 catalyst Substances 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- OGMSGZZPTQNTIK-UHFFFAOYSA-N 1-methyl-2-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1C OGMSGZZPTQNTIK-UHFFFAOYSA-N 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 12
- 230000001070 adhesive effect Effects 0.000 description 12
- 239000011541 reaction mixture Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 235000011089 carbon dioxide Nutrition 0.000 description 6
- 229920000058 polyacrylate Polymers 0.000 description 6
- 229920001519 homopolymer Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- -1 alicyclic hydrocarbons Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- VENBJVSTINLYEU-UHFFFAOYSA-N phenol;trifluoroborane Chemical compound FB(F)F.OC1=CC=CC=C1 VENBJVSTINLYEU-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000004831 Hot glue Substances 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 2
- 239000003522 acrylic cement Substances 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003613 toluenes Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910015900 BF3 Inorganic materials 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229930007927 cymene Natural products 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920002635 polyurethane 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
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、新規な炭化水素樹脂に関し、特には樹脂中に水酸基を含有する芳香族系炭化水素樹脂に関する。
【０００２】
【従来の技術】
ゴム系感圧接着剤及びエチレン・酢酸ビニル共重合体系及びスチレンブロックコポリマー系ホットメルト接着剤に配合される粘着付与樹脂として、スチレン、ビニルトルエン、α−メチルスチレン等の低分子量重合体や石油樹脂を使用することが知られている。しかし、エチレン・酢酸ビニル共重合体との相溶性不足により高い接着強度が発現しない、また通常の不飽和炭化水素を含有する留分から製造された石油樹脂は、色相、熱安定性が不十分である等の問題を有している。
【０００３】
本発明者らは、これらの問題を改良するものとして、イソプロペニルトルエンと石油精製や石油分解の際に副生する炭素数４〜５の留分から選ばれる任意の留分とを、特定割合で重合して得られる重合体を用いること、及びイソプロペニルトルエンの単独重合体を用いることを先に提案した。（特開昭４９−１１８７２９号公報、特開昭４９−１２８９４５号公報，特公昭５４−３４０３３号公報）
【０００４】
しかし、これらの炭化水素樹脂は分子内に極性基を有しておらず、また分子量分布が広いために、例えばアクリル樹脂等の極性樹脂との相溶性は未だ十分とは言えなかった。さらに、軟化点を維持するためには分子量を高くする必要があり、これも他樹脂との相溶性を阻害する原因となっていた。分子内に水酸基を含有した炭化水素樹脂としてテルペン・フェノール樹脂が知られているが、これらは色相が不良であり、色相改良のために水素添加を行うと、その反応経路が煩雑になるため生産コストが上昇するという問題を抱えている。
【０００５】
【発明が解決しようとする課題】
そこで本発明の課題は、上記問題を解決するために水酸基を分子内に含有した分子量分布が狭く、一定軟化点を維持しつつ分子量が低い、色相に優れた炭化水素樹脂を提案することである。
【０００６】
【課題を解決するための手段】
本発明は、次の炭化水素樹脂に関する。
下記一般式（Ｉ）で表されるスチレン系モノマーと、下記一般式（ＩＩ）で表されるフェノール系モノマーとの共重合体であり、
（Ａ）（Ｉ）／（ＩＩ）のモル比が９９／１〜５０／５０であり、
（Ｂ）重量平均分子量が２００〜３０００であり、
（Ｃ）分子量分布Ｍｗ／Ｍｎが１．５以下である
ことを特徴とする炭化水素樹脂。
【０００７】
【化３】
【化４】
【０００９】
以下に本発明につき、詳細に説明する。
本発明の炭化水素樹脂は、前記一般式（Ｉ）で表されるスチレン系モノマーと、一般式（ＩＩ）で表されるフェノール系モノマーの共重合によって得られる樹脂である。この樹脂は一般式（Ｉ）で表されるスチレン系モノマーと、一般式（ＩＩ）で表されるフェノール系モノマーの組み合わせによる、二元共重合体、三元共重合体、四元共重合体等の多元共重合体のいずれでも良い。
【００１０】
本発明において、前記一般式（Ｉ）で表されるスチレン系モノマーは、１種単独でも２種以上を組み合わせて用いてもよい。
【００１１】
また、フェノール系モノマーを表す前記一般式（ＩＩ）において、Ｒ5、Ｒ6及びＲ7は同一でも異なってもよく、水素原子または炭素数４以下のアルキル基である。この炭素数４以下のアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基等が挙げられる。
この一般式（ＩＩ）で表されるフェノール系モノマーの具体例としては、ビニルフェノール、イソプロペニルフェノール等を挙げることができる。
【００１２】
本発明の炭化水素樹脂における前記スチレン系モノマーとフェノール系モノマーの含有割合は、モル比で９９／１〜５０／５０の割合、好ましくは９７／３〜６０／４０の割合である。
【００１３】
本発明の炭化水素樹脂の製造は、前記スチレン系モノマー、フェノール系モノマーを触媒の存在下に共重合反応させて行うことができる。
重合に用いられる触媒は、一般にフリーデルクラフツ触媒として知られるものであり、例えば塩化アルミニウム、臭化アルミニウム、ジクロルモノエチルアルミニウム、四塩化チタン、四塩化スズ、３フッ化ホウ素の各種錯体等を挙げることができる。
【００１４】
触媒の使用量はスチレン系モノマーとフェノール系モノマーの合計量に対して、０．０１〜５．０重量％の範囲にあることが好ましく、さらに０．０５〜３．０重量％の範囲にあることが好ましい。
また、重合反応の際に、反応熱の除去や反応混合物の高粘度化の抑制等のために、芳香族炭化水素、脂肪族炭化水素及び脂環族炭化水素から選ばれた少なくとも１種の炭化水素溶媒中で重合反応を行うことが好ましい。好ましい炭化水素溶媒として、トルエン、キシレン、エチルベンゼン、メシチレン、クメン、シメン等の芳香族炭化水素、あるいはこれらの混合物、またはこれらとペンタン、ヘキサン、ヘプタン、オクタン等の脂肪族炭化水素及び／またはシクロペンタン、シクロヘキサン、メチルシクロヘキサン等の脂環式炭化水素との混合物を挙げることができる。また、重合の際には、反応混合物中のモノマーの初期濃度が１０〜８０重量％の範囲になるように、炭化水素溶媒の量を調整することが好ましい。
【００１５】
重合温度は使用するモノマーならびに触媒の種類及びその量によって異なるが、通常、−３０℃〜５０℃の範囲で行うことが好ましい。
また、重合時間は、一般には０．５〜５時間程度であり、通常、１〜２時間で重合はほとんど完結する。
重合様式としては、回分式または連続式のいずれを採用することもできる。さらに、多段重合も行うことができる。
【００１６】
重合終了後に洗浄により触媒残さを除去する。洗浄液は通常、水酸化カリウム、水酸化ナトリウム等を溶解したアルカリ水溶液あるいは、メタノール等のアルコールを用いることが好ましく、特にはメタノールによる洗浄脱灰が好ましい。洗浄終了後に未反応モノマー、重合溶媒等を減圧留去して、本発明の炭化水素樹脂を得る。
【００１７】
本発明の炭化水素樹脂の重量平均分子量は２００〜３０００であり、さらに好ましくは、３００〜２０００の範囲である。また、重量平均分子量／数平均分子量で表される分子量分布Ｍｗ／Ｍｎは１．５以下の範囲である。
本発明の炭化水素樹脂の軟化点は５０〜１５０℃の範囲にあることが好ましい。
【００１８】
本発明の炭化水素樹脂には、必要に応じて、さらに本発明の目的を損なわない範囲において、各種の配合剤、例えば耐候安定剤、酸化防止剤等を配合することができる。
【００１９】
本発明の炭化水素樹脂は、ホットメルト接着剤及び感圧接着剤用粘着付与剤、印刷インキ、塗料用接着剤、紙処理剤、熱転写インクリボンバインダー及びトナー等の配合物としても使用することができる。
【００２０】
以下に本発明の実施例を示し、本発明をより具体的に説明するが、本発明はこれらの実施例により何ら制限されるものではない。
【００２１】
以下の実施例において樹脂の物性は以下の方法により測定した。
【００２２】
＜アクリル重合体の調製＞
（参考例１：ブチル系アクリル重合体）
攪拌装置、冷却管、滴下ロート及び窒素導入管を備えた反応装置に酢酸エチル１００ｇを仕込み、８０℃まで昇温した。次いで、予めアクリル酸ブチル９７ｇ、アクリル酸３ｇ及び過酸化ベンゾイル０．２ｇからなる混合液を仕込んだ滴下ロートより、窒素気流下に３時間かけて滴下し、さらに温度を保ったまま１時間加熱攪拌し、反応を完結させた。得られた重合体は固形分濃度５０％であった。
【００２４】
（参考例２：２−エチルヘキシル系アクリル重合体）
一方社油脂工業製 バインゾールＲ−５０（固形分濃度４４％）を使用した。
【００２５】
実施例１
軟化点９６℃のＩＰＴ／ＩＰＰ共重合体の重合
撹拌機、温度計、及びコンデンサー付きベント管を取り付けた１Ｌの４ツ口フラスコに、イソプロペニルトルエン(ＩＰＴ）１６０ｇ、イソプロペニルフェノール（ＩＰＰ）４０ｇ及び脱水精製したトルエン３００ｇを仕込み室温で良く撹拌する。均一に分散した混合液を、ドライアイスで冷却したアルコール浴を使用することによって２０℃まで冷却する。一方、触媒供給用の２５ｍＬ滴下ロートに、窒素雰囲気下でボロントリフロライドフェノラート錯体（フェノール１．７倍当量）０．２４ｇと、脱水精製したトルエンを触媒の１０倍量入れ、該滴下ロートを１Ｌ４ツ口フラスコに取り付ける。その後、触媒を徐々に反応器へ供給し反応を開始する。反応混合物の温度はドライアイスで冷却したアルコール浴を使用することによって２０℃に保持する。
【００２６】
１０分間で触媒の供給を完了させ、触媒供給開始３０分後に反応混合物の温度を５℃まで低下させそのまま２時間後反応を行う。重合終了後、反応混合物にメタノールを添加し重合反応を停止させた。得られた反応混合物を多量の水で５回洗浄した後エバポレーターで溶媒及び未反応モノマーを減圧留去してイソプロペニルトルエン・イソプロペニルフェノール共重合体を得た。この時の重合条件（モノマー供給比，触媒量，樹脂組成，収率）を表１に示し、又、得られたイソプロペニルトルエン・イソプロペニルフェノール共重合体の樹脂物性（軟化点，色相，溶融粘度，分子量，分子量分布）を測定した。結果を表２に示した。
【００２７】
比較例１
撹拌機、温度計、及びコンデンサー付きベント管を取り付けた１Ｌの４ツ口フラスコに、イソプロペニルトルエン２００ｇ、及び、脱水精製したトルエン２００ｇを仕込み良く撹拌する。均一に分散した混合液を、ドライアイスで冷却したアルコール浴を使用することによって５℃迄冷却する。一方、触媒供給用の２５ｍＬ滴下ロートに、窒素雰囲気下でボロントリフロライドフェノラート錯体（フェノール１．７倍当量）０．４ｇと、脱水精製したトルエンを触媒の１０倍量入れ、該滴下ロートを１Ｌ４ツ口フラスコに取り付ける。その後、触媒を徐々に反応器へ供給し反応を開始する。反応混合物の温度はドライアイスで冷却したアルコール浴を使用することによって５℃に保持する。１０分間で触媒の供給を完了させ、温度を５℃に保ったまま２時間後反応を行う。重合終了後、反応混合物に１ＮのＮａＯＨ水溶液を添加し重合反応を停止させた。得られた反応混合物を多量の水で５回洗浄した後エバポレーターで溶媒及び未反応モノマーを減圧留去してイソプロペニルトルエンの単独重合体を得た。この時の重合条件（モノマー供給比，触媒量，樹脂組成，収率）を表１に示し、又、得られたイソプロペニルトルエン単独重合体の樹脂物性（色相，軟化点，分子量，分子量分布，溶融粘度）を測定した。結果を表２に示した。
【００２８】
比較例２
撹拌機、温度計、及びコンデンサー付きベント管を取り付けた１Ｌの４ツ口フラスコに、イソプロペニルトルエン２００ｇ、及び、脱水精製したトルエン２００ｇを仕込み良く撹拌する。均一に分散した混合液を、ドライアイスで冷却したアルコール浴を使用することによって５℃迄冷却する。一方、触媒供給用の２５ｍＬ滴下ロートに、窒素雰囲気下でボロントリフロライドフェノラート錯体（フェノール１．６倍当量）０．６ｇと、脱水精製したトルエンを触媒の１０倍量入れ、該滴下ロートを１Ｌ４ツ口フラスコに取り付ける。その後、触媒を徐々に反応器へ供給し反応を開始する。反応混合物の温度はドライアイスで冷却したアルコール浴を使用することによって５℃に保持する。１０分間で触媒の供給を完了させ、温度を５℃に保ったまま２時間後反応を行う。重合終了後、反応混合物に１ＮのＮａＯＨ水溶液を添加し重合反応を停止させた。得られた反応混合物を多量の水で５回洗浄した後エバポレーターで溶媒及び未反応モノマーを減圧留去してイソプロペニルトルエンの単独重合体を得た。この時の重合条件（モノマー供給比，触媒量，樹脂組成，収率）を表１に示し、又、得られたイソプロペニルトルエン単独重合体の樹脂物性（軟化点，色相，溶融粘度，分子量，分子量分布）を測定した。結果を表２に示した。
【００２９】
【表１】
【表２】
＜アクリル接着剤の調製及び接着力評価＞
評価は以下のように行った。
接着剤外観：目視により○〜△〜×の３段階に分類した。
○：透明
△：一部、濁りあり
×：濁りあり
接着強度 ：１８０°剥離試験により行った。
【００３２】
実施例２
参考例１で合成したアクリル系重合体と実施例１で重合した炭化水素樹脂を固形分比で９０／１０の割合で混合し、十分攪拌した後、コロネートＬ（ポリイソシアネート系化合物：日本ポリウレタン社製）を２．７部添加してアクリル系接着剤とした。接着剤の外観は透明であった。
該接着剤を厚さ４０μｍのＰＥＴフィルム上に、乾燥後の膜厚が３０μｍとなるように塗布し、８０℃で５分乾燥し、粘着テープを作成した。この粘着テープをＰＥＴフィルムに５００ｇ圧着下に張り付け試料とし、接着強度を測定した。結果を表３に示した。
【００３３】
実施例３
参考例２で合成したアクリル系重合体を用いる以外は実施例２と同様に接着剤を調製し、接着強度を測定した。結果を表３に示した。
【００３４】
比較例３〜６
参考例１、２で合成したアクリル系重合体と、比較例１、２で重合した炭化水素樹脂を用いる以外は実施例２と同様に接着剤を調製し、接着強度を測定した。結果を表３に示した。
【００３５】
【表３】
BACKGROUND OF THE INVENTION
The present invention relates to a novel hydrocarbon resin, and more particularly to an aromatic hydrocarbon resin containing a hydroxyl group in the resin.
[0002]
[Prior art]
Low molecular weight polymers such as styrene, vinyltoluene, α-methylstyrene, and petroleum resins as tackifier resins blended in rubber pressure sensitive adhesives, ethylene / vinyl acetate copolymer systems, and styrene block copolymer hot melt adhesives Is known to use. However, high adhesive strength is not expressed due to insufficient compatibility with ethylene / vinyl acetate copolymer, and petroleum resins produced from fractions containing ordinary unsaturated hydrocarbons have insufficient hue and thermal stability. It has some problems.
[0003]
In order to improve these problems, the inventors of the present invention specified isopropenyltoluene and an arbitrary fraction selected from fractions having 4 to 5 carbon atoms produced as a by-product during petroleum refining and petroleum decomposition at a specific ratio. It was previously proposed to use a polymer obtained by polymerization and to use a homopolymer of isopropenyltoluene. (Japanese Patent Laid-Open No. 49-118729, Japanese Patent Laid-Open No. 49-128945, Japanese Patent Publication No. 54-34033)
[0004]
However, these hydrocarbon resins do not have a polar group in the molecule and have a wide molecular weight distribution, so that compatibility with a polar resin such as an acrylic resin has not been sufficient. Furthermore, in order to maintain the softening point, it is necessary to increase the molecular weight, which has also caused the compatibility with other resins to be inhibited. Terpene / phenolic resins are known as hydrocarbon resins containing hydroxyl groups in the molecule, but these have poor hues, and if hydrogenation is performed to improve hues, the reaction route becomes complicated, producing There is a problem that the cost increases.
[0005]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to propose a hydrocarbon resin excellent in hue that has a narrow molecular weight distribution containing a hydroxyl group in the molecule, a low molecular weight while maintaining a constant softening point, in order to solve the above problems. .
[0006]
[Means for Solving the Problems]
The present invention relates to the following hydrocarbon resins.
A copolymer of a styrene monomer represented by the following general formula (I) and a phenol monomer represented by the following general formula (II):
(A) The molar ratio of (I) / (II) is 99/1 to 50/50,
(B) The weight average molecular weight is 200 to 3000,
(C) A hydrocarbon resin having a molecular weight distribution Mw / Mn of 1.5 or less.
[0007]
[Chemical 3]
[Formula 4]
[0009]
Hereinafter, the present invention will be described in detail.
The hydrocarbon resin of the present invention is a resin obtained by copolymerization of a styrene monomer represented by the general formula (I) and a phenol monomer represented by the general formula (II). This resin is a binary copolymer, ternary copolymer, or quaternary copolymer comprising a combination of a styrene monomer represented by general formula (I) and a phenol monomer represented by general formula (II). Any of multi-component copolymers such as
[0010]
In the present invention, the styrene monomer represented by the general formula (I) may be used alone or in combination of two or more.
[0011]
Moreover, in the said general formula (II) showing a phenol-type monomer, R < 5 >, R < 6 > and R < 7 > may be same or different and are a hydrogen atom or a C4 or less alkyl group. Examples of the alkyl group having 4 or less carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group.
Specific examples of the phenolic monomer represented by the general formula (II) include vinylphenol and isopropenylphenol.
[0012]
The content ratio of the styrene monomer and the phenol monomer in the hydrocarbon resin of the present invention is a ratio of 99/1 to 50/50, preferably 97/3 to 60/40, in molar ratio.
[0013]
The hydrocarbon resin of the present invention can be produced by copolymerizing the styrene monomer and phenol monomer in the presence of a catalyst.
The catalyst used for the polymerization is generally known as a Friedel-Crafts catalyst, and examples thereof include various complexes of aluminum chloride, aluminum bromide, dichloromonoethylaluminum, titanium tetrachloride, tin tetrachloride, and boron trifluoride. be able to.
[0014]
The amount of the catalyst used is preferably in the range of 0.01 to 5.0% by weight, more preferably in the range of 0.05 to 3.0% by weight, based on the total amount of the styrene monomer and the phenol monomer. It is preferable.
Further, at the time of the polymerization reaction, at least one kind of carbon selected from aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons is used for removing heat of reaction and suppressing increase in viscosity of the reaction mixture. The polymerization reaction is preferably performed in a hydrogen solvent. Preferred hydrocarbon solvents include aromatic hydrocarbons such as toluene, xylene, ethylbenzene, mesitylene, cumene, and cymene, or mixtures thereof, and aliphatic hydrocarbons such as pentane, hexane, heptane, and octane and / or cyclopentane. And mixtures with alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. In the polymerization, the amount of the hydrocarbon solvent is preferably adjusted so that the initial concentration of the monomer in the reaction mixture is in the range of 10 to 80% by weight.
[0015]
The polymerization temperature varies depending on the monomer used and the type and amount of the catalyst, but it is usually preferably in the range of −30 ° C. to 50 ° C.
The polymerization time is generally about 0.5 to 5 hours, and the polymerization is usually almost completed in 1 to 2 hours.
As the polymerization mode, either a batch system or a continuous system can be adopted. Furthermore, multistage polymerization can also be performed.
[0016]
After the polymerization is completed, the catalyst residue is removed by washing. In general, it is preferable to use an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, or the like is dissolved, or an alcohol such as methanol, and cleaning deashing with methanol is particularly preferable. After completion of washing, unreacted monomers, polymerization solvent and the like are distilled off under reduced pressure to obtain the hydrocarbon resin of the present invention.
[0017]
The weight average molecular weight of the hydrocarbon resin of the present invention is 200 to 3000, and more preferably 300 to 2000. Further, the molecular weight distribution Mw / Mn represented by weight average molecular weight / number average molecular weight is in the range of 1.5 or less.
The softening point of the hydrocarbon resin of the present invention is preferably in the range of 50 to 150 ° C.
[0018]
In the hydrocarbon resin of the present invention, various compounding agents, for example, a weather resistance stabilizer, an antioxidant, and the like can be blended as necessary within a range not impairing the object of the present invention.
[0019]
The hydrocarbon resin of the present invention may also be used as a blend of hot melt adhesives and pressure sensitive adhesive tackifiers, printing inks, paint adhesives, paper treatment agents, thermal transfer ink ribbon binders, toners, and the like. it can.
[0020]
EXAMPLES Examples of the present invention will be shown below, and the present invention will be described more specifically. However, the present invention is not limited to these examples.
[0021]
In the following examples, the physical properties of the resin were measured by the following methods.
[0022]
<Preparation of acrylic polymer>
(Reference Example 1: Butyl acrylic polymer)
A reactor equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introducing tube was charged with 100 g of ethyl acetate and heated to 80 ° C. Next, from a dropping funnel previously charged with a mixed solution composed of 97 g of butyl acrylate, 3 g of acrylic acid and 0.2 g of benzoyl peroxide, the mixture was dropped over 3 hours under a nitrogen stream, and further heated and stirred for 1 hour while maintaining the temperature. To complete the reaction. The obtained polymer had a solid content concentration of 50%.
[0024]
(Reference Example 2: 2-ethylhexyl acrylic polymer)
On the other hand, Vinesol R-50 (solid content concentration: 44%) manufactured by Yushi Kogyo Co., Ltd. was used.
[0025]
Example 1
To a 1 L 4-necked flask equipped with a polymerization stirrer, a thermometer, and a vent tube with a condenser having a softening point of 96 ° C., 160 g of isopropenyl toluene (IPT) and 40 g of isopropenyl phenol (IPP) And 300 g of dehydrated and purified toluene is charged and stirred well at room temperature. The uniformly dispersed mixture is cooled to 20 ° C. by using an alcohol bath cooled with dry ice. On the other hand, in a 25 mL dropping funnel for supplying catalyst, 0.24 g of boron trifluoride phenolate complex (1.7 times equivalent of phenol) and 10 times the amount of dehydrated toluene were added under a nitrogen atmosphere, and the dropping funnel was added. Is attached to a 1 L 4-neck flask. Thereafter, the catalyst is gradually supplied to the reactor to start the reaction. The temperature of the reaction mixture is kept at 20 ° C. by using an alcohol bath cooled with dry ice.
[0026]
The supply of the catalyst is completed in 10 minutes, and 30 minutes after the start of the catalyst supply, the temperature of the reaction mixture is lowered to 5 ° C., and the reaction is carried out after 2 hours. After completion of the polymerization, methanol was added to the reaction mixture to stop the polymerization reaction. The obtained reaction mixture was washed 5 times with a large amount of water, and then the solvent and unreacted monomers were distilled off under reduced pressure using an evaporator to obtain an isopropenyltoluene / isopropenylphenol copolymer. The polymerization conditions (monomer supply ratio, catalyst amount, resin composition, yield) at this time are shown in Table 1, and the resin physical properties (softening point, hue, melting) of the obtained isopropenyltoluene / isopropenylphenol copolymer Viscosity, molecular weight, molecular weight distribution) were measured. The results are shown in Table 2.
[0027]
Comparative Example 1
Into a 1 L four-necked flask equipped with a stirrer, a thermometer, and a vent pipe with a condenser, 200 g of isopropenyl toluene and 200 g of dehydrated and purified toluene are charged and stirred well. The uniformly dispersed mixture is cooled to 5 ° C. by using an alcohol bath cooled with dry ice. On the other hand, in a 25 mL dropping funnel for supplying catalyst, 0.4 g of boron trifluoride phenolate complex (1.7 equivalents of phenol) and dehydrated and purified toluene in a nitrogen atmosphere were added 10 times the amount of the catalyst. Is attached to a 1 L 4-neck flask. Thereafter, the catalyst is gradually supplied to the reactor to start the reaction. The temperature of the reaction mixture is maintained at 5 ° C. by using an alcohol bath cooled with dry ice. The supply of the catalyst is completed in 10 minutes, and the reaction is carried out after 2 hours while keeping the temperature at 5 ° C. After completion of the polymerization, 1N NaOH aqueous solution was added to the reaction mixture to stop the polymerization reaction. The obtained reaction mixture was washed 5 times with a large amount of water, and then the solvent and unreacted monomers were distilled off under reduced pressure using an evaporator to obtain a homopolymer of isopropenyltoluene. The polymerization conditions (monomer supply ratio, catalyst amount, resin composition, yield) at this time are shown in Table 1, and the resin physical properties (hue, softening point, molecular weight, molecular weight distribution, isopropenyltoluene homopolymer) Melt viscosity) was measured. The results are shown in Table 2.
[0028]
Comparative Example 2
Into a 1 L four-necked flask equipped with a stirrer, a thermometer, and a vent pipe with a condenser, 200 g of isopropenyl toluene and 200 g of dehydrated and purified toluene are charged and stirred well. The uniformly dispersed mixture is cooled to 5 ° C. by using an alcohol bath cooled with dry ice. On the other hand, in a 25 mL dropping funnel for supplying catalyst, 0.6 g of boron trifluoride phenolate complex (phenol 1.6 times equivalent) and dehydrated toluene in a nitrogen atmosphere were added 10 times the amount of the catalyst. Is attached to a 1 L 4-neck flask. Thereafter, the catalyst is gradually supplied to the reactor to start the reaction. The temperature of the reaction mixture is maintained at 5 ° C. by using an alcohol bath cooled with dry ice. The supply of the catalyst is completed in 10 minutes, and the reaction is carried out after 2 hours while keeping the temperature at 5 ° C. After completion of the polymerization, 1N NaOH aqueous solution was added to the reaction mixture to stop the polymerization reaction. The obtained reaction mixture was washed 5 times with a large amount of water, and then the solvent and unreacted monomers were distilled off under reduced pressure using an evaporator to obtain a homopolymer of isopropenyltoluene. The polymerization conditions (monomer supply ratio, catalyst amount, resin composition, yield) at this time are shown in Table 1, and the resin properties (softening point, hue, melt viscosity, molecular weight, isopropenyltoluene homopolymer) Molecular weight distribution) was measured. The results are shown in Table 2.
[0029]
[Table 1]
[Table 2]
<Preparation of acrylic adhesive and evaluation of adhesive strength>
Evaluation was performed as follows.
Adhesive appearance: Visually classified into three stages of ○ to Δ to ×.
○: Transparent Δ: Partly turbid ×: Turbidity Adhesive strength: Measured by a 180 ° peel test.
[0032]
Example 2
The acrylic polymer synthesized in Reference Example 1 and the hydrocarbon resin polymerized in Example 1 were mixed at a solid content ratio of 90/10, and after sufficient stirring, Coronate L (polyisocyanate compound: Nippon Polyurethane Co., Ltd.) 2.7 parts) was added to make an acrylic adhesive. The appearance of the adhesive was transparent.
The adhesive was applied onto a PET film having a thickness of 40 μm so that the film thickness after drying was 30 μm, and dried at 80 ° C. for 5 minutes to prepare an adhesive tape. This adhesive tape was applied to a PET film under a pressure of 500 g as a sample, and the adhesive strength was measured. The results are shown in Table 3.
[0033]
Example 3
An adhesive was prepared in the same manner as in Example 2 except that the acrylic polymer synthesized in Reference Example 2 was used, and the adhesive strength was measured. The results are shown in Table 3.
[0034]
Comparative Examples 3-6
An adhesive was prepared in the same manner as in Example 2 except that the acrylic polymer synthesized in Reference Examples 1 and 2 and the hydrocarbon resin polymerized in Comparative Examples 1 and 2 were used, and the adhesive strength was measured. The results are shown in Table 3.
[0035]
[Table 3]
Claims (2)
（Ａ）（Ｉ）／（ＩＩ）のモル比が９９／１〜５０／５０であり、
（Ｂ）重量平均分子量が２００〜３０００であり、
（Ｃ）分子量分布Ｍｗ／Ｍｎが１．５以下である
ことを特徴とする炭化水素樹脂。
(A) The molar ratio of (I) / (II) is 99/1 to 50/50,
(B) The weight average molecular weight is 200 to 3000,
(C) A hydrocarbon resin having a molecular weight distribution Mw / Mn of 1.5 or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18985899A JP3835950B2 (en) | 1999-07-05 | 1999-07-05 | Hydrocarbon resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18985899A JP3835950B2 (en) | 1999-07-05 | 1999-07-05 | Hydrocarbon resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001019719A JP2001019719A (en) | 2001-01-23 |
| JP3835950B2 true JP3835950B2 (en) | 2006-10-18 |
Family
ID=16248369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18985899A Expired - Lifetime JP3835950B2 (en) | 1999-07-05 | 1999-07-05 | Hydrocarbon resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3835950B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116082981A (en) * | 2022-09-07 | 2023-05-09 | 太仓金煜电子材料有限公司 | Semi-transparent packaging adhesive tape for MiniLED lamp, production process thereof and acrylic ester adhesive |
-
1999
- 1999-07-05 JP JP18985899A patent/JP3835950B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001019719A (en) | 2001-01-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6184308B1 (en) | Thermally polymerized dicyclopentadiene/vinyl aromatic resins | |
| US8829105B2 (en) | Low molecular weight polystyrene resin and methods of making and using the same | |
| EP0023061B1 (en) | Hydrocarbon resins, their preparation and their use in adhesives | |
| WO2000018815A1 (en) | Process for producing hydrogenated c9 petroleum resin and hydrogenated c9 petroleum resin obtained by the process | |
| JP3987587B2 (en) | Method to lighten resin by hydrogen treatment | |
| US11512234B2 (en) | Farnesene-based tackifying resins and adhesive compositions containing the same | |
| EP0240762B1 (en) | Vinyl aromatic/terpene/phenol/terpolymers | |
| US4707526A (en) | Tackifier composition | |
| US4845182A (en) | Adhesive compositions with block copolymer tackifiers | |
| JP3835950B2 (en) | Hydrocarbon resin | |
| JPH06184249A (en) | Hot melt adhesive composition | |
| EP0210706B1 (en) | Resinous copolymer composition based on hydrocarbons and use thereof in adhesives and coatings | |
| JPH01188550A (en) | Polymer composition and use thereof | |
| NL8502134A (en) | HYDROGENATED HYDROCARBON RESIN AND USE THEREOF IN ADHESIVES. | |
| JP2001139631A (en) | Hydrocarbon resin | |
| CN117567684B (en) | Modified petroleum resin and preparation method thereof | |
| JP3513578B2 (en) | Manufacturing method of styrene resin | |
| US4797460A (en) | Tackifier resin composition and process for preparing same | |
| JPH07103187B2 (en) | Method for producing styrene polymer | |
| EP0190868B1 (en) | Hydrocarbon resins | |
| CA1271294A (en) | Vinyl aromatic/terpene/phenol/terpolymers | |
| JP2619868C (en) | ||
| IL34043A (en) | Copolymers and preparational method therefor | |
| JPS6270412A (en) | Manufacture of composition containing alkenyl aromatic monomer butadiene rubber | |
| JPH0121161B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20040528 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20060317 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20060530 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060627 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20060725 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20060725 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 3835950 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100804 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100804 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110804 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120804 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120804 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130804 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130804 Year of fee payment: 7 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |