TW585951B - Offset printing paper - Google Patents
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- TW585951B TW585951B TW90121718A TW90121718A TW585951B TW 585951 B TW585951 B TW 585951B TW 90121718 A TW90121718 A TW 90121718A TW 90121718 A TW90121718 A TW 90121718A TW 585951 B TW585951 B TW 585951B
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五、發明說明() 【發明之詳細說明】 在印刷用紙原紙上,以水溶性高分子、苯乙烯系單體 及陰離子性單體之共聚物,即含笨乙稀系單體20〜8〇重 量%之水溶性共聚物為主體之表面上膠劑、及含稀系單體 及陰離子性單體之共聚物2G〜8G重量%之水溶性共聚物 為主體之表面上膠劑3成分為主體之表面處理劑加以塗 佈,並使其乾燥。 【發明所屬之技術領域】 本案發明係有關於-種適合用於彩色印刷之優良平 版印刷用紙,特別是平版印刷用新聞用紙。 【習知技術】 β近年來’印刷技術已高度進步至平版印刷化、高速 ^里印刷化、自動化等,隨之而來的是對於印刷用紙的要 求,其作業性、印刷適合度等方面也需加以改良。 特別是平版印刷,由於在印刷機中同時使用墨水及 液體,對用紙的負擔與習知凸版印刷相比,明顯地變大, 因此,對於平版印刷用紙來說,具適度吸水抵抗性(亦即 上膠性)是為必要的。 賦予印刷用紙上膠性之方法,有内添上膠及外添上 膠(表面上膠)兩種方法,前者即所謂的濕端内添,於紙浆 中添加内添上膠劑(例如··松香膠料劑、強化松香膠料劑、 中性松香膠料劑、烷基乙烯酮二聚體(AKD)、脂烯基琥珀 酸無水物(ASA)等),為於造紙的同時,使紙的内部含有藥 品之方法;後者為,於造紙後利用壓膠機、或洗口輥塗機 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) --------------裝·1.1 (請先閱讀背面之注意事項再填寫本頁) . 經濟部智慧財產局員工消費合作社印製 585951 A7 B7_ 五、發明說明() 等代表性塗工機,以表面上膠劑(例如:苯乙烯/順丁烯二 酸系共聚物、苯乙烯/丙烯酸系共聚物、烯/順丁烯二酸系 共聚物、尿烷系共聚物等)加以塗布之方法。 但,.内添上膠於(1)藥品必須添加於低濃度紙漿内、 (2)藥品於紙座上的附著量不一定(藥品附著量低)、(3)白 水污染等成本、品質、操作性等方面皆有諸多問題,相反 的,由於外添上膠沒有内添上膠之諸多問題,是為可行之 方法。 另一方面,作為印刷用紙之表面強度對策,以澱粉、 化工澱粉、聚乙烯醇(PVA)、或聚丙烯醯(PAM)等水溶性高 分子進行表面塗佈為一般方法,因此,在外添上膠中,將 表面上膠劑與該等材料並用為基本。 例如,將含苯乙烯系單體水溶性共聚物為主體之表 面上膠劑(苯乙烯系表面上膠劑)與澱粉並用之處方等,已 廣為普及,可列舉出:特開昭60-185894號公報、特開平 5-247888號公報、特開平11-140791號公報等為例。 又,表面上膠劑之代表例,以含烯系單體(乙烯、丙 烯、異丁烯、異辛烯、辛烯、癸烯等)水溶性聚合物為主 體之表面上膠劑(烯系表面上膠劑),亦廣為人知。 例如,特開昭50-89603號公報中揭示出異辛烯•順 丁烯二酸系之表面上膠劑,特開昭55-67094號公報、特 開昭60-9994號公報中揭示出異辛烯•無水順丁烯二酸系 之表面上膠劑,特開平2-200896號公報、特開平2-269895 號公報、特開平3-8894號公報中揭示出由含α-烯及(曱 -4—- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) -H ϋ -11 n ϋ n 一 ^ I i^i n *1 I . 經濟部智慧財產局員工消費合作社印製 585951 經濟部智慧財產局員工消費合作社印製 A7 Β7 五、發明說明() 基)丙烯酸酯之水溶性共聚物組成之表面上膠劑等。 表面上膠劑,基本上是一種由疏水性基與親水性基 兩者合用之材料,有其發泡性之問題,因此在少量使用下 而具高上膠性能者是為眾所期望。 * ' * . 另一方面,彩色印刷的增加亦為明顯現象,因此用 紙之彩色印刷適性(例如:墨水附著性的改良等)也是必要 的。 特開平11-140791號公報中揭示出,水溶性高分子 與苯乙烯系表面上膠劑並用而使彩色印刷適性提高之方 法。 印刷用紙中,報紙(新聞卷筒紙),一般以機械紙漿 或脫墨紙衆(DIP)為主體之紙,被歸為中、下等級的紙, 而且報紙印刷必須再指定時間帶的指定時間内,確實地印 刷出指定的份數,比一般印刷用紙有更嚴格的品質要求。 即使是報紙,其所謂表面強度對策仍是指以澱粉、 PVA、或PAM加以塗佈之方法,而報紙之塗佈方法,在日 本國内一般多使用能高速塗佈形成被膜轉寫方式之澆口輥 塗機(GRC),又GRC方式之特徵於,例如紙漿技協誌ν〇1· 43, No· 4(1989) ρ36、紙漿技術時代 ν〇1· 36, No. 12(1993) ρ20 有做一簡單之整理。 【發明欲解決之問題】 本案發明以提供一種具適度上膠性(吸水抵抗性), 且適於彩色印刷之優良平版印刷用紙,特別是印刷用報紙 用紙。 本紙張尺度適用中國國家標準(CNS)A4規格(21〇 X 297公釐) (請先閱讀背面之注意事項再填寫本頁)V. Description of the invention () [Detailed description of the invention] On the base paper of printing paper, a copolymer of a water-soluble polymer, a styrene monomer and an anionic monomer, that is, a stupid vinyl monomer containing 20 to 80. The surface sizing agent based on the water-soluble copolymer as the main body, and the copolymer containing dilute monomers and anionic monomers. The surface treating agent is applied and allowed to dry. [Technical field to which the invention belongs] The present invention relates to an excellent lithographic paper suitable for color printing, especially a newsprint paper for lithographic printing. [Knowledge technology] β In recent years, the printing technology has been highly advanced to lithography, high-speed printing, automation, etc., and the requirements for printing paper have followed, and its workability and printing suitability have also Need to be improved. Especially for lithographic printing, due to the simultaneous use of ink and liquid in the printing press, the burden on the paper is significantly larger than that of conventional letterpress printing. Therefore, for lithographic printing paper, it has moderate water absorption resistance (that is, Sizing) is necessary. There are two methods to give printing paper sizing properties: internal sizing and external sizing (surface sizing). The former is the so-called wet-end internal sizing, and an internal sizing agent (such as rosin gum) is added to the pulp. Agent, reinforced rosin size agent, neutral rosin size agent, alkyl ketene dimer (AKD), fatty alkenyl succinic anhydride (ASA), etc.) The method of containing medicines; the latter is to use a laminator or a mouthwash roll coater after papermaking. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) --------- ----- Equipment · 1.1 (Please read the precautions on the back before filling out this page). Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, 585951 A7 B7_ V. Description of invention () and other representative coating machines A method of applying a sizing agent (for example, a styrene / maleic acid copolymer, a styrene / acrylic copolymer, an olefin / maleic copolymer, a urethane copolymer, etc.). However, adding glue to (1) medicines must be added to low-concentration pulp, (2) the amount of medicines attached to the paper base is not necessarily (the quantity of medicines is low), (3) the cost, quality, and operation of white water pollution There are many problems in terms of sex and so on. On the contrary, it is a feasible method because there are many problems of adding glue outside and not adding glue inside. On the other hand, as a measure of the surface strength of printing paper, a general method is to coat the surface with water-soluble polymers such as starch, chemical starch, polyvinyl alcohol (PVA), or polypropylene (PAM). It is basically to use a surface sizing agent in combination with these materials. For example, a surface sizing agent (styrene surface sizing agent) containing a styrene-based monomer water-soluble copolymer as a main body and starch are widely used together, and examples include: JP-A-60- Examples are 185894, JP 5-247888, and JP 11-140791. A typical example of a surface sizing agent is a surface sizing agent (on an olefinic surface) containing a water-soluble polymer containing an olefin-based monomer (ethylene, propylene, isobutylene, isooctene, octene, decene, etc.) as a main body. Glue), is also widely known. For example, Japanese Unexamined Patent Publication No. 50-89603 discloses an isooctene-maleic acid-based surface sizing agent, and Japanese Unexamined Patent Publication No. 55-67094 and Japanese Unexamined Patent Publication No. 60-9994 disclose differences. The surface sizing agent of octene and anhydrous maleic acid is disclosed in Japanese Patent Application Laid-Open No. 2-200896, Japanese Patent Application Laid-Open No. 2-269895, and Japanese Patent Application Laid-Open No. 3-8894. -4—- This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) -H ϋ -11 n ϋ n 一 ^ I i ^ in * 1 I. Printed by the Consumers 'Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 585951 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention () Base surface adhesive composed of water-soluble copolymer of acrylic ester, etc. The surface sizing agent is basically a material composed of both a hydrophobic group and a hydrophilic group, and has a problem of foamability. Therefore, a high sizing performance with a small amount of use is expected. * '*. On the other hand, the increase in color printing is also an obvious phenomenon, so the suitability of color printing on paper (for example, improvement of ink adhesion, etc.) is also necessary. Japanese Patent Application Laid-Open No. 11-140791 discloses a method for improving the suitability of color printing by using a water-soluble polymer in combination with a styrenic surface sizing agent. Among printing papers, newspapers (news roll papers), generally papers with mechanical pulp or deinked paper (DIP) as the main body, are classified as middle and lower grades, and newspapers must be printed at a specified time in a specified time zone. In addition, the specified number of copies are printed reliably, which has stricter quality requirements than general printing paper. Even for newspapers, the so-called surface strength measures still refer to the method of coating with starch, PVA, or PAM, and newspaper coating methods are generally used in Japan. The mouth roll coater (GRC) and the GRC method are characterized by, for example, the Pulp Technical Association ν〇1 · 43, No · 4 (1989) ρ36, the pulp technology era ν〇1 · 36, No. 12 (1993) ρ20 Have a simple finishing. [Problems to be Solved by the Invention] The present invention is to provide an excellent lithographic printing paper with moderate sizing property (water absorption resistance) and suitable for color printing, especially a printing paper. This paper size applies to China National Standard (CNS) A4 (21〇 X 297 mm) (Please read the precautions on the back before filling this page)
585951 A7 B7_ 五、發明說明() 【解決問題之方法】 本案發明者,於印刷用紙原紙(特別是報紙用原紙) 上,以含苯乙烯系表面上膠劑與烯系表面上膠劑兩者之表 面處理劑塗布,使其乾燥,發現藉由表面上膠劑的混合能 發揮相乘效果,即使是低塗佈量,也能得到充分的上膠效 果(吸水抵抗性的附加效果),並得到優良的彩色印刷適 性,解決了本案發明之課題。 【發明之實施型態】 本案發明係有關將下述所示,以成分A、成分B及成 分C為主體之表面處理劑加以塗佈、乾燥形成之平版印刷 用紙。 成分A:水溶性高分子 成分B :苯乙烯系單體及陰離子性單體之共聚物,含苯乙 烯系單體20〜80重量%之水溶性共聚物為主體之表面上 膠劑 成分C:烯系單體與陰離子性單體之共聚物,含烯系單體 20〜80重量%之水溶性共聚物為主體之表面上膠劑 本案發明之課題,係於新聞用紙中較為困難的課題, 以下,針對以上述成分A、成分B及成分C之3成分為主 體之表面處理劑加以塗佈、乾燥而成平版報紙用紙做一說 明。 本案發明表面處理劑中使用成分A之水溶性高分子, 可列舉出澱粉、酵素變性澱粉、熱化學變性澱粉、氧化澱 粉、酯化澱粉、醚化澱粉(羥乙基化澱粉等)、陽離子化澱 -— 6— 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁)585951 A7 B7_ 5. Explanation of the invention () [Solution to the problem] The inventor of this case used printing paper base paper (especially newspaper base paper) with both a styrene-based surface sizing agent and an olefin-based surface sizing agent. The surface treatment agent is applied and dried, and it is found that the mixing effect of the surface sizing agent can exert a synergistic effect. Even at a low coating amount, a sufficient sizing effect (additional effect of water absorption resistance) can be obtained, and The excellent color printability is obtained, and the problem of the invention of the present invention is solved. [Implementation Mode of the Invention] The present invention relates to a lithographic printing paper formed by coating and drying a surface treating agent mainly composed of component A, component B, and component C as shown below. Component A: Water-soluble polymer component B: Copolymer of styrenic monomer and anionic monomer, 20 to 80% by weight of water-soluble copolymer containing styrenic monomer as the main surface sizing agent component C: A copolymer of an olefinic monomer and an anionic monomer, and a water-soluble copolymer containing 20 to 80% by weight of an olefinic monomer as the main surface sizing agent. The subject of the present invention is a difficult subject in newsprint. Hereinafter, a lithographic newspaper paper made by coating and drying a surface treating agent mainly composed of the three components of the above-mentioned component A, component B, and component C will be described. The water-soluble polymer using component A in the surface treating agent of the present invention includes starch, enzyme-modified starch, thermochemically modified starch, oxidized starch, esterified starch, etherified starch (such as hydroxyethylated starch), and cationization. Dian-— 6— This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)
-I5J'111111· 經濟部智慧財產局員工消費合作社印製 585951 A7 ___B7 : ------_ 五、發明說明() 粉等殿粉類,聚乙稀醇、完全鹼化聚乙稀醇、部分驗化聚 乙烯醇、羧基變性聚乙烯醇、硅烷醇聚乙烯醇、陽離子^ 性聚乙烯醇、末端烷基變性聚乙烯醇等聚乙烯醇類,聚丙 烯醯、陽離子性聚丙烯醯、障離子性聚丙烯醯、兩性聚丙 烯醯等聚丙烯醯類,羧基曱基纖維素、羥基乙基纖維素、 曱基纖維素等纖維素類等,以單獨或兩種類以上混和使 用。 本案發明表面處理劑所使用之成分A,對加強表面強 度(即紙粉抑制)這點來說,確實達到其作用,但,另一方 面,成分A亦會形成新聞用紙固有之黏結問題(新聞用紙 於大s印刷時,表面處理劑轉移、蓄積於表面所引發之問 題),考慮到表面強度加強效果與黏結問題間的平衡,本 案發明之成分A,以前述例子中,以使用澱粉類為理想, 其中,又以氧化澱粉、醚化澱粉、酯化澱粉最為理想。 本案發明表面處理劑所使用之成分B為,苯乙烯系 單體及陰離子性單體共聚物,即含苯乙烯系單體20〜80 重量%之水溶性共聚物;作為苯乙烯單體者,例如:苯乙 烯、α-甲基苯乙烯、氯基苯乙烯、氰基苯乙烯;作為陰 離子性單體者,例如:丙烯酸系單體(丙烯酸、甲基丙烯 酸、丁烯酸、異丁烯酸、2—乙基丙烯酸、3—第三—丁基丙 烯酸、丙烯酸曱基、丙烯酸乙基、丙烯酸iso-丁基、丙 烯酸辛基等),順丁烯二酸系單體(順丁烯二酸、甲基順丁 =二酸、苯基順丁烯二酸、氯基順丁烯二酸、反式丁烯二 酸、甲叉丁二酸、己二烯二酸、順丁烯二酸甲基、順丁烯 本紙張尺巧國家標準χ挪公7 )--- (請先閱讀背面之注意事項再填寫本頁) 111111. 經濟部智慧財產局員工消費合作社印製 585951 A7 五、發明說明( 二酸tert-丁基、順丁烯二酸乙基等)。 作為成分B使用之水溶性共聚物,具體來說即為苯 乙烯/丙烯酸共聚物、苯乙烯/(甲基)丙締酸共聚物(其中, ' (甲基)丙烯酸係指「丙烯酸、及/或甲基丙稀酸」)、苯乙 烯/(甲基)丙烯酸/(甲基)丙稀酸酿共聚物、苯乙稀/順丁 烯二酸共聚物、笨乙烯/順丁二烯酸半酯共聚物、苯乙烯/ 順丁烯二義絲物㈣適該絲物作域鹽、卸鹽、 頁 或銨鹽使用亦可,且該共聚物是以單獨或2種類以上混和 使用。 該共聚物中,苯乙烯系單體與陰離子性單體之比例 以80 ·· 20〜20 : 80為理想,其中,苯乙烯系單體、及陰 離子性單體,各自使用至少i種以上即可,又,於本案發 明無限定的範圍内’與上述苯乙婦系單體及/或陰離子性 單體有聚合可能之單體產生少量共聚亦可。 〜▲共聚物之f造方法,可列舉出··水溶液聚合法、 溶媒聚合法、逆相乳化聚合法、沈搬聚合法、懸濁聚合法 等方法。 該共聚物以〇· 1萬〜100萬程度之重量平均分子量即 可,而以0·1萬〜10萬之範圍為理想,分子量若小於〇1 萬,該共聚物無法形成充分之被膜,表面強度加強效果亦 不理想,另外,分子量若大於100萬,恐有因塗佈液高黏 度化等所引起操作上問題的產生。 本案發明表面處理劑所使用之成分C為,烯系單體 與陰離子性單體之絲物,即⑽系單體2G〜8G重量% 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公 585951 五、發明說明() 二x二二;聚:’作為烯系單體者,可列舉出:乙烯、丙 者,可列舉出了 3酸ίί體=等’作為陰離子性草體 烯酸、異丁烯酸、2-乙=仏丙烯酸、甲基丙埽酸、丁 丙烯酸甲基、丙烯酸乙m、3,rt~T基丙烯酸' 基等^順丁 單基體^;=丁基、丙烯酸辛 酸H脂丁祕…、體(1丁稀一酸、甲基順丁婦二 甲又丁1酸、p :氯基順丁烯二酸、反式丁烯二酸、 一 一烯二酸、順丁烯二酸甲基、順丁稀二酸 tert-丁基、順丁烯二酸乙基等)。 /丙使用之烟_物者,具體來說以乙烯 /丙狀共承物、異丁烯/丙烯酸共聚物、 :烯酸/(甲基)丙烯酸酯共聚物、丙烯/順丁烯二酸“) 物、乙烯/順丁烯二酸共聚物等 =r細亦可,且該共聚物是=納類 2〇〜二共广系單趙與陰離子性單趙之比例以t 2〇〜20. 80為理想,其中’烯系單體、及陰離子-I5J'111111 · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 585951 A7 ___B7: ------_ V. Description of the invention () Powder and other powders, polyvinyl alcohol, fully alkalized polyvinyl alcohol Polyvinyl alcohols such as polyvinyl alcohol, carboxy-denatured polyvinyl alcohol, silanol polyvinyl alcohol, cationic polyvinyl alcohol, terminal alkyl-denatured polyvinyl alcohol, polypropylene 醯, cationic polypropylene 醯, Polypropylenes such as ion-blocking polypropylene, amphoteric polypropylene, and the like; celluloses such as carboxyl-cellulose, hydroxyethylcellulose, and fluorenyl-cellulose; etc. may be used alone or as a mixture of two or more. The component A used in the surface treatment agent of the present invention does achieve its effect in terms of strengthening the surface strength (that is, the suppression of paper powder), but on the other hand, the component A also forms the inherent sticking problem of newsprint (news When printing on paper with large s, the problem caused by the transfer and accumulation of the surface treatment agent on the surface). Considering the balance between the surface strength enhancement effect and the adhesion problem, the component A of the present invention uses the starch as the example in the previous example. Among them, oxidized starch, etherified starch, and esterified starch are the most desirable. The component B used in the surface treatment agent of the present invention is a styrene-based monomer and an anionic monomer copolymer, that is, a water-soluble copolymer containing 20 to 80% by weight of a styrene-based monomer; as a styrene monomer, For example: styrene, α-methylstyrene, chlorostyrene, cyanostyrene; as anionic monomers, for example: acrylic monomers (acrylic acid, methacrylic acid, butenoic acid, methacrylic acid, 2 —Ethylacrylic acid, 3—third-butylacrylic acid, ethyl acrylate, ethyl acrylate, iso-butyl acrylate, octyl acrylate, etc.), maleic acid monomers (maleic acid, methyl Methyl maleic acid = dicarboxylic acid, phenyl maleic acid, chloro maleic acid, trans maleic acid, mesuccinic acid, adipic acid, maleic acid methyl, National Paper Standard for Cis-Butene Paper XX No. 7) --- (Please read the notes on the back before filling out this page) 111111. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 585951 A7 V. Description of Invention (2 Acid tert-butyl, ethyl maleate, etc.). The water-soluble copolymers used as component B are specifically styrene / acrylic acid copolymers, styrene / (meth) acrylic acid copolymers (wherein ((meth) acrylic acid) means "acrylic acid and / Or methacrylic acid "), styrene / (meth) acrylic acid / (meth) acrylic acid copolymer, styrene / maleic acid copolymer, stupid ethylene / maleic acid half Ester copolymers, styrene / cis butadiene filaments are suitable for use as domain salts, desalting salts, sheet or ammonium salts, and the copolymers are used alone or as a mixture of two or more types. In this copolymer, the ratio of the styrene-based monomer to the anionic monomer is preferably 80..20 to 20:80. Among them, the styrene-based monomer and the anionic monomer are each used at least i or more. Yes, within a range not limited by the present invention, a small amount of copolymerization is possible with a monomer that is polymerizable with the styrene ethyl monomer monomer and / or anionic monomer. The method for producing the copolymer includes methods such as aqueous solution polymerization, solvent polymerization, reverse phase emulsion polymerization, sink polymerization, and suspension polymerization. The copolymer may have a weight average molecular weight of about 10,000 to 1 million, and is preferably in the range of 10,000 to 100,000. If the molecular weight is less than 10,000, the copolymer cannot form a sufficient film and the surface The strength-enhancing effect is also unsatisfactory. In addition, if the molecular weight is more than 1 million, there may be problems in operation due to high viscosity of the coating liquid. The component C used in the surface treatment agent of the present invention is a silk material of an olefinic monomer and an anionic monomer, that is, a fluorene-based monomer 2G to 8G% by weight. The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 public 585951 V. Description of the invention (two) two two; Poly: 'As the olefinic monomers, there can be listed: ethylene, propyl, can be listed as the 3 acid ί body = etc.' as anionic grass alkene Acid, methacrylic acid, 2-ethyl = methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, 3, rt ~ T-based acrylic acid, etc. ^ cis butyrate ^; butyl, octanoic acid H fat butyl ..., body (1 butanedioic acid, methyl maleic acid, butanedioic acid, p: chloromaleic acid, trans butenedioic acid, monoenedic acid, cis Methyl butene diacetate, tert-butyl maleate, ethyl maleate, etc.) / Protectors of cigarettes, specifically ethylene / propene co-containers, isobutylene / Acrylic acid copolymer,: acrylic acid / (meth) acrylate copolymer, propylene / maleic acid ", ethylene / maleic acid copolymer, etc. = r is fine, and the Is satisfied based prepolymer = 2〇~ two broad-based monomer ratio of total anionic monoethylenically Zhao Zhao 2〇~20 to t 80 is over, where '-based monomer, and an anionic
各^吏用至少i種以上即可,又,該共聚物於本案發明益 限疋的範圍内,與上述烯系單體及/或陰離子性單體…、 合可能之單體產生少量共聚亦可。 K 該共聚物之製造方法,可列舉出··水溶液聚合法、 合法、逆相乳化聚合法、沈澱聚合法、懸濁聚合法 該共聚物以0.1萬〜100萬程度之重量平均分子量即 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公| ) _ttr--------- (請先閱t#背面之注意事項再填寫本頁) 585951 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明() 可,而以〇·1萬〜1〇萬之範圍為理想,分子量若小於Q1 萬,該共聚物無法形成充分之被膜,表面強度加強效果亦 不理心另外,分子量若大於100萬,恐有因塗佈液高黏 度化等所引起操作上問題的產生。 本案發明表面處理劑各成分之比例(重量比), 報紙用紙製造所要求的品質,而不一定有所限制,;^若 要加以限定的話,則以成分A、成分B、成分C比例(α ··β : C)為l00:0·1〜50··0·1〜50範圍内為適當,成分β及c, 相對於成分Α,未滿0」時,有上膠性發現性之問題點, 又,超過50時,有經濟性、及操作性之問題點,而又以 A 1〇〇 : 2〜20 : 2〜20範圍内為理想。 、本案發明之表面處理劑,係由混和3種成分調製而Each of them can be used with at least i kinds, and the copolymer is within the scope of the present invention, and a small amount of copolymerization with the above-mentioned ethylenic monomers and / or anionic monomers ... can. K The manufacturing method of the copolymer includes: aqueous solution polymerization method, legal method, reverse phase emulsion polymerization method, precipitation polymerization method, and suspension polymerization method. The copolymer has a weight average molecular weight of about 10,000 to 1 million, that is, this paper. Standards are applicable to China National Standard (CNS) A4 specifications (210 X 297 male |) _ttr --------- (Please read the precautions on the back of t # before filling out this page) 585951 Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Cooperative printed A7 V. Description of invention () Yes, but ideally in the range of 0.1 million to 100,000. If the molecular weight is less than Q10,000, the copolymer cannot form a sufficient film, and the effect of surface strength enhancement is ignored. In addition, if the molecular weight is more than 1 million, there may be problems in operation due to the increase in viscosity of the coating liquid. The ratio (weight ratio) of each component of the surface treatment agent of the invention of this case is not limited to the quality required for the manufacture of newspaper paper; ^ To be limited, the ratio of component A, component B, and component C (α ·· β: C) is l00: 0 · 1 ~ 50 ·· 0 · 1 ~ 50 is appropriate. When the components β and c are less than 0 relative to the component A, there is a problem of discoverability of gumming properties. When it exceeds 50, there are problems in terms of economy and operability, and the range of A 100: 2 to 20: 2 to 20 is ideal. The surface treatment agent of the present invention is prepared by mixing three ingredients
成,但於混和時,會生成不溶性沈澱物之組合,於本案 明是為不理想。 ' X 卜又,本案發明之表面處理劑,在不影響本案發明的 範圍内,含有黏結防止劑、防腐劑、消泡劑、紫外線防止 劑、褪色防止劑、螢光增白劑、黏度安定化劑、滑劑、防 滑劑等助劑或填料亦可。 、本案發明所使用之報紙用原紙,以機械木漿(Gp)、 感熱機製木漿(TMP)、化學感熱機製木漿(CTMp)、半化學 紙漿等機製木漿(MP),以硫酸鹽紙漿(KP)作為代表之化t學 紙漿(CP),將含該等紙漿之舊紙脫墨後得到之脫墨紙漿予 (DIP),及分解造紙工程中之廢紙所得之回收紙漿等,將 其單獨、或以任意比例混和,即成一般公知公用造紙機之 本紙張尺錢財關家標罕(CNS)A4規格(210 X 297公邊) . --------^---------.» (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 赚尺度適用中國國 M5951It is not ideal because the combination of insoluble precipitates will be generated during mixing. 'X Bu, the surface treatment agent of the present invention, within the scope of not affecting the invention of the present case, contains an adhesion preventive agent, a preservative, a defoamer, an ultraviolet preventive agent, a discoloration preventive agent, a fluorescent whitening agent, and a viscosity stabilizer. Additives or fillers such as agents, slip agents, anti-slip agents, etc. may also be used. The newspaper base paper used in the invention of this case is made of mechanical wood pulp (Gp), thermo-mechanical wood pulp (TMP), chemical thermo-mechanical wood pulp (CTMp), semi-chemical pulp and other mechanism wood pulp (MP), and sulfate pulp (KP) is the representative chemical pulp (CP), deinked pulp obtained after deinking old paper containing these pulps (DIP), and recycled pulp obtained by decomposing waste paper in papermaking engineering. It can be used alone or mixed at any ratio to form the standard paper rule of the public paper machine (CNS) A4 (210 X 297 male). -------- ^ ----- ----. »(Please read the notes on the back before filling out this page) Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the earning scale applies to China M5951
、發明說明( :紙_之配合率,就最近dip高配合話流程來 ^ 〜100%範圍較理想,又,原紙之米坪量並盖特 別限定,約為34〜45g/nf。 卡坪里並”、、特 八用原紙,視其必要性,可適當添加一般公知 用真料、造紙用藥品,作為填料者,可添加白炭 /崎m石t石、滑石、氧化欽、碳酸詞、合成樹脂填料 ^ ^^ 土十脂、聚笨乙烯樹脂、尿素甲醛水樹脂、三 脂、苯乙烯/ 丁二烯系共聚物系樹脂等)等;特 ΐ: 中:碳酸鈣為有效者,又,作為造紙用藥 ^γ右3有·聚丙烯醯系高分子、聚乙烯醇系高分 ='尿素/甲駿水樹脂、三聚氛胺樹脂等 力’丙_/氨基甲基丙烯酿共聚物之鹽、陽離 :化Μ又粕:聚乙烯亞胺、聚乙烯氧化物、丙烯醯/丙烯酸 斗:、水物等打聚性/出成率向上劑、松香膠料劑、乳膠膠 ^ ^ 基乙烯_二聚體(AKD)、脂烯基_酸無水物(ASA) 4 _,硫酸紹(硫酸蓉土)、紫外線防止劑、褪色防止 劑、消泡劑等助劑等亦可,該原紙之物性,對平版印刷機 之印刷作業有其必要性,即具普通報紙用紙程度之拉張強 度、撕裂強度、延伸等物性。 該報紙用原紙使用施以内添上膠之原紙亦可,惟本 案發月有解決别述伴隨内添而生問題之意,是以使用不施 加内添^膠之H較能發揮本案發明之效果 ,亦即,本 ,明,由表面處理劑之外添上膠,即使不進行内添上 夕賦予與内添上膠同樣或更好之吸水抵抗性,例如, 297公查) (請先閱讀背面之注意事項再填寫本頁)、 Explanation of the invention: The blending ratio of paper_ is from the recent dip high-matching process. The range of ^ ~ 100% is ideal, and the amount of rice paper on the base paper is particularly limited, which is about 34 ~ 45g / nf. Kapingli "Band", and special eight base papers, depending on their necessity, can be appropriately added with commonly known genuine materials, papermaking chemicals, and as filler, white charcoal / sakimite t-stone, talc, oxanthine, carbonate words, synthesis Resin fillers ^ ^^ Earth ten fat, polyethylene resin, urea formaldehyde water resin, tri-ester, styrene / butadiene copolymer resin, etc .; etc .; Special: Medium: Calcium carbonate is effective, and, As a medicine for paper making ^ γRight3Polypropylene 醯 -based polymers, polyvinyl alcohol-based high scores = 'Urea / Jiajun water resin, melamine resin, etc.' Propylene / aminomethyl propylene copolymer Salt, Anion: Chemicals and Meal: Polyethyleneimine, Polyethylene Oxide, Acrylic Acid / Acrylic Acid Bucket :, Water Polymers, etc. Additive / Productivity Upward Agent, Rosin Rubber Agent, Latex ^ ^ Ethylene _ dimer (AKD), fatty alkenyl _ acid anhydrous (ASA) 4 _, sulphuric acid sulphate (sulfuric acid sulphate), UV protection Additives such as anti-fading agents, anti-foaming agents, and defoaming agents are also available. The physical properties of the base paper are necessary for the printing operation of lithographic printing presses, that is, the tensile strength, tear strength, and extension of ordinary newspaper paper are the same. The paper used as the base paper can also use the base paper coated with glue. However, the issue of this case has the intention to solve the problems associated with the internal filling. The use of H without the internal glue is more effective in the invention of this case. The effect, that is, Ben, Ming, the addition of glue from the surface treatment agent, even if not added, the same or better water absorption resistance with internal glue, such as 297 public inspection) (Please read the back first (Notes to fill out this page)
585951 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明() 本案發明之表面處理劑,以點滴吸水度法(JaPan TAPPI No· 33中使用之方法(於紙面上滴下1的水,測量水滴 被紙面吸收為止的時間)),對未滿1 〇秒之報紙用紙,能 充分適用。 又,本案發明之報紙原紙,使用酸性製造報紙原紙 亦可,中性、或鹼性製造報紙原紙亦可,本案發明之表面 處理劑以使用中性、或鹼性製造報紙原紙時,較能彰顯其 效果。 本案發明之平版印刷用新聞用紙,係以成分A〜c為 主體構成之表面處理劑塗布於報紙原紙上,經乾燥後所 得。 本案發明表面處理劑之塗布量(亦即,成分A、成八B 及成分C之固形分合計) 刀 ,係因應報紙用紙製造品質(上膠性、彩色印刷適性等)所 決定,並無特別限定,但以塗佈量(兩面)〇.丨〜丨^以…。 度為適當,例如,塗佈量未滿〇· 1 g/m2時,在上膠性賦王 予、及表面強度加強點上,無法充分發揮表面處理劑之饮 果;相反地,塗佈量高於g/m2時,引發所謂黏結問夕 題的可能性變高;又,於本案發明之表面處理劑中,者、 分A為澱粉類時,考慮到其表面強度加強效果,是以二成 處理劑之塗佈量以〇·2〜1.2 g/m2程度為適當,但,在^ 紙用紙以外之平版印刷用紙的情況下,則不為此限,^ 塗佈量0· 5〜4· 0 g/m2程度。 、 本案發明表面處理劑之塗佈量,需考慮到與黏結強 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公1iy (請先閱讀背面之注咅?事項再填寫本頁) 裝585951 Printed by A7 B7 of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention () The surface treatment agent in this case was prepared by the dripping method (JaPan TAPPI No. 33 (1 drop of water on paper, Measure the time until water droplets are absorbed by the paper surface)), and it can be fully applied to newspaper paper less than 10 seconds. In addition, the newspaper base paper invented in the present case may be produced using acidic newspaper base paper, and the newspaper base paper in neutral or alkaline form may also be used. The surface treatment agent in the present invention is more prominent when the newspaper base paper is produced in neutral or alkaline form. Its effect. The lithographic newsprint invention of the present invention is obtained by applying a surface treatment agent composed mainly of components A to c on a newspaper base paper and drying it. The coating amount of the surface treatment agent of the present invention (that is, the total solid content of component A, 80% B, and component C) The knife is determined according to the quality of newspaper paper (sizing, color printing, etc.), and there is no special Limited, but with the coating amount (both sides) 〇. 丨 ~ 丨 ^ 以…. The degree is appropriate. For example, when the coating amount is less than 0.1 g / m2, the sizing property of Wang Yu and the surface strength strengthening point cannot fully exert the effects of the surface treatment agent. On the contrary, the coating amount When it is higher than g / m2, the possibility of causing the so-called sticking problem becomes high. In addition, in the surface treatment agent of the present invention, when A is starch, taking into account its surface strength enhancing effect, The coating amount of the treating agent is appropriate to be about 0.2 to 1.2 g / m2. However, in the case of lithographic printing paper other than ^ paper, this is not a limitation, and ^ coating amount is 0.5 to 4 · About 0 g / m2. The coating amount of the surface treatment agent of the invention of this case needs to take into account the strength and adhesion. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 male 1iy (please read the note on the back? Matters before filling this page) Hold
585951 A7 B7 五、發明說明( 度之平衡,本案發明之平版印刷用新聞用紙,在後述之 結實驗法中,可知黏結強度於70gf/3cm(0.69N/3cm)以| 者為適當;本案發明表面處理劑成分A為澱粉類之新聞用 紙的情況下,與以殿粉類及成分B、或澱粉頬與成分c 組合進行塗佈、乾燥後之新聞用紙相較之下,強声有上 昇傾向,此意謂著成分B與成分C間有其相乘作用,^此 本案發明之平版印刷用新聞用紙必須達到與黏結強产門、’ 平衡。 本案發明表面處理劑之塗佈裝置(塗佈機),〇 e 普通製紙用塗佈裝置外,並無特別限制,例如可列舉^. 2輥式壓膠機、片型儀錶轉換壓膠雞、棒型儀錶轉^壓^ 機、澆口輥塗機、棒塗機、氣動刮塗機等裝置;該等枣膠 中,以代表澆口輥塗機之被膜轉寫型塗佈機為理^置 聞用紙則以.澆口輥塗機(GRC)為常見,於本案發明 ^ 為理想。 *用最 在新聞用紙的製造中,表面處理劑的塗佈一般皆r 機檯上來進行,其塗佈速度約同普通新聞用紙造紙 紙速度,在800〜1800m/分之範圍内。 ' ^ 本案發明之平版印刷用新聞用紙,在經表面處理 塗佈、乾燥後,為了得到適於平版印刷之紙厚、平滑性 還需經壓延處理,而壓延機通常使用硬質夾壓延機π或铲 質夾壓延機(例如,紙漿技術時代vol 43,No l(2〇〇(j八 等中整理出),考慮到今後新聞用紙的輕量化,本案發S 3 之平版印刷用新聞用紙,以經軟質夾壓延處理者為理邦、, 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297 ^ (請先閱讀背面之注音?事項再填寫本頁} 裝585951 A7 B7 V. Description of the invention (balance of degrees, newsprint for lithographic printing invented in this case, in the knot experimental method described below, it can be seen that the bond strength is 70gf / 3cm (0.69N / 3cm) | In the case where the surface treatment agent component A is starch-based newsprint, compared with newsprint paper coated and dried with starch powder and component B, or starch starch and component c in combination, the strong sound tends to rise. This means that there is a synergistic effect between component B and component C. ^ The lithographic printing newsprint invented in this case must achieve a balance with strong adhesion. The coating device (coating) for the surface treatment agent of the present invention Machine), 〇e There is no particular limitation on the coating device for ordinary paper making, for example, ^. 2 roller type laminator, sheet meter conversion laminating chicken, rod meter conversion ^ press ^, gate roll Coating machine, rod coating machine, pneumatic blade coating machine, etc .; among these jujubes, the film transfer type coating machine representing the gate roller coating machine is used as the principle. GRC) is common and is invented in this case ^ Ideal. * Used most in news In the manufacture of coatings, the surface treatment agent is generally applied on a machine, and the coating speed is about the same as that of ordinary newsprint papermaking paper, in the range of 800 to 1800 m / min. ^ ^ News for lithographic printing of the invention of this case For paper, after surface coating and drying, in order to obtain the thickness and smoothness of the paper suitable for lithography, it needs to be calendered. The calender usually uses a hard nip calender π or a shovel nip calender (for example, pulp Technology Times Vol 43, No 1 (reorganized in J Ya et al.). In consideration of the future weight reduction of newsprint, the case of S 3's lithographic newsprint was issued in this case. State, this paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 ^ (Please read the note on the back? Matters before filling out this page})
經濟部智慧財產局員工消費合作社印製 585951 A7 經濟部智慧財產局員工消費合作社印製 五、發明說明( 在使用高速軟質夾壓延處理的條件為,因應於所求新聞用 紙之品質(紙厚、平滑性等),以溫度30〜150°C,線壓2〇 〜150kN/m之範圍内為宜;若從彩色印刷適性一點來看, 本案發明之.表面處理劑,.與軟質夾壓延處理配合即可。 本案發明平版印刷用新聞用紙之吸水抵抗性(上膠 ^ ) ^ ^ °口的作法’做適當決定即可,並無特別限制, 若以前述點滴吸水度法加以限定,則點滴吸水度在1〇〜 1000秒範圍内為佳,更理想為15〜3〇〇秒之範圍;又, 如特開平8-232193號公報、或特開平u_14〇791號公報 中a己載之依水滴接觸角方法(水滴落下至紙面指定時間後 之接觸角)加以限定時,以5以水滴滴落紙面經0. 1秒後 2觸角為90度以上者為理想,特開平8_232193號公報 落下經5秒後測定其接觸角,特開平1H40791 1°二二疋=1秒後測定其接觸角’ ^考慮到實際報紙平 牵杯明ί之f要時間,接觸角的測定時間應盡量縮短,本 ^ \欠則是以G·1秒後之接觸角進行評價;點滴吸水度 角來看’皆屬靜態上膠性的評價,惟依其接觸 機中附著濕水後,作為印刷物至排出為止這段時 後者為,例如,如輔助機般之彩色印刷機, 做二:間Γ應對用紙動作者,各自以不同事象來 :在二 =平版印刷用新聞用紙,其點滴吸水 10 _秒之範圍’且5糾水滴滴下經(U秒後之 本紙張尺度適 297公Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 585951 A7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (The conditions for the use of high-speed soft clip calendering are based on the quality of the newsprint (paper thickness, (Smoothness, etc.), a temperature of 30 to 150 ° C and a linear pressure of 20 to 150 kN / m are appropriate; if the color printing is suitable, the surface treatment agent of the present invention and the soft sandwich calendering process The water absorption resistance (glueing ^ ^ ^ ^ ° of the invention of lithographic newsprint paper of the present invention) can be determined appropriately, and there is no particular limitation. If it is limited by the aforementioned dripping water absorption method, dripping The water absorption is preferably in the range of 10 to 1000 seconds, and more preferably in the range of 15 to 300 seconds. In addition, as described in Japanese Unexamined Patent Publication No. 8-232193 or Japanese Unexamined Patent Publication U_14〇791 When the water droplet contact angle method (the contact angle after the paper drops to the specified time on the paper surface) is limited, it is desirable that 5 drops of water are dropped on the paper surface after 0.1 second and the antenna angle is 90 degrees or more. JP-A-8_232193 The contact angle was measured after 5 seconds, and JP 1H40791 1 ° 22 was measured after 1 second. ^ Considering the actual time required for the newspaper to hold the cup, the measurement time of the contact angle should be as short as possible. ^ \ Under evaluation is based on the contact angle after G · 1 second; from the point of view of the drop water absorption angle, they are all static sizing properties. However, after the wet water is attached to the contact machine, it is printed until it is discharged. The latter is, for example, a color printing press like an auxiliary machine, doing two: time Γ to deal with paper actors, each with different things: in two = lithographic newsprint paper, its dripping water in the range of 10 _ seconds' And 5 correction water drops dripping (the paper size after U seconds is suitable for 297 meters
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(請先閱讀背面之注意事項再填寫本頁) 585951 五、發明說明( 接觸角在90度以上者為理想。 本案發明平版印刷用新聞用紙之彩色印刷適性中, 有關彩色印刷適性也可能無適當評價方法,由於並沒有特 別限疋疋以貫際Λ使用彩色郎刷機印刷時,只要印面良 好即可。 意 【作用】 本案發明之平版印刷用新聞用紙,係利用以成分Α〜 C 3成分為主體之表面處理劑,於新聞用紙原紙上以 1. 5g/m範圍之塗佈區域,藉由澆口輥塗機進行塗佈, 而得到點滴吸水度為10〜麵秒,且5 W水滴滴下經〇1 秒後之接觸角在90度以上之上膠性之具優越彩色印刷適 訂 性之平版印刷用新聞用紙。 有關本案發明之表面處理劑能賦予高上膠性一點, 本案發明所使用表面處理劑之成分β、及成分^,由於常 用做表面上膠劑使用,故有可靠性,但,成分β及成分c 混和後,比起成分B、或成分C單獨使用,其上膠性加強 效果加倍提高之理由,至今仍不明,惟當成分β之點滴吸 水I*生提同打,成分C之接觸角亦有變大傾向一點是被承認 的,是以有由於其滅予上膠性之機械理論不同,而出現上 膠性提高之加倍效果。 另外,就彩色印刷適性一點來說,由於成分c與墨 水間具優良相溶性,是以使得用紙墨水受理性、附著之 提兩。 本紙張尺度適用中國國家標準(CNS)A4規格(210 x 297公七 585951 A7 _____B7_ 五、發明說明() 【實施例】 (請先閱讀背面之注意事項再填寫本頁) 以下,以本案發明之實施例做一說明,想當然爾, 本案發明亦不限於該等使用物,又,實施例中,部、及% •若無特別限定,則是表示各別之t量。部及重量%。 〈表面處理劑〉 · 有關表面處理劑,將以下之各成分進行合成或取用 現成者。 〈成分A〉 A-1 :氧化澱粉(商品名:SK-20,日本Constouch股份有 限公司製) A-2 :經乙基化殿粉(商品名·· PG-280,Penford公司製) A-3 :酯化澱粉(商品名:Filmkote-370,Nashonalstouch 公司製) A-4 :陰離子性聚丙烯醯(商品名:P-120,星光化學工業 股份有限公司製) 〈成分B〉 B-1 :苯乙烯·(曱基)丙烯酸共聚物(Mw=56000) 經濟部智慧財產局員工消費合作社印製 B-2 :苯乙烯•丙烯酸系表面上膠劑(商品名:KN-520, Harima化成(股份)製) B-3 :苯乙婶•順丁二烯酸共聚物(Mw= 48000) B-4 :苯乙烯•順丁烯二酸系表面上膠劑(商品名: CorobarM-150,星光化學工業股份有限公司製) 〈成分C〉 C-1 :異丁烯•順丁二烯酸共聚物(Mw= 34000) 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公1ί ) 經濟部智慧財產局員工消費合作社印製 585951 A7 -—- ___ B7 __ 五、發明說明() C-2 :乙烯·丙烯酸共聚物(Mw=15〇〇〇) C-3 :烯系表面上膠劑(商品名:AK—5〇5,Misawaseramic 股份有限公司製) 又’ B-1〜B-4之苯乙烯系單體的比例為2〇〜8〇重量 %範圍内,而,C-1〜C-3之烯系單體的比例為20〜80重 量%範圍内,則無須再度說明。 〈新聞用紙原紙A之製造〉 以 DIP (打衆度 180ml) 40 部、TMP (打漿度 100ml) 50 部、NBKP (打漿度600ml) 10部之比例混和浸潰後調製成 之紙漿中,每對絕乾紙漿中添加白炭黑1 %,以小擘成型 造紙機酸性造紙,得到無上膠、無壓延,米坪量42g/m2 之新聞用紙原紙A,新聞用紙原紙a之點滴吸水度為6秒。 〈新聞用紙原紙B之製造〉 DIP (打漿度 _180ml) 50 部、TMP (打漿度 l〇〇mi) 3〇 部、NBKP (打漿度 600ml) 10 部、GP (打漿度 8〇ml) 1〇 部之比例混和浸潰後調製成之紙漿中,每對絕乾紙漿添加 碳酸鈣1.5%,以小擘成型造紙機中性造紙,得到無上膠、 無壓延,米坪量42g/m2之新聞用紙原紙,新聞用紙原紙6 之點滴吸水度為5秒。 〈新聞用紙之製造〉 [實施例1〜2 ] 於成分A-1之澱粉水溶液中,將成分β-丨水溶液、 及成刀C-1水浴液以表1之配合比例混和,調製成表面處 理劑,將得到之表面處理劑,於前述新聞用紙原紙A上, (請先閱讀背面之注意事項再填寫本頁)Binding --------- ^^ 丨! (Please read the precautions on the back before filling this page) 585951 V. Description of the invention (The contact angle is more than 90 degrees is ideal. In this case, the color printing suitability of the newsprint for lithographic printing is not suitable for color printing suitability. The evaluation method is not particularly limited. When printing with a color brush machine, the printing surface may be good. [Action] The lithographic newsprint paper of the present invention uses the components A to C 3 as The surface treatment agent of the main body is coated on a newsprint base paper with a coating area in the range of 1.5 g / m by a gate roll coater to obtain a droplet water absorption of 10 to surface seconds, and 5 W drops The lithographic newsprint paper with superior color printing suitability with a contact angle of 90 degrees or more after 0 seconds. The surface treatment agent of the present invention can impart a high sizing property, which is used in the present invention. The components β and ^ of the surface treatment agent are reliable because they are commonly used as surface sizing agents. However, after mixing the component β and the component c, it is compared with the component B or the component C. The reason why it is used alone, and its sizing effect is doubled, is still unknown, but when the component β absorbs water I *, it will also increase the contact angle of component C. It is recognized that Due to its different mechanical theory of sizing, there is a double effect of improving sizing. In addition, in terms of the suitability for color printing, due to the excellent compatibility between component c and ink, paper and ink are accepted. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 x 297 Gongqi 585951 A7 _____B7_ V. Description of the invention () [Example] (Please read the precautions on the back before filling this page ) In the following, an example of the invention of the present invention will be described. As a matter of course, the invention of the present invention is not limited to these uses, and in the examples, parts and%. • If there is no special limitation, it means the respective t quantities. 。Part and weight%. <Surface treatment agent> · Regarding the surface treatment agent, the following components are synthesized or used off-the-shelf. <Component A> A-1: Oxidized starch (brand name: SK-20, Japan) Constouch Co., Ltd.) A-2: Ethylated powder (trade name: PG-280, manufactured by Penford) A-3: Esterified starch (trade name: Filmkote-370, manufactured by Nashonalstouch) A- 4: Anionic polypropylene samarium (trade name: P-120, manufactured by Starlight Chemical Industry Co., Ltd.) <component B> B-1: styrene (fluorenyl) acrylic copolymer (Mw = 56000) Intellectual property of the Ministry of Economic Affairs Printed by the Bureau ’s Consumer Cooperatives B-2: Styrene / Acrylic Surface Sizing Agent (Trade name: KN-520, manufactured by Harima Kasei Co., Ltd.) B-3: Phenylacetic acid • maleic acid copolymer ( Mw = 48000) B-4: Styrene and maleic acid-based surface sizing agent (brand name: CorobarM-150, manufactured by Starlight Chemical Industry Co., Ltd.) <ingredient C> C-1: isobutylene and maleic acid Ethylene copolymer (Mw = 34000) This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 public 1 liter) Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 585951 A7 ----- ___ B7 __ V. Description of the invention () C-2: ethylene · acrylic copolymer (Mw = 150,000) C-3: on olefinic surface Agent (trade name: AK-505, manufactured by Misawaseramic Co., Ltd.) The ratio of styrene-based monomers of B-1 to B-4 is in the range of 20 to 80% by weight, and C-1 The proportion of the olefinic monomer of ~ C-3 is in the range of 20 to 80% by weight, so it need not be explained again. <Manufacturing of Newsprint Base Paper A> 40 pairs of DIP (180ml beating degree), 50 TMP (100ml beating degree), and 10 NBKP (600ml beating degree) are mixed and impregnated into pulp prepared by dipping. 1% white carbon black was added to the absolute dry pulp, and acid paper was made on the Koito molding paper machine to obtain a newsprint base paper A with a size of 42g / m2 without sizing and calendering, and a water absorption of 6 for a newsprint base paper a second. 〈Manufacture of newsprint base paper B〉 50 DIP (beating degree_180ml), 30 TMP (beating degree 100mi), 30 NBKP (beating degree 600ml) 10, GP (beating degree 80ml) 10 In the pulp prepared by mixing and impregnating, 1.5% calcium carbonate is added to each pair of absolutely dry pulp, and the papermaking process is made on a small papermaking machine with neutral paper, and there is no sizing and calendering. The news is 42g / m2. The paper base paper and newsprint base paper 6 have a water absorption of 5 seconds. <Manufacturing of Newsprint Paper> [Examples 1 to 2] In a starch aqueous solution of component A-1, the component β- 丨 aqueous solution and the knife C-1 water bath were mixed at the mixing ratio of Table 1 to prepare a surface treatment. Agent, the surface treatment agent will be obtained on the aforementioned newsprint base paper A, (Please read the precautions on the back before filling this page)
585951585951
經濟部智慧財產局員工消費合作社印製 以澆口輥塗機塗佈(塗佈速度:1150111/分,兩面塗佈),塗 佈後,進行高溫軟質夾壓延處理(輥塗溫度11(rc,線面 塗佈),製造平版印刷用新聞用紙。 得到之平版印刷用新聞用紙,以下述項目作一評價, 結果如表1所示。 •點滴吸水度測定··以Japan TAPPI No· 33 (具吸收性 紙之吸水速度實驗方法)為基準,以滴下水量丨# i進行測 定。Printed by gatekeeper roller coater (coated speed: 1150111 / min, coating on both sides) by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. After coating, high temperature soft sandwich calendering (roller coating temperature 11 (rc, Line surface coating) to produce lithographic newsprint paper. The obtained lithographic newsprint paper was evaluated by the following items, and the results are shown in Table 1. • Drop water absorption measurement • Japan TAPPI No. 33 (with The test method of water absorption rate of absorbent paper) was used as a reference, and the amount of dripping water was measured.
•接觸角測疋.使用 Dynamic Absorption Tester 1100DAT (Fibro公司製)’於新聞用紙滴下5 # i之水滴,於滴下】 秒後測定其接觸角。 .強度測定:將平版印刷用新聞用紙,切割成4X6cm兩 張’將塗佈面以溫度2(rc的水浸潰5秒後,將兩塗佈面 貼合,於該貼合紙上,以50kgf/ffl2之壓力輥塗處理,再 以25t:、60%RH調濕24小時,將實驗片切割成3X6cm 後’於拉張貫驗機以拉張速度3〇_/分的設定下進行測試, 測定值越大越不易剝落(亦即,黏著性越強),強度在° 7〇gf/3cin以下者,可稱為良好之印刷用新聞用紙。 •彩色印刷適性評價:使时版輪轉機(東芝平版輪轉機: 0A-4B2T-600),進行彩色四色印刷(藍 ' 紅、黃 色順序)’第四色之里單色部、;5番# ☆ …早巴〇丨及重疊四色重色部之濃度 评價、及濃度變化,以目視進行評價。 ◎:第四色黑之印面濃度非常高,濃度無變化, 色部得到非常均一之畫像。 、更 本紙張尺度_中國國家標準(CNS)^^ (21。x 297公邊)_ --------^--------- (請先閱讀背面之注意事項再填寫本頁) 585951• Contact angle measurement. Using Dynamic Absorption Tester 1100DAT (manufactured by Fibro) ', a 5 # i drop of water was dropped on the newsprint paper, and the contact angle was measured after dropping for 5 seconds. .Strength measurement: Cut lithographic newsprint paper into 2 sheets of 4 × 6 cm '. After coating the coated surface with water at a temperature of 2 (rc for 5 seconds), bond the two coated surfaces to the bonding paper at 50 kgf. / ffl2 pressure roller coating treatment, and then humidity 25t: 60% RH for 24 hours, cut the test piece into 3X6cm, and then test in the tensile tester at a setting of 30_ / min, The larger the measured value, the more difficult it is to peel off (that is, the stronger the adhesiveness), and the strength below ° 70 gf / 3cin can be called a good newsprint for printing. • Evaluation of the suitability of color printing: the time-type rotary machine (Toshiba Lithographic rotary machine: 0A-4B2T-600), color four-color printing (blue 'red, yellow order') in the fourth color of the single color section; 5fan # ☆… Zaoba 丨 and overlapping four-color heavy color The density evaluation and density change were evaluated visually. ◎: The density of the printed surface of the fourth color black is very high, there is no change in density, and the color department gets a very uniform portrait.。 本 paper scale_Chinese National Standard (CNS ) ^^ (21. x 297 male) _ -------- ^ --------- (Please read the precautions on the back first Write Page) 585 951
〇:第四色黑之印面濃度高,濃度幾無變化,又, 部得到均一之畫像。 △:第四色黑之印面濃度偏低,可看出濃度變化,又,於 重色部得到不均一且鮮明度偏差晝像。 ' X·第四色黑之印面濃度低,濃度明顯變化,又,於重 部得到不均一且鮮明度差之晝像。 [比較例1 ] 除了使用將成分A-1澱粉水溶液、及成分水溶 液以表1之配合比例混和而成之表面處理劑外,在與^施 例1〜2相同條件下,製造平版印刷用新聞用紙,所得平^ 版印刷用新聞用紙,以前述項目作一評價,結果如表' 1所 示0 [比較例2 ] 除了使用將成分A-1殿粉水溶液、及成分c— 1水溶 液以表1之配合比例混和而成之表面處理劑外,在與實施 例1〜2相同條件下,製造平版印刷用新聞用紙,所得平 版印刷用新聞用紙,以前述項目作一評價,結果如表1所 示。 [比較例3] 除了僅使用成分A-1澱粉水溶液而成之表面處理劑 外,在與實施例1〜2相同條件下,製造平版印刷用新聞 用紙,所得平版印刷用新聞用紙,以前述項目作一評價, 結果如表1所示。 ' 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公髮) ----- - -------I (請先閱讀背面之注意事項再填寫本頁)〇: The print surface of the fourth color black has a high density, with little change in density, and a uniform image is obtained in part. △: The density of the printed surface of the fourth color black is relatively low, and it can be seen that the density changes, and a non-uniform and sharpness deviation day image is obtained in the heavy color portion. 'The density of the printed surface of X · Four-color black is low, and the density changes significantly, and a day image with unevenness and poor sharpness is obtained on the heavy part. [Comparative Example 1] A lithographic printing press was produced under the same conditions as in Examples 1 to 2 except that the surface treatment agent obtained by mixing the component A-1 starch aqueous solution and the component aqueous solution in the mixing ratio of Table 1 was used. Using paper, the obtained lithographic printing newsprint was evaluated based on the above items, and the results are shown in Table '1. 0 [Comparative Example 2] In addition to using the component A-1 powder solution and the component c-1 solution as the table, Except for the surface treatment agent obtained by mixing the mixing ratio of 1, the lithographic newsprint was produced under the same conditions as in Examples 1 to 2. The obtained lithographic newsprint was evaluated by the aforementioned items. The results are shown in Table 1. Show. [Comparative Example 3] A lithographic newsprint was produced under the same conditions as in Examples 1 to 2 except that the surface treatment agent was prepared using only a starch aqueous solution of component A-1. As an evaluation, the results are shown in Table 1. '' This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 issued) ------------- I (Please read the precautions on the back before filling this page)
經濟部智慧財產局員工消費合作社印製 585951 A7 B7 五、發明說明(Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 585951 A7 B7 V. Description of the invention (
【表1】 成分A 成分B 成分C 配合比 (A:B:C) 塗佈量 (兩 點滴吸水度 (秒) 接觸角 (度) 強度 (gf/3cm) 彩色印 刷適性 實施例1 A-1 B-l C-l 100:5:5 0.62 189 102 29 ◎ 實施例1 A-1 B-l C-l 100:8:2 0.58 248 97 28 ◎ 比較例1 A-1 B-l — 100:10:0 0.60 54 · 89 17 〇〜△ 比較例2 A-1 — C-l 100:0:10 0.64 12 95 15 〇 比較例3 A-1 — — 100:0:0 0.61 6 70 19 X 經濟部智慧財產局員工消費合作社印製 [實施例3〜5] 於成分A-2之殿粉水溶液中,將成分B-3水溶液、 及成分C-2水溶液以表2之配合比例混和,調製成表面處 理劑,將得到之表面處理劑,於前述新聞用紙原紙B上, 以澆口輥塗機塗佈(塗佈速度:1300m/分,兩面塗佈),塗 佈後,進行高溫軟質夾壓延處理(輥塗溫度110°C,線壓 130kN/m),製造平版印刷用新聞用紙,所得之平版印刷用 新聞用紙,以前述項目作一評價,結果如表2所示。 [比較例4 ] 除了使用將成分A-2澱粉水溶液、及成分B-3水溶 液,以表2之配合比例混和而成之表面處理劑外,在與實 施例3〜5相同條件下,製造平版印刷用新聞用紙,所得 平版印刷用新聞用紙,以前述項目作一評價,結果如表2 所示。 [比較例5] 除了使用將成分A-2澱粉水溶液與成分C-2水溶液, 以表2之配合比例混和而成之表面處理劑外,在與實施例 (請先閱讀背面之注意事項再填寫本頁)[Table 1] Component A Component B Component C Compound ratio (A: B: C) Coating amount (two-point water absorption (seconds) Contact angle (degrees) Strength (gf / 3cm) Color printing suitability Example 1 A-1 Bl Cl 100: 5: 5 0.62 189 102 29 ◎ Example 1 A-1 Bl Cl 100: 8: 2 0.58 248 97 28 ◎ Comparative Example 1 A-1 Bl — 100: 10: 0 0.60 54 · 89 17 〇 ~ △ Comparative Example 2 A-1 — Cl 100: 0: 10 0.64 12 95 15 〇 Comparative Example 3 A-1 — — 100: 0: 0 0.61 6 70 19 X Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs [Example 3 ~ 5] In the powder solution of component A-2, the aqueous solution of component B-3 and the aqueous solution of component C-2 are mixed at the mixing ratio of Table 2 to prepare a surface treatment agent. The obtained surface treatment agent is used in The newsprint base paper B was coated by a gate roll coater (coating speed: 1300 m / min, coating on both sides). After coating, high-temperature soft nip calendering was performed (roll coating temperature 110 ° C, line pressure 130 kN). / m) to produce lithographic newsprint paper. The obtained lithographic newsprint paper was evaluated by the aforementioned items, and the results are shown in Table 2. [Comparative Example 4] Except for use The surface treatment agent obtained by mixing the aqueous solution of the component A-2 and the aqueous solution of the component B-3 at the mixing ratio shown in Table 2 was produced under the same conditions as in Examples 3 to 5, and the resulting lithographic printing paper was produced. The newsprint for printing was evaluated based on the above items, and the results are shown in Table 2. [Comparative Example 5] Except that the component A-2 starch aqueous solution and the component C-2 aqueous solution were mixed at the mixing ratio of Table 2 In addition to the surface treatment agent, please refer to the examples (please read the precautions on the back before filling this page)
言 r 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公售) 585951 五、發明說明( 經濟部智慧財產局員工消費合作社印製 私紙張尺度翻中關家標準(CNS)A4^i^ A7 B7 3〜5相同條件下,製造平版印刷用新聞用紙,所得平版 印刷用新聞用紙,以前述項目作一評價,結果如表2所示 [比較例6] - 除了僅使用成分A-2澱粉水溶液而成之表面處理劑 外,在與實施例3〜5相同條件下,製造平版印刷用新聞 用紙,所得平版印刷用新聞用紙,以前述項目作一評價, 結果如表2所示。 、 【表2】Language r This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 is publicly available) 585951 V. Description of the invention (Printing of private paper size by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Standards (CNS) A4 ^ i ^ A7 B7 3 ~ 5 Under the same conditions, the lithographic newsprint paper was produced. The obtained lithographic newsprint paper was evaluated based on the aforementioned items. The results are shown in Table 2 [Comparative Example 6]-except that only component A- Except for the surface treatment agent made of 2 starch aqueous solution, lithographic newsprint paper was produced under the same conditions as in Examples 3 to 5. The obtained lithographic newsprint paper was evaluated by the aforementioned items. The results are shown in Table 2. , 【Table 2】
[實施例6〜10] 於成分A-1〜A-3之澱粉水溶液中,將成分B-1〜b_4 水洛液、及成分C-1〜C-3水溶液,以表3之配合比例混 和,調製成表面處理劑,將得到之表面處理劑,於前述新 ,用紙原紙A上’以洗口輕塗機塗佈(塗佈速度:i〇5〇m/ ^ ’兩面塗佈)’塗佈後’進行高溫軟質錢延處理(輕塗 2 1UTC ’線壓i3_/m),製造平版印刷用新聞用紙, :::::印刷用新聞用紙,以前述項目作-評價,結果 X 297 公$ (請先閱-it背面之注意事項再填寫本頁)[Examples 6 to 10] In the starch aqueous solution of the components A-1 to A-3, the components B-1 to b_4, the hyaluronic acid solution, and the components C-1 to C-3 aqueous solution were mixed at the mixing ratio of Table 3. To prepare a surface treatment agent, and apply the obtained surface treatment agent to the above-mentioned new paper, and apply it on a paper base paper A by using a mouthwash light coater (coating speed: i050m / ^ 'both-side coating)' After the cloth ', high-temperature soft money extension treatment (light coating 2 1UTC' line pressure i3_ / m) was used to produce lithographic newsprint papers ::::: printing newsprint papers, with the foregoing items as evaluations, the result was X 297 $ (Please read the notes on the back of -it before filling this page)
585951 A7 B7 五、發明說明() [實施例11] 於成分A-2之澱粉水溶液中,將成分B-1水溶液、 及成分C-2水溶液,以表3之配合比例混和,調製成表面 處理劑,將得到之表面處理劑,於前述新聞用紙原紙A上, 以澆口輥塗機塗佈(塗佈速度:1050m/分,兩面塗佈),塗 佈後,進行硬質夾壓延處理(5段4夾、輥塗溫度6〇°C, 線壓35kN/m),得到平版印刷用新聞用紙,所得之平版印 刷用新聞用紙’以前述項目作一評價,結果如表3所示。 [實施例12] 於成分A-4之陰離子性聚丙烯醯水溶液中,將成分B—i 水溶液、及成分C-2水溶液,以表3之配合比例調製成表 面處理劑,將得到之表面處理劑,於前述新聞用紙原紙A 上’以洗口親塗機塗佈(塗佈速度:1000m/分,兩面塗佈), 塗佈後,進行硬質夾壓延處理(5段4夾、輥塗溫度60。〇, 線壓35kN/m),製造平版印刷用新聞用紙,所得之平版印 刷用新聞用紙,以前述項目作一評價,結果如表3所示。 【表3】 (請先閱讀背面之注意事項再填寫本頁) 裝 · 經濟部智慧財產局員工消費合作社印製 成分A 成分B 成分C 配合比 (A:B:C) 塗佈量 (兩面 點滴吸水 度(秒) 接觸角 (度) 強度 (gf/3cm) 彩色印 刷適性 實施例6 A-1 B-2 C-1 100:15:20 0.40 798 106 29 實施例7 A-1 B-3 C-1 100:5:10 0.46 298 100 31 ◎ 實施例8 A-1 B-4 C-1 100:3:3 0.98 392 98 52 實施例9 A-2 B_1 02 100:5:5 0. 65 165 104 28 實施例10 A-3 B-1 C-3 100:3:5 0.57 82 103 28 實施例11 A-2 B-1 C-2 100:5:5 0.60 141 103 27 ®^〇~ 實施例12 A-4 B-1 02 100:30:30 0.28 45 103 28 ^紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公货) 經濟部智慧財產局員工消費合作社印製 585951 A7 _____B7_ 五、發明說明() 【發明之效果】 以本案發明含有成分A、成分B、成分C3成分之表 面處理劑塗布、乾燥,所得之平版印刷用新聞用紙,其點 滴吸水度、接觸角均·明顯提高厂另外,以含有成分A與成 分B、或成分A與成分C之2種成分之表面處理劑塗佈、 乾燥,所得之平版印刷用新聞用紙,其點滴吸水度及接觸 角並無同時明顯提高;又,本案發明之新聞用紙原紙不管 是酸性造紙或中性造紙均能得到同樣效果,且,本案發明 之平版印刷用新聞用紙具優越之彩色印刷適性。 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公智) (請先閱讀背面之注意事項再填寫本頁)585951 A7 B7 V. Description of the invention (Example 11) In the starch aqueous solution of the component A-2, the aqueous solution of the component B-1 and the aqueous solution of the component C-2 were mixed at the mixing ratio of Table 3 to prepare a surface treatment. The obtained surface treatment agent was coated on the aforementioned newsprint base paper A by a gate roll coater (coating speed: 1050 m / min, coating on both sides), and then applied with a hard nip calendering treatment (5 Segment 4 was clamped, roller coating temperature was 60 ° C, linear pressure was 35 kN / m) to obtain lithographic newsprint paper. The obtained lithographic newsprint paper was evaluated based on the foregoing items. The results are shown in Table 3. [Example 12] The component B-4 aqueous solution and the component C-2 aqueous solution were prepared into the surface treatment agent in the mixing ratio shown in Table 3 in the anionic polypropylene / aqueous solution of component A-4, and the obtained surface was treated. Coating agent on the aforementioned newsprint base paper A with a mouthwash applicator (coating speed: 1000m / min, coating on both sides), and after coating, a hard nip calendering process (5 sections, 4 nips, roller coating temperature) 60. 0, linear pressure 35 kN / m), to produce newsprint for lithographic printing. The obtained newsprint for lithographic printing was evaluated by the aforementioned items. The results are shown in Table 3. [Table 3] (Please read the precautions on the back before filling out this page.) Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Component A Component B Component C Mixing ratio (A: B: C) Water absorption (seconds) Contact angle (degrees) Strength (gf / 3cm) Color printing suitability Example 6 A-1 B-2 C-1 100: 15: 20 0.40 798 106 29 Example 7 A-1 B-3 C -1 100: 5: 10 0.46 298 100 31 ◎ Example 8 A-1 B-4 C-1 100: 3: 3 0.98 392 98 52 Example 9 A-2 B_1 02 100: 5: 5 0. 65 165 104 28 Example 10 A-3 B-1 C-3 100: 3: 5 0.57 82 103 28 Example 11 A-2 B-1 C-2 100: 5: 5 0.60 141 103 27 ® ^ 〇 ~ Example 12 A-4 B-1 02 100: 30: 30 0.28 45 103 28 ^ Paper size applies to China National Standard (CNS) A4 (210 X 297 public goods) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives 585951 A7 _____B7_ 5 Description of the invention () [Effect of the invention] The surface treatment agent containing the component A, component B, and component C3 of the present invention is applied and dried, and the obtained newsprint paper for lithographic printing has a significantly improved water absorption and contact angle. Factory, Coating and drying with a surface treatment agent containing two components of component A and component B, or component A and component C, and the resulting newsprint lithographic printing paper did not have significantly improved water absorption and contact angle at the same time; The newsprint base paper invented in this case can obtain the same effect regardless of whether it is acid paper or neutral papermaking. In addition, the newsprint paper for lithographic printing invented in this case has superior color printing suitability. This paper standard is applicable to China National Standard (CNS) A4 specification ( 210 X 297 public wisdom) (Please read the precautions on the back before filling this page)
告本 修 申請曰期 案 號 9 01217 1Q 類 别 以上各欄由本局填註)(This case, the application date is 9 01217 1Q category. The above columns are filled out by this bureau.)
A4 C4 585951 發明 新型 專利説明書 中 文 發明 $版印刷用紙 英 文 姓 名 國 籍 (1) 高野 (2) 小野 (3) 藤原 幸司樹 俊裕秀 均曰本 發明 創作 人 住、居所 $ i Ϊ 屢慶lif 姓 名 (名稱) 國 籍 曰本製紙股份有限公司 曰本 申請人 住、居所 (事務所) 代表人 姓 名 曰本國東京都北區王子5丁目21番1號 河澄和夫 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)A4 C4 585951 Inventive New Patent Specification Chinese Invention $ Printing Paper English Name Nationality (1) Takano (2) Ono (3) Fujiwara Yukiji Toshiki Yuu Hideki said the creator of the present invention, residence $ i Ϊ 庆庆 lif Name ( (Name) Nationality Japan Paper Manufacturing Co., Ltd. Japan applicant's residence, residence (office) Representative name: Japan, Oji 5 Chome 21, No. 1, Kita-ku, Tokyo, Japan Kawasaki Kazuo Paper size applies to Chinese National Standard (CNS) A4 (210X297 mm)
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TWI401163B (en) * | 2009-06-05 | 2013-07-11 | Jujo Paper Co Ltd | Thermal record |
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JP5501975B2 (en) * | 2008-10-31 | 2014-05-28 | Mtアクアポリマー株式会社 | Method for dissolving water-soluble polymer |
US8871678B2 (en) | 2010-03-15 | 2014-10-28 | Nippon Paper Industries Co., Ltd. | Thermosensitive recording medium |
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JPH08291497A (en) * | 1995-04-20 | 1996-11-05 | Harima Chem Inc | Paper coating agent |
JP2939971B2 (en) * | 1995-06-23 | 1999-08-25 | 日本製紙株式会社 | Printing paper with improved water absorption, newspaper printing paper, and method for producing the same |
JP3518290B2 (en) * | 1997-11-06 | 2004-04-12 | 王子製紙株式会社 | Newsprint paper for offset printing |
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2001
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