TW585951B - Offset printing paper - Google Patents

Abstract

The present invention provides excellent offset printing paper, particularly offset newsprint suitable for colour printing.

Description

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_ 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 · 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

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

It 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

、 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 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 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})

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

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)

585951

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.

• 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: 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)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 585951 A7 B7 V. Description of the invention (

[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)

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】

[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 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)

(This case, the application date is 9 01217 1Q category. The above columns are filled out by this bureau.)

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)

Claims (1)

Λ8 B8 C8 D8 Ingredients C Patent application scope Lithographic printing paper, attached to the base paper of printing paper, with the following principles; And the obtained after drying; component A ·· water-soluble polymer;, a copolymer of a styrene monomer and an anionic monomer, and a water-soluble copolymer containing 2% to 8G of styrene ethyl monomer as a main component Surface sizing agent; copolymer of olefinic monomer and anionic monomer, water-soluble copolymer containing 20 to 80% by weight of olefinic monomer as the main surface sizing agent. 2: A kind of newsprint for lithographic printing, tied to newsprint base paper, will apply. The component A, component B, and component c described in item 1 of the monthly patent are the surface treatment agents composed of the three components, which are obtained by coating and drying. 3. The lithographic newsprint as described in any one of the items in the scope of the application for patents, wherein the drop water absorption (measured according to the method in Japan TAPPI ^ 0.33, the amount of dripping water is 1 // 1) at 1 Within a range of 0 seconds to 300 seconds, and the contact angle (the contact angle after 0.1 seconds after 1 drop of water drops) is 90 degrees or more. twenty three