TW571013B - Surface-sizing agent - Google Patents

Abstract

Disclosed is a surface-sizing agent for papermaking, which agent is excellent in mechanical stability and storage stability, and has excellent properties for sizing acidic to neutral papers. When applied to communication paper, especially to ink-jet printing paper, the sizing agent provides the paper with excellent properties suitable for ink-jet printing. Also, when a coating liquid including the sizing agent is prepared, the liquid has significantly reduced foaming. The agent is excellent in the compatibility with other chemicals to be used in combination. The surface-sizing agent is obtained by polymerizing (b) a nonionic hydrophilic monomer and (d) a hydrophobic monomer in the presence of (a) an alkaline salt of shellac, and then mixing a polymeric dispersant with the polymerized monomers.

Description

571013 ---- Case No. 89128114 _ Only Zheng _ V. Description of the invention (1) ------ Technology The present invention relates to surface adhesives, more specifically, to mechanical stability, preservation Stability, adhesiveness for acid paper to neutral paper 疋 coincidence ^ the suitability of data paper, low foaming in the coating solution, and other drugs. It is a surface adhesive for papermaking with excellent compatibility. μ Background technology The surface adhesives used in papermaking in the future include styrene-maleic acid copolymers, styrene- (fluorenyl) acrylic copolymers, and α ~ diluted maleic acid An aqueous solution of an alkali metal salt such as an acid copolymer. Although the surface adhesive of styrene-maleic acid copolymer shows good adhesive effect on acid papermaking using many alumina sulfates, it does not apply to neutral papermaking using aluminum sulfate and aluminum sulfate. Paper with a low amount of soil and neutral papermaking has significantly worse adhesive properties. In addition, when the surface is coated, because the adhesive itself foams a lot, it is necessary to increase the amount of the defoaming agent. As a result, the coating surface is depressurized and the adhesive effect is deteriorated. Although the surface adhesive of styrene- (fluorenyl) acrylic copolymer shows good st ^ chigt viscosity j for the above neutral papermaking paper, it has poor adhesiveness in ink writing, so it has Text leakage and other issues. Also, the coating prepared by using this surface adhesive), because the son-in-law property to metal ions is significantly poor, so it has many operations such as agglomerates (referred to as / meal in factories) and foaming Problem. Although the surface adhesive of α-ene-maleic acid-based copolymer shows a good ink viscosity, if it is used for paper, the toner will be fixed.

571013 Month Amendment—Case No. 891 ^ 114 V. Description of the Invention (2) Low adhesiveness' If used for printing paper problems, use 敁 矣 and be jealous h ^ There are many problems in the workability of ink adhesion . The coating liquid of W, which has foaming properties, and the second type of latex-type surface adhesive by the emulsion polymerization method are reported in the prior art type. [Special] Several people have disclosed in Japanese Patent Application Laid-Open No. 8-246391, "In an aqueous solution containing ⑻ 3 (1) 3 carboxy unsaturated monomers and (2) hydrophobic unsaturated ◦ parts by weight, Α] Hydrophobic Fuji 10 ~ 50 0 reset emulsion emulsion polymerization: adhesive. μ Rewind surface adhesive for clothes and paper This particle-type surface adhesive is more soluble than the previous solution-type surface adhesives, and is more compatible with other drugs used in combination, and is more stable to dissolve broad metal ions when preparing coating solutions. Properties, or the foamability of this coating solution has been improved, = its adhesive properties are still insufficient. ° One more and more 'in JP-A 4 9-5 0 2 0 9, it is disclosed that "in the test solution of shellac, styrene and styrene derivatives are produced to ^-^ monomers Or, if necessary, it can be mixed with other copolymerizable monomers, and a free radical polymerization catalyst can be added to the surface processing agent of the paper obtained from the aqueous dispersion obtained by copolymerization. " However, the aforementioned surface processing agent is an emulsion polymerization of styrene and styrene derivatives in an aqueous ammonia solution of shellac. Although the water resistance and gloss of the paper can be improved, agglomerates and the like occur during the emulsion polymerization. Manufacturing problems and insufficient water resistance. In addition, the stability of the obtained surface processing agent to metal ions and mechanical stability is extremely poor, so it is produced in actual operations.

571013 Fifth, the invention of the month _ ^ is causing various problems. In addition, suspension, fi * require the use of single ^ not only for inkjet only, paper, but also for PPC paper, but also require the printing of color oily ink by the inkjet method of the printing quality bleed out of the boundary of the print quality = ^, feathery Echoing (feathering), peeling inside, edge adhesive. , W is suitable, and it is expected that the glue that meets this suitable paper is excellent, and provides mechanical stability and adhesive stability of the adhesive itself. Paper = paper to neutral paper has excellent adhesive properties. Coated, night ink 1 ink paper has excellent inkjet suitability, and is more suitable for the preparation of chemicals. The foaming properties of this coating solution are significantly smaller, and combined with other inventions > a, 杬 良 之Surface adhesives for paper making are used for this purpose. In at least *: et al., '' The research was repeated to solve the aforementioned problems, and the result was that the hydrophilicity was a salt, and the order of the hydrophobic monomers and non-ionic protons was to make it a hydrophobic early body and non-ionic hydrophilic. After polymerizing the anionic monomer and anion or polymerizing it, the polymer dispersant is mixed, and the following are: substances other than salts, which have interfacial activity, non-: raw T f: non-ionic hydrophilic monomer, or hydrophobic The monomer consisting of γ human% ^ premature precursor and anionic monomer is used to complete ^ ΐ ί 5 Glue metal test salt and polymer dispersion 胄, to reach 1 surface adhesive for papermaking that can overcome the aforementioned problems . That is, in the first aspect of the present invention, polymer molecules 571013 89128114 are mixed in a reaction solution obtained by polymerizing a polymer and a hydrophobic monomer in the presence of a metal test salt of gluten.

V. Description of the invention (4) The surface adhesive obtained by the method (2) The second aspect of the present invention is that the alkali metal salt of shellac (a) exists (b), the anionic monomer & In the ionic hydrophilic monomer solution, the third state of the reaction obtained by polymerization of the polymer dispersant monomer ⑷ is the obtained surface adhesive, the alkali metal salt of gray shellac (in the presence of (f), The surface adhesive obtained by dispersing Λ mixed and cut gold test paper and polymer knife and moon tablet K e) with non-isolated; ^ f fourth aspect of the present invention is square% shellac Non-alkali metal salts (a), other substances with interfacial activity, are below, in non-ionic hydrophilic monomers (b), anionic monomers, (:) / sparse t! In the reaction solution obtained by the polymerization of the body, 'mixed insect wins: the surface adhesive obtained by the test (a) and the molecular dispersant (e), the fifth aspect of the present invention is an alkali metal salt containing shellac ( a), with a non-ionic hydrophilic monomer (b) and a hydrophobic monomer ((1) as a repeating unit of the polymer, or ^ = child hydrophilic monomer (b), anionic monomer The body (c) and water list = the polymer of the repeating unit, and the surface adhesive of the polymer II, 7 ~ dande is the sixth aspect of the present invention is any one of the foregoing first to fifth State-like shellac, other than alkali metal salts (a), substances with interfacial activity (^)

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571013-Case Long V. Description of the invention ^-^ ~ Correction __ is a boundary adhesive with a polymerizable group, the seventh aspect of the present invention described in the above item 3 or 4 of the sex agent is # Interface with a polymerizable group: The reactive emulsifier of allyl in the fifth aspect, the sexing agent is fluorenylpropenyl and / g The eighth aspect of the present invention is # In the aspect of any one of the foregoing non-ionic hydrophilicity σσ to ~ 5, the acrylonitrile and (meth) acrylic acid ^ (b) are the ninth state of (meth) acrylamide and propyl. "At least one kind is selected from the ㈡ group, and the aforementioned hydrophobic monomer (d) is θ; ^ In the fifth aspect,

In the group consisting of alkyl esters, one is selected from ... a small styrene derivative and (meth) acrylic acid king), and the tenth aspect of the invention is the state of any one of the foregoing anionic monomers (5th and 5th) In the present invention, the twelfth Γ sample of the present invention) / monomer having an acid-acid group, in ... the aforementioned polymer dispersant (e) or (formaldehyde C) Copolymerization of dilute acid I is the material. Acetyl acrylic acid copolymer salt and /

The surface adhesive of the present invention is a latex-type surface adhesive. The surface adhesive is passed through the shellac metal test 赜 (㈢ * ㈢ This surface is adhesive ^ ^ (b) ^^ ^ ^ ^^ ^ ⑴, anionic monomer (e ) And hydrophobic unisex monomers: mixed with the polymer dispersant (e) can obtain heart-stage polyalkali metal salt (a) with the ability of interfacial activity = in the presence of shellac ") ,

571013 The fifth revision of the month, description of the invention (6) The non-ionic hydrophilic is placed into the hydrophilic monomer ⑻, the heart 3 di-aqueous monomer ⑷, ★ non-ionic-stage polymer in the anion / 乂 early body ⑷ and Hydrophobic monomers (d) and polymeric powders (e) are available. Acetic acid private metal salt (a) and macromolecules The shellac used in the present invention is composed of the secreted resin-like substance made from shellacs that are produced from plants, such as shellac and lac Shell: 4 acid: J ί ί: f mixture and a combination of several such softening resins. The softening resin of ... = the so-called alkali metal salt of shellac 2 was neutralized. In order to obtain worms, there are two; knee: test substance if the shellac is substantially soluble in water: test, but caustic alkali, caustic soda and ammonia are preferred. ;, F 2 is particularly limited, the acid value relative to the contact adhesive is equal to or higher than the equivalent value, then, the stability and the resulting surface adhesive of the ancient and 2 hydration on this day " "Six:" It is better in terms of. 厶 is # 人, 隹-there is an alkali metal salt that touches the glue, so that poly =; = 'fine particles can be obtained during polymerization; and: minus: ::::: The compound has good stability. 'Improved water resistance, and the substance (f) other than the alkali metal salt of shellac used in the present invention can be a well-known emulsifier or dispersant. Liesheng: Polymeric base surfactant, two-sided adhesive, and poly :: A: r:; r excellent foaming table ... Qiaolaikou τ violent interface activity sword is # The aforementioned low molecular surfactant is usually Suitable for emulsifying polymer 571013 5. Description of the invention (7) From the viewpoint of using non-ionic, anionic, amphoteric and cationic low stability, non-ionic; Low-molecular surfactants are preferred? Low-knife surfactants and anionic surfactants can be exemplified by polyoxybenzyl benzene Extension, elementary bond, polyoxyalkylene fatty acid, polyoxypropylene fatty acid ester, sorbitan fatty acid ester, polyglycol fatty acid ester, polyoxyethylene polysaccharide Acid saccharine, fatty acid esters of alkyd anhydride, saccharose fat = fatty acid diethanolamine, polyoxypropylene polyoxyethyl low-molecular interface activity 彳 Use-more than one kind of non-ionic sleeve: Examples of the active agent include phosphoric acid, salts, and acid salts of polyoxyalkylene benzene scales, polyoxylate-benzylphenylsulfonium, polyoxyalkylene groups, polyoxyalkylene fatty acids, and vinegar. , No. station acid and vinegar = acid vinegar salt, and alkyl benzoate, methyl naphthalate, condensed europium, dilute succinate, pine resin = metal salt. In the present invention, can be used alone -1 type, or a combination of the aforementioned anionic low-molecular-weight surfactants of 1 = gold. Examples of the cationic surfactants include tetrakismonium chloride, gasified benzyl ammonium, carbamoylamine, mono- and polyoxyethylene. Amines, etc. Used in this group, or a combination of two or more of the aforementioned cationic low fractions 4 * Surfactant with a polymerizable group described above a It is generally called a reactive emulsion 'and has a hydrophobic group, a hydrophilic group, and a carbon-carbon double bond compound in the molecule. 57013 Case No. 891 ^^ 5. Description of the invention (8). The so-called carbon-carbon double pentamidine 7, Double bonds in 2-methyl + propanyl, 2 (methyl) propenyl, propenyl, etc. "Alkenyl, ethyl, and (fluorenyl) propenyl have more than polymerized The pre-polyoxyalkylene sulfonate has a monophenyl ether-based sulfalyl diacid, a decylhexadecyl salt, and the like. The aforementioned has a polymerizable property of ~ 5 weight of gold alone. #Helmet surfactant can be used usually suitable for emulsification. Ten-Official IA 1 is limited, and specific examples can be exemplified by a molecule with a druid b Glycogen alkyl phenyl ethers, alkyl alkane ethers, polyoxyalkylene aralkyl ethers, sulfonium sulfate, monophenyl and diphenylethenylbenzene, etc. Succinate salt, tr group in the molecule: polyoxyalkylene alkyl ether or polyoxyalkylene of g energy group, spargan carboxylate, acid phosphate (fluorenyl) acrylate ^ ^ ^ methyl ) Glycidyl ester-based compounds, and benzyl ether disulfonic acid compounds, such as hexyldiphenyl ether-sulfodiphenyl adipic acid, dodecyl diphenyl ...

One, one's human I, acid and its sodium salt, potassium salt and other metal salts and ammonium formula, preparation, can be used alone or in combination of two or more kinds of surfactants with f-synthetic group. '1 Said surfactant (f) in the alkali metal salt without using shellac and ^ ^ with respect to the hydrophobic monomer (d) 100 parts by weight is used 0.5 parts, and in the base of B and shellac When the metal salt is used in combination, it is in a range of 20 parts by weight based on 100 parts by weight of shellac. '' The aforementioned polymer dispersant (e) used in the present invention can basically be a synthetic polymer having a hydrophobic group, a non-ionic group and / or an ionic group, or a general natural polymer dispersant. An example of a synthetic polymer is polyvinyl alcohol and its modified product, anionic styrene— (曱

571013 V. Description of the invention (9) ~ Partial or complete neutralization of acrylic acid-based copolymers, anionic or cationic (fluorenyl) acrylate copolymers or (fluorenyl) acrylamines. Resins, polyesters, amino acid esters, alkyds, and polyamines, etc. ^ =: Examples of high emulsifiers include casein, namely phospholipids, acetylenes, starches, and processed starches. Wait. In the present invention Yes! These polymer dispersants are used alone or in combination of two or more kinds. Suitable polymer dispersions in the present invention are: Moqiu Extraction Order * is an ethylene methyl) acrylic acid copolymer. And (fluorenyl) acrylate. The aforementioned polymer dispersant (e) can be used in combination with an alkali metal salt before polymerization, but it can be added after polymerization. Blade stability, mechanical stability and dilution with water containing metal ions ± ^ = mechanically good. ^ Dilution stability with dilute material The amount of the molecular dispersant (e) used is relative to 1. 〇Parts by weight 5 to 100 parts by weight, more preferably = Cao Shui said monomers ⑷ Even if more is added, the range of ^ 5,0 ^ parts in which the above-mentioned effect is not observed, it is not good because it can be reduced. In the present invention, the cause of adhesion is caused by the non-ionic hydrophilic component, which can particularly suppress the by-products generated during the emulsification polymerization: as a polymerization and has the advantage of being easy to manufacture, and also the occurrence of aggregates 'The stability of storage, the advantages of surface adhesive for metal ions =. Good bio- and mechanical stability The non-ionic hydrophilic group and anionic used in the present invention are hydrophilic ^ is ^ has a cationic monomer, its legs page 13 (:: \ 总 段\ 89 \ 89128114 \ 89128114 (replacement Bu; 1.1) {(: 571013 month revision date 8912RJ2 £ V. Description of the invention (ίο) For example, (fluorenyl) acrylamide, alkanol, etc. can be listed separately in the present invention Use a non-ionic hydrophilic monogroup of di- and (meth) acrylic hydroxy groups, or use two or more kinds of polymers together if it is a polymerizable monomer that does not have an ionizing Wk dual-use ionic hydrophilic mono-aqueous group, It is a H-ionic group and has a parent. The aforementioned non-ionic hydrophilic monomers are preferably non-ionic and water-soluble monoenefluorene amines. 2 'In the present invention, a cheap and easily available propyl group is used, which is hydrophobic The surface adhesive obtained from the polymer sheet has good water resistance.) U is a polymerization component, which can make the hydrophobic monomer used in the present invention (the hydrophobic monomer can be exemplified by phenethyl /, and GS water-insoluble monomers. This group Stupidity of toluene, divinylbenzene, etc. Shaped (fluorenyl) acrylic acid vinegar, cis. Materials: (Methyl) propanoic acid, dialkyl diesters, 5 to 10 carbons of quinone, and fumaric acid diene esters Vinyl esters, N alkyl (vinyl dicarboxylate, vinyl propionate, etc.) These various kinds of hydrophobic mono "propylamines" and methyl ethyl are used in more than two kinds. Use (methyl) =-species Or when mixed, the blending ratio is such that the amount of the hydrophobic monomers of other hydrophobic monomers of methyl methenoate is at least 25% by weight, which is better than all for the adhesive performance., It is preferably 40 to 100% by weight. In the present invention, if anionic sculpting is used to improve the stability 2 C of emulsion polymerization as the polymerization component, the mechanical stability of the adhesive is further improved. 2 The advantages, and the obtained surface of the anionic mono fe (c) used in the present invention is C with an anionic group: \ Total file \ 89 \ 89128114 \ 89128114 (replace) -1.ptc Page 14 / 丄 υ丄 j / 丄 υ 丄 j Revised fifth, description of the invention (iG '~--^ year _____ a monomer, which can be exemplified by diacid, itaconic acid, ^ methyl Acrylic acid, maleic acid, transbutylene ethylene sulfonic acid, (methacrylic acid, butenoic acid and other monomers with a slow acid group, acid, sulfonated styrene, acrylic acid, 2-propane Dilute acid amines " " 2-methyl propylene sulfonate phosphoric acid r and other monomers having a continuous acid group, (meth) acrylic acid hydroxyl body can be used alone 9-i having a phosphate group Monomers. These anionic monomers with an anion group are used in combination of two or more. Among them, they also have characteristics, so it is better, and the body is good for imparting low foaming properties to surface adhesives. ", , ', And (meth) acrylic acid and itaconic acid are also specifically combined with 3: =). Non-reactive ionic monomers such as Hurricane, σ, and nonionic hydrophilic monomers ( b) in combination with yin and early limbs (c) and hydrophobic monomer (d). By using a combination of non-ionic monomer (b) and hydrophobic monomer (d), the cost can be reached: _ 纟, and the right uses non-ionic hydrophilic monomer (b) and anionic :: / dihydrate monomer The combination of the body's can obtain an excellent surface adhesive with improved mechanical stability. That is, the surface adhesive of the present invention contains a non-ionic hydrophilic body (b) and a hydrophobic monomer ((0 as a polymer of repeating unit, and a non-ionic hydrophilic monomer (b), an anionic monomer The body (C) and the hydrophobic monomer ^ (d) are used as the polymer of the repeating unit. Early makeup The shellac alkali metal step (and the sub-soap body (c), the hydrophobic monomer) Body (d) and polymer dispersant (the amount of "magic" is relative to 100 parts by weight of hydrophobic monomer (d), and the alkali metal salt of shellac C: \ Total file \ 89 \ 89I28] M \ 89128114 ( Replace) -1.ptc page 15571013

Case No. 891 ^ 114 V. Description of the invention (12) 20 parts by weight and substances with interfacial activity (f) 05 ~ 5 heavy deniers Nonionic hydrophilic monomer (b) 1 ~ 20 parts by weight and The anionic monomer (c) is 0.1 to 10 parts by weight, and the polymer dispersant (e) is 5 to 100 parts by weight: m] is better in terms of stability and adhesive properties, and particularly preferred is relative : 100 parts by weight of lyophilic monomer (d), 5 parts by weight of alkali metal salt of shellac; parts, substance with interfacial activity (f) 0 5 ~ 3 parts by weight, and hydrophilic monomer (b) 5 ~ 15 Parts by weight, anionic monomers (0.5 to 5 parts by weight, two molecules of dispersant (e), 5 to 50 parts by weight. Still, the amount of the aforementioned substance (f) having interface = sexual ability is not used before Combined use of shellac's alkali gold ': It is the amount used when used alone, and it is used in combination with the worm test gold heart (the next j is used relative to the alkali metal salt (a) of shellac. 20% by weight J • range When manufacturing the surface adhesive of the present invention, the previous public method can be applied, and the solution polymerization method and the block polymerization method can be applied. L Qing: The emulsification polymerization method is used as ", ... existed before In the case of shellac, it is thought that this shellac also participates in the polymerization of free radical polymerization catalysts used by the polymer / polymerization method. Examples include persulfate, persulfate, sodium persulfate, third persulfate, etc. 2 t, peroxides such as hydrogen peroxide, redox polymerization catalysts of these persulfates or peroxidase combinations, or 2,2, azo month, 2,2-lice Bis-2-methylpropane dichloride can be used again and again. If necessary, a well-known chain-moving agent can be used together. Horse milk can be used as a catalyst. The base paper used in the surface adhesive of the present invention is "paper used in Qianzhong"

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_Ά 8912R1U Correction g, description of invention (13) Pulp can--1— Pulp, broken wood, ί: T :: J :: bleached or unbleached chemical f yield pulp, old newspaper, paper, old machine : Old paper pulp such as bleached or unbleached paper such as pulp. ~, Old corrugated cardboard or deinked old adhesive, alkyl diene sulfonate, rosin resin for acid papermaking: rosin resin for sex papermaking. ::: Adhesive for neutral papermaking. Filler can be stone 丨: *, as required physical properties as required = Filling can be listed as clay, talc, oxidant ::? Calcium find. They can be used alone or in combination. Negative m inverse acid is used to apply the surface adhesive of the present invention to a press, a film press, and a mouthwash light coating. A glue coater, a calender, a bar coater, Knife & Machine, To Tech Line Coating. Congratulatory coating machine When the surface adhesive of the present invention is coated on the surface of the base paper, it can also be used for cellulose such as oxoesterified starch, acid modified starch, cation ... Water-soluble polymers such as polyacetic acid and soda are mixed in the coating liquid towel, and other surface adhesives, anti-slip agents, preservatives, rust inhibitors, additives, viscosity modifiers, dyes, pigments and other additives are added. Also helmet. … The paper obtained by coating the surface adhesive of the present invention on the aforementioned base paper can be various papers and board papers. Examples include, for example, paper for ppc, inkjet, etc. *

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Recording paper, laser printing paper, format recording paper, recording paper, Kolo paper, thermal transfer paper, thermal paper, coated paper, kraft paper, pure white paper, coated paper, high-quality coated paper 、 Other note-taking paper. Paper, packaging paper such as 'book = paper', photo paper such as foreign paper, Manila board, paper: printing paper, news board, liner board, etc. For paper machines such as reverse paper, wood board, etc. The surface adhesive of the present invention is usually coated with a concentration of 0.1 to 5 denier. In the coating liquid used in τ, the adhesive effect is less than 0. 1% by weight, preferably 0. 2 to 1% by weight. If it is more than 5% by weight, the adhesion is hardly improved enough, and even if it is used, it is not good. 'It is fruitless and economically uninteresting. Therefore, the coating amount is usually solid-type ·· lg / m2. If the F range is 0 · 01 ~ lg / m2, preferably 0.002 ', the adhesive effect is particularly effective. The following examples and comparative examples are used to further describe the present invention in detail, but The invention is not limited to these examples. (Synthesis Example 1) According to Reference Example 2 of Japanese Patent Application Laid-Open No. 8-2 4 6 3 9 1, an aqueous solution of an ammonium salt (g-1) of a styrene-acrylic copolymer as the molecular dispersant in the present invention was used. That is, the polymer dispersant solution (S-1 solution) is synthesized by the following treatment. In a 1-liter four-neck flask equipped with a stirrer, thermometer, reflux cooling tube, and nitrogen introduction tube, add 00 parts of water and 75 parts of 95% isopropanol, and heat while taxing to raise the temperature to 80 ° c. until. In this, 45 parts of styrene and 55 parts of acrylic monomer were mixed, and 5 parts of potassium persulfate was mixed.

571013 Case No. 89128114

V. Description of the invention (15) The polymerization initiation solution dissolved in 1 to 20 parts of water lasted for 3 hours to complete the reaction. After that, 46.4 parts of the aqueous solution of diisopropylamine were distilled (added to 100% of acrylic acid, adjusted to make the concentration of the copolymer to 20%, and ears) and diluted with water. The salt of the acid copolymer (s—water, volume = water-soluble copolymer styrene ethyl solution (S-Π solution). The liquid 'is the polymer dispersant (Synthesis Example 2). It is equipped with a stirrer, thermometer, and reflux cooling. Tube and nitrogen introduction tube into a four-liter flask, charged with 586 parts of water, 80 parts of styrene, 39 parts of α-fluorenylstyrene, 22 parts of fluorenyl acrylate, 75 parts of methacrylic acid, = dodecyl 3.3 parts of thiol, soda dodecylbenzenesulfonic acid] parts, 33 parts of 30% ammonium persulfate aqueous solution was added and heated at 80 ° C, and heated at 80 ° C for 2 hours to complete the reaction. Thereafter Add 30% caustic soda solution to 2 parts (relative to 95 mol% of fluorenyl acrylic acid), and keep it at 80 t for 30 minutes. Dilute with water '' to make the copolymer concentration 25% 'to obtain water-soluble Polymer dispersion solution (S-2 solution), which is an aqueous solution of the sodium salt (S ~ 2) of styrene-acrylic acid-fluorene-based acrylic copolymer. Example 1) A 1-liter four-necked flask equipped with a stirrer, thermometer, reflux cooling tube, and nitrogen introduction tube was charged with 5 3 5 parts of water and shellac (N 8 1 1 manufactured by Gifu SHELLAC Co., Ltd.) 1 3 · 2 Parts (8 parts by weight when the entire apparent hydrophobic monomer is 100 parts by weight), 4.2 parts by ELEMINOL JS-2 (manufactured by Sanyo Kasei) (1 part by weight when the entire hydrophobic monomer is 100 parts by weight), 4 份 ， 12.9 parts of acrylamide (depending on 100 parts by weight of the hydrophobic monomer as a whole), 48% caustic alkali 3.4 parts,

C: \ total file \ 89 \ 89128114 \ 89128114 (replacement) -l.ptc page 19 5. Description of the invention (16) and then add 64 · 5 parts of styrene (depending on the hydrophobic monomers as 100 parts by weight) 40 parts by weight), 96.7 parts of n-butyl acrylate (60 parts by weight for 100% of total weight of hydrophobic monomers), and 0.8 parts of ammonium persulfate, mixed under a nitrogen stream Stir while heating up to 8 ° C. Hold at 8 ° C for 2 hours to complete the emulsion polymerization reaction. Add 161 parts of polymer dispersant solution (S-1 solution) (depending on the weight of the hydrophobic monomer as 100%). Part, s— 丨 is 20 parts by weight) to obtain a latex-type surface adhesive with a solid portion concentration of 25.3%. (Implementation 2-9, Comparative Examples 1-4) Except 々XJX 5 shovel as The types and amounts of powders, nonionic hydrophilic monomers, and anionic monomers, the types and amounts of hydrophobic monomers, and the types and amounts of dispersants after polymerization are changed as shown in Table 丨. Latex type surface adhesive. (Comparative Example 5) Comparative Example 5 uses commercially available styrene-propionic acid SS315 (manufactured by Japan PMC). J ^ (Experimental Example 1) Evaluation of acid-quality high-quality paper (1) Manufacture of base paper for acid-quality high-quality paper, 380 milliliters of pulp (mixed pulp of wide pair 1) mashed to Canadian Standard Freeness (c_di Standard Freeness) 5t τ τ stay W of λ water ratio Feng y in pulp (absolutely dry heavy water 'and added relative weight basis) sulfuric acid soil, 2% (absolute dryness basis) acid paper rosin for paper ^ ^ After 0.3% of absolute water (but absolute dry weight D, glue point (manufactured by Japan PMC, · AL120), M 571013-tH "month 9128114 _ ^ _ ^ V. Description of the invention (17) '--- The pulp slurry was diluted to a concentration of 0. 25% with diluent water of PH4 · 5. Thereafter, a yield enhancer (NR12MLS manufactured by H ^ M0) was added to the pulp, and Noble & Wood papermaking machine, making paper with a basis weight of 65g / m2. At this time, the papermaking pH was 4.5. The wet paper was dried using a drum dryer at 1000 ° C for 80 seconds. (2) Method for adjusting coating liquid Dilute oxidized starch (MS3800 Japan Food Chemical Co., Ltd.) with water to a concentration of 10% It was gelatinized at 95 ° C, and the surface adhesive was mixed with the gelatinized solution to prepare a coating solution. At this time, the oxide powder and the solid part of the surface adhesive in the coating solution were mixed. The concentration is adjusted to the following value. Then, the coating solution 2 is adjusted to pH 8 with caustic soda or sulfuric acid, or adjusted to pH ρ with sulfuric acid, so that a coating solution of pH 8 and a coating solution of pH 6 can be prepared. Solid part concentration of oxidized starch in the coating solution: 6% Solid part concentration of the surface adhesive in the coating solution: 0.2% (3) The production and evaluation of acidic high-quality paper are described in (1) above. On the copied base paper, the coating liquid prepared in the above (2) was coated with an adhesive press to obtain an acidic high-quality paper. The obtained test paper was conditioned for 24 hours in a strange temperature and humidity (20 ° C, 65% relative concentration) environment, and the St ΰ chigt viscosity (based on Jis P8122) and the ink writing viscosity (based on J TAPPI pulp test) were measured. Method No. 1 2-76). The evaluation results are shown in Table 2. Still, the higher the values of S t 6 ch i g t adhesive and ink writing adhesive, the better the display. / (Test Example 2) Evaluation on neutral high quality paper (1) Manufacture of base paper for neutral high quality

\\ Eight 326 \ Overall files \ 89 \ 89128114 \ 89128114 (replacement) -1. Mouth 571013 --- Age L89128114__Year month and month Amendment V. Description of invention (18) " " ~ " --- will 380 milliliters of pulp pulverized to Canadian standard beating degree (mixed pulp of broadleaf to needlewood pulp ratio of 9 pairs 丨) to make a 2.5% flow pulp, and 2% (relative to pulp) Absolute dry weight basis) of calcium carbonate (manufactured by Okutama Industries; TP1 215). Amphoteric starch (Nati〇nai) was added in order to 0.5% (absolute dry weight basis) of the paper.

Manufactured by Stajrch Corporation; Cato 3210) and a fire-based diketene-based adhesive (made by PMC; AS2 63) based on pulp (0.08% (absolutely dry heavy star basis)). Then, this pulp slurry was diluted to a concentration of 0.25 / 〇f L with a dilution water of PΗ7.5, and then 8% (absolute dry weight basis) of the pulp was added to the diluted pulp slurry. Calcium Carbonate (manufactured by Okutama Industry Co., Ltd .; TP 1 2 1 S), a yield enhancer (η j M0; NR12MLS) relative to pulp, and a Noble & Wood & paper machine, The bang amount was 65 g / m2. At this time, the papermaking Ph at this time was 7.5. The wet paper was dried using a drum dryer at 80 ° C for 80 seconds. (2) Preparation method of coating liquid Dilute oxidized starch (MS 3800 Japan Food Chemical Co., Ltd.) with water to a concentration of 10%, gelatinize at 95, and mix the aforementioned surface with this gelatinized liquid An adhesive is prepared into a coating liquid. At this time, the concentration of the oxidized starch and the solid portion of the surface adhesive in the coating liquid were adjusted to the following values. Then, this ^ cloth solution is prepared into p Η 8 with caustic soda or sulfuric acid, and a coating solution of ρ η 8 can be prepared. Solid part concentration of oxidized powder in coating solution: 6% Solid part concentration of surface adhesive in coating solution: 0.2% (3) Manufacturing and evaluation of neutral high-quality paper

571013 Fix

Case No. 89128Π4 V. Description of the invention (19) On the base paper copied in (1) above, apply the coating adhesive pressure machine configured in (2) above to obtain a neutral high-quality paper. The obtained test: 调 Adjust the humidity for 24 hours under a constant temperature and humidity (20 t, 65 relative humidity) ^ R Test Example 1, and perform St dchigt viscosity and ink writing glue. The results are shown in Table 2. Then, (Experiment Example 3) Based on the evaluation of inkjet recording paper *, 38G milliliters of pulp pulverized to Canadian standard beating degree (mixed pulp of broadleaf tree with a pulp ratio of 9 to 1) was made into a 2.5% slurry, It is advisable to add carbonic acid to the pulp ％ (absolute dry weight basis)… (manufactured by Okutama Industrial Co., Ltd .; TP121S) & 5% talc (manufactured by Fuji Tin ALc Engineering Co., Ltd .: ND TALC). Amphoteric starch (manufactured by National Star Co., Ltd.) relative to pulp (absolutely dry basis weight basis) and amphiphilic starch 0.5% (absolutely dry weight basis basis) of pulp was added sequentially.

Ca t 〇 3 2 1 0) and 0.3% (absolute dry weight basis) of paper pulp based rosin-based adhesive (manufactured by Japan PMC; CC167) for neutral paper. The pulp slurry was diluted to a concentration of 0.25%. Thereafter, 4% (absolute dry weight basis) of carbonic acid (manufactured by Okutama Industry Co., Ltd .; TP1 21 S) with respect to the pulp was added to the diluted pulp slurry, and a yield improver of 0.01% with respect to the pulp was added. (Manufactured by ΗΙΜ0; NR12MLS), and Noble &

The Wood Papermaking Machine 'performs papermaking with a basis weight of 65 g / m2. At this time, the papermaking pH at this time was 7.5. The wet paper was dried using a drum dryer under conditions of 800 seconds. (2) Preparation method of coating liquid Dilute oxidized starch (manufactured by Japan Food Chemical Co., Ltd.) with water to a concentration

Dagger \ Total file \ 89 \ 891281 14 \ 89128114 (replacement) -1. Port 1 Page 23 571013 _Case No. 89128114_ Year Month Revision_ V. Description of the invention (20) Degree 10%, and at 95 ° C is gelatinized, and the above-mentioned surface adhesive and common salt are mixed with this gelatinized liquid to prepare a coating liquid. At this time, the concentration of the solid portion of the oxidized starch, the surface adhesive and the common salt in the coating liquid was adjusted to the following values. This coating liquid is then adjusted to pH 8 with caustic soda or sulfuric acid, and then it can be adjusted to a coating liquid of PH 8. Solid part concentration of oxidized starch in coating liquid: 8% Solid part concentration of surface adhesive in coating liquid · 0.2% Solid part concentration of table salt in coating liquid: 0.5% (3) Manufacture of recording paper On the base paper copied in the above (1), the coating liquid prepared in the above (2) was coated with an adhesive press to obtain the recording paper. The obtained test paper was conditioned under a constant temperature and humidity (20 ° C, 65% relative concentration) environment for 24 hours. (4) Evaluation of recording paper The test paper obtained in the above (3) was humidity-conditioned for 24 hours under a constant temperature and humidity (20 ° C, 65% relative density) environment, and the following inkjet suitability test was performed. (Testing method for inkjet suitability) Evaluation of inkjet suitability is performed by calendering the test paper obtained in the above-mentioned adhesive effect test, and then performing the test in a constant temperature and humidity (20 ° C, 65% relative concentration) environment. 2 4 After conditioning for more than one hour, use Bubb 1 e J et Printer BJ-220 JCII manufactured by Ca η ο η Co., Ltd. and perform the following method. The results are shown in Table (a) Printing density test. The / 3 printing was performed on the test paper, and the printing density of the / 5 part was measured with a M A C B A S E oil-based ink density meter. The larger the value, the higher the print density.

C: \ Total file \ 89 \ 89128114 \ 891281 14 (replacement) -l.ptc Page 24 571013 Case No. 89128114 Amendment V. Description of the invention (21) (b) The line width of the plume echo on the test paper will be orthogonal Certain lines and characters are printed, and the exudation of the lines and characters is visually evaluated in five stages. ’Those who have no plume echoes are 5 and those whose oily ink oozes and cannot discern the text are regarded as 1. Can withstand printing quality of 4 or more. (C) Inside peeling test Perform / 5 printing on a type 5 inspection paper 'to evaluate the degree of oily ink on the inside of the / 5 printing portion, and evaluate it visually and in 5 stages. The oil-free water exudation inside is regarded as 5 and the cold part is completely inside falling off as 1. The printing quality can be 4 or more for normal use. (Test Example 4) Foamability test (1) Preparation of test solution for foaming evaluation Test solution was oxidized powder (MS 3800 Japan Food Chemical Co., Ltd.) in order to release 10%, and at 95 The gelatinization was carried out at ° C, and the gelatinization solution was mixed with the aforementioned surface adhesive and common salt to prepare a coating solution. At this time, the concentration of the solid part of the surface adhesive and common salt of fenzhong oxidized oxidized powder 二 is less than or equal to the value. ° Concentration of solid part of oxidized starch in positive coating solution · 5 〇 Concentration of solid part of surface adhesive in coating solution · Concentration of solid part of table salt in coating solution: ^ · Q · 2% (2) Evaluation of foaming property of coating liquid ° Put the coating liquid mixed with the above (1) at the age of 600, say ^ ^ degree 50, in a foam measuring cell, and follow the instructions below. Two degrees (mm). The results are shown in Table 3. Shield long

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Page 25

571013 _Case No. 89128114__Year Month Day V. Description of the invention (22) The temperature of the coating liquid is 60 ° C, the circulation pump flow rate is 9 liters / minute, and the circulation time is minutes. In Table 3, the lower the foam height, the lower the foamability (less foaming amount). (Test Example 5) Mechanical stability test 50 g of the coating liquid adjusted by (1) of Lishu (Test Example 4) was placed in a cup at a temperature of 60 ° C. (:, Load 20 kg, rotation speed 800 rpm for 10 minutes

Maron-type stability test. The formed agglomerates were filtered with a metal having a mesh size of 32 5 meshes, and the amount of precipitation with respect to the entire solid portion was measured and expressed as an octave ratio. The results are shown in Table 3. The knife (Test Example 6) used the stability test of metal ions for the stability of metal ions at 70 ppm (calculated as CaC03). If no change is observed, it will be n. The surface adhesives of the examples of acidic high quality paper and neutral paper are flat adhesives for the coating solution, and the surface adhesives are better. The viscosity of the writing path is compared with Comparative Example 1. The ink concentration of the inkjet recording paper in Table 3 is the printing density, feather shape, and ". It can be seen that the surface examples 1, 3, and 4 of the embodiment are more sticky: more mouthful. It is Pi Liang ^ From the evaluation results in Table 3, it can be seen that the foaming properties of the surface adhesives of the surface comparative examples of the examples are > ^ training is more than all X. The results are shown in the case of slight turbidity, and

(:: \ Total file \ 89 \ 89128114 \ 89128114 (replace) -1. Page 571571013 Γ: --- ^ 89128114-year "" ^ Revision_ V. Description of the invention (23) Except for Comparative Example 5, implement The surface adhesives of the examples are better than all the surface adhesives. The stability to metal ions is that the surface adhesives of the examples are better than the surface adhesives of all the comparative examples. [Table 1 ] (One) — Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Polymerized Shellac Shellac Shellac JS-2 JS-2 Shellac Shellac Pre-weight 8 12 5 2 2 12 7 Powder type JS-2 MS-6 0 weight 1 part 1 Non-isolated type A Am A Am A Am A Am AAm AAm AAm Child weight 8 8 10 10 5 20 10 Hydrophilic monomer monomer Isolated species MAA AA MAA MAA Child weight 2 2 2 7 Monomer part hydrophobic. Type St iBMA nBMA iBMA St iBMA nBMA Single weight 40 40 60 55 50 40 70 Body type nBA nBA nBA iB A iBA nBA iBA Weight 60 60 40 45 50 60 30 servings Polymerization type Sl S-2 S-2 S-2 S-2 S-2 Sl After weight 20 15 20 20 20 15 30 Powder parts type Shellac 5 Shellac 7 Shellac 5 parts by weight-solid part 25.3 25.0 25.2 24.7 2 4.8 25.0 23.5 (° / 〇)

C: \ total file \ 89 \ 89128114 \ 891281 14 (replacement) -l.ptc page 27 571013 _ 銮 training. 89128114_ year, month and year V. Description of the invention (24) [Table 1] (Second) Example 8 Example 9 Comparative Example 1 Comparative ~ Example 2 tblS Example 3 — 2 Comparative Example 4 Sl 50 Type of dispersant before polymerization by weight of shellac 13 Shellac 3 Shellac 8 Shellac 12 species by weight JS-2 1 Nonionic hydrophilic AAm 12 AAm 8 AAm 8 Anionic monomer type MAA 2 MAA 2 MAA 2 MAA 2 hydrophobic monomer type nBMA 60 St 40 St 40 iBMA 40 St 50 St 50 weight part nBA 40 nBA 60 nBA 60 nBA 60 iBA 50 iBA 50 Type of dispersant after polymerization S-2 15 S-2 15 Sl 20 Solid part 5 25.1 25.0 23.5 25.0 25.2 24.7 The abbreviations in the table indicate the following substances. AAm: acrylamide MAA: methacrylic acid AA: acrylic acid St: styrene iBMA: isobutyl methacrylate nBMA: n-butyl methacrylate iBA: isobutyl acrylate nBA: n-butyl acrylate MS-6 0: ANTOX MS-60 (manufactured by Japan Emulsifier Co., Ltd.) (with methacrylic acid)

(:: \ Overall file \ 89 \ 89128114 \ 891281 14 (replacement), 1.ptc page 28 571013 case number 89128114 Amendment 5 、 Explanation of the invention (25) The hydrazone-based reactive emulsifier has the following Structural formula) 〇ch3

Ο- (EO) R

II I —C〇—C — C = CH n

-S〇3X Ο— (EO) However, in the foregoing formula, R is a sintered group, η is an integer, and X is a test metal representing nanometers. JS-2: ELEMIN0L JS-2 (manufactured by Sanyo Kasei) (reactive emulsifier with allyl group, having the following structural formula) ch2-coor

I

Na03S ~ CH-C00CH2CH = CH2 Shellac: N811 (manufactured by Gifu She 1 lac Co., Ltd.), all of which is 100% neutralized with koH.

C: \ Total file \ 89 \ 89128114 \ 89128114 (replacement) -l.pt c Page 29 571013 Case No. 89128114 Revised in five. Description of the invention (26) [Table 2] Test example 1 Test example 2 Coating liquid 3H8 Coating liquid pH6 Coating liquid] H8 St b chigt Adhesive ink writing adhesive st b chigt Adhesive ink writing adhesive st 〇chigt Adhesive ink writing adhesive Example 1 28 6 27 6 26 5 Example 2 29 6 26 5 26 5 Example 3 25 5 25 5 23 5 Example 4 22 4 20 4 19 4 Example 5 20 4 18 4 18 4 Example 6 19 4 17 4 18 4 Example 7 18 4 17 4 18 4 Implementation Example 8 18 4 17 4 17 4 Example 9 17 4 15 4 15 4 Comparative example 1 12 2 6 2 9 2 Comparative example 2 26 5 24 5 23 5 Comparative example 3 8 2 7 2 5 1 Comparative example 4 9 2 6 2 3 1 Comparative Example 5 24 5 16 5 21 3

(:: \ Total file \ 89 \ 891281 14 \ 891281 14 (replace) -l.ptc Page 30 571013 _Case No. 89128114_ Year Month Day Amendment V. Description of Invention (27) [Table 3]

Test Example 3 Test Example 4 Test Example 5 Test Example 6 Printing concentration Feather echoes Foaming mechanical foaming stability Metal ion stability Example 1 1.34 6 6 19 < 0.5% Example 2 1.34 6 6 14 & lt 0.5% 〇 Example '3 1.33 6 6 21 < 0.5% 〇 Example 4 1.30 5 5 25 < 0.5% 〇 Example 5 1.29 5 5 40 < 0.5¾ 〇 Example 6 1.30 5 5 36 < 0.5% 〇 Example 7 1.28 5 5 30 < 0.5% 〇 Example 8 1. 1.25 5 4 53 < 0.5% 〇 Example 9 1.24 4 4 49 < 0.5% 〇 Comparative Example 1 1.17 2 2 74 1. 3 ° / 〇X Comparative Example 2 1.32 5 5 ^ 70 0.9% △ Comparative Example 3 1.17 2 2 130 3.5% X Comparative Example 4 1.15 2 2 90 1.0¾ Δ Comparative Example 5 1.30 5 5 150 < 0.5% X (: : \ Overall files \ 89 \ 89128114 \ 89128114 (replacement) -1.ptc page 31 571013 _ case number 89128114_ year month and month revision_ V. Description of the invention (28) Industrial availability The surface adhesive of the present invention The agent is excellent in mechanical stability, low foaming property and storage stability. It can improve the adhesive properties of acid paper to neutral paper, and for information paper, especially inkjet paper It has excellent suitability, low foaming properties of the coating solution, compatibility with other drugs used in combination, and excellent stability to dissolved metal ions.

C: \ Total file \ 89 \ 89128114 \ 89128114 (Replace) -1.ptc Page 32 571013 _Case No. 89128114_ Year, month and day correction diagram, simple explanation Page 33 (:: \ Total file \ 89 \ 891281 14 \ 891281 14 (replace) -1.?^

Claims (1)

Γί is obtained from the shellac's test metal salt ⑷ ancient eighty-two, the reaction solution obtained by the polymerization of heavy parts, mixed with the molecular dispersant (e) 5 to 100 parts by weight can be obtained. ;: A surface Θ surface adhesive, characterized by the presence of a wide range of shellac alkali metal salts ^ f 'in non-ionic hydrophilic monomers ⑻ 20 100 weight; Λ daughter monomer (C ) ° · Bu 10 parts by weight and hydrophobic monomer ⑷ 5 can be obtained by mixing a polymer dispersant Le 5 ~ 1000 parts by weight.表面 A surface adhesive characterized by non-ionic hydrophilicity in the presence of scratches in shellac's metal test salt (a ^^ O parts by weight of an interfacial active substance (f) 05 ~ 5) Monomer (b Η ~ 20 wt. Parts 4 aqueous monomer (d) 100 wt. Parts in the reaction solution obtained by polymerization, mixed with the insect metal's alkali metal salt (a) and polymer dispersant (e) 5 ~ It can be obtained by 100 parts by weight. 4. A surface adhesive characterized by alkali metal salt of shellac [a] 1 to 20 parts by weight of the stomach (f) having an interfacial activity ability. In the presence of 5 to 5 parts by weight, in the nonionic hydrophilic monomer (b) 丨 ~ 2 〇 weight injury: anionic monomer (c) 〇. 1 ~ 丨 〇 and 1 part of the hydrophobic monomer (d) In the reaction solution obtained by polymerization in aliquots, 5 to 100 parts by weight of the alkali metal salt (a) of the shellac and the sub-dispersant (e) can be obtained. 5 ·-Surface adhesive It is characterized by 1 to 20 parts by weight of alkali metal salt (a) in shellac, 1 to 20 parts by weight with nonionic hydrophilic monomer (b) and hydrophobic monomer (d) 1 Billion parts by weight of the polymer as a repeat unit, the or C: \ total file \ 89 \ 891281 14 \ 89128114 (replacement) -1.? [Page 34 571013 _ case number 89128114_ year month month amendment _ 6. scope of patent application and non-ionic hydrophilic monomer (b ) 1 to 20 parts by weight, anionic monomer (c) 0.1 to 10 parts by weight and 100 parts by weight of hydrophobic monomer (d) as repeating units of polymer, and polymer dispersant (e) 5 ~ 100 parts by weight. 6. The surface adhesive described in item 3 or 4 of the scope of the patent application, wherein the substance (f) having an interfacial active ability other than the alkali metal salt (a) of shellac is a surfactant having a polymerizable group. 7. The surface adhesive as described in item 6 of the scope of the patent application, wherein the surfactant having a polymerizable group is a reactive emulsifier having a methyl propyl fluorenyl group and / or a dilute propyl group. 8. The surface adhesive according to any one of claims 1 to 5, wherein the non-ionic hydrophilic monomer (b) is composed of (fluorenyl) acrylamide, acrylonitrile, and (fluorenyl) ) At least one selected from the group consisting of hydroxyalkyl acrylate. 9. The surface adhesive according to any one of items 1 to 5 of the scope of the patent application, wherein the aforementioned hydrophobic monomer (d) is selected from the group consisting of a styrene derivative and (fluorenyl) alkyl acrylate At least one. 10. The surface adhesive according to item 2, 4, or 5 of the scope of the patent application, wherein the anionic monomer (c) is a monomer having a carboxylic acid group. 1 1. The surface adhesive according to any one of items 1 to 5 of the scope of patent application, wherein the polymer dispersant (e) is a salt of styrene-acrylic copolymer and / or (meth) acrylic acid Ester-based copolymer. (:: \ Total file \ 89 \ 89128114 \ 89128114 (replacement) -l.ptc Announcement on page 35 of this year's revision and replacement This application date: 89.12, 28 Case number: 89128114 Category: (The above columns are filled in by the Office ) Invention Patent Specification 571〇13 Chinese Surface Adhesive > Invention Name English Surface-Sizing Agent Name (Chinese) 1. Ikeda 2. Keane Chika 3. Yoshino Fumio Inventor Name (English) 1. 2 · 3. Nationality 1. Japan 2. Japan 3. Japanese residence and residence 1. Japan 17-2, Hachimankai-dori, Hara-shi, Chiba, Chiba Prefecture, Japan, Japan, Japan, Japan, Japan, Japan, Japan, Japan, etc. 2-3-37, Onodai, Midori-ku, Chiba City, Japan, Japan, Japan, Japan, Japan, Japan, Japan, Japan, Japan, Japan, Japan, Japan, Japan, etc. Japan (£-· 工 厶 · シ-Co., Ltd.i Nationality 1 · Japanese applicant's residence, domicile (office) 1. Saito 6-8, Kamanda, Chiyoda-ku, Tokyo, Japan / Representative name (Chinese) 1 . Representative names of Kawai and his party (English) 1. (:: \ Total file \ 89 \ 89128114 \ 89128114 (Replace) -1 邛 "Page 1