TWI239988B - Lithographic printing inks - Google Patents

Abstract

A single fluid lithographic printing ink composition includes a hydrophobic phase and a hydrophilic fluid phase. The hydrophilic fluid phase contains water or a liquid polyol or both. The hydrophobic phase contains a hydrogen bonding vinyl polymer that can hydrogen bond with the hydrophilic fluid phase. The vinyl polymers are preferably branched, but remain soluble in the hydrophobic phase. The invention provides stable inks that can be used as single fluid inks with excellent fountain stability and resistance to toning.

Description

1239988 A7 ____B7_ V. Description of the invention (1) Cross-references to related applications This application is US Patent Application No. 09 / 856,408 filed on May 3, 2001 (which is a PCT filed on November 29, 1999 / US99 / 28173 (which is US Patent Application No. 09 / 201,411 filed on November 30, 1998 (now US Patent No. 6,14,392, promulgated on October 31, 2000) ) Of the National Stage); and this application is part of the provisional US Patent Application No. 60 / 3009,617 filed on August 2, 2001. Consecutive cases, each of which is incorporated herein for reference. TECHNICAL FIELD The present invention relates to a lithographic printing ink and a lithographic printing method. BACKGROUND OF THE INVENTION Printing inks generally include one or more vehicle polymers or resins and one or more coloring agents as main components. The ink vehicle must meet several performance requirements, including those related to the printing method (such as clearness of the consistency and viscosity of the image to avoid flying hairs) or the appropriate length of mist or Proper drying characteristics), and requirements related to printed images (such as gloss, chemical resistance, durability, or color). Generally, the ink vehicle contains one or more materials such as vegetable oils or fatty acids, resins, and polymers that contribute to the properties of the final product, and may contain other groups such as organic solvents, water, rheology modifiers, and the like. Ingredients, which can affect body, stickiness or drying characteristics. In lithographic printing, in particular, the inked printing plate contacts and transfers the inked image to a rubber blanket, and then this blanket touches and transfers. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297). Public love)

1239988 A7 ---------_____ V. Description of the invention (2) " A This image is to the surface to be printed. Lithographic plates are prepared by treating the image areas of this plate with a lipophilic material and ensuring that the non-image areas are hydrophilic. In a typical lithographic printing method, the plate cylinder is first contacted with a damping roller, which transfers the aqueous ink reservoir solution to the hydrophilic non-image area of the plate. Then, the damping plate contacts the inking roller and receives ink only in the lipophilic image area. The imprint operator needs to continuously monitor the printing process to ensure that the correct balance of the ink reservoir solution and ink is maintained so that the ink adheres to the printing area of the board (but only in the printing area) to produce a clear print. The industry has long sought an offset printing method and related materials that do not require individual ink reservoir solutions. Anhydrous panels have been made by coating silicones with very low surface energy and non-wetting with ink in non-image areas. However, silicone-modified boards are expensive and require expensive special cooling embossing devices because the ink reservoir solution of the traditional two-fluid method also serves as a coolant. Other efforts have been directed at producing lithographic inks for a single fluid, i.e., inks that do not require a separate ink reservoir solution, which can be used with industry standard methods and all metal plates. Parkinson in U.S. Patent No. 4,045,232 (the entire contents of which are expressly incorporated herein by reference) describes lithographic printing and earlier efforts related to lithographic inks that produce a single fluid and single fluid Instability. Parkinson pointed out that an ink emulsion containing a solution of glycerin and salt is easy to break, and as a result, glycerin wets the ink roller and prevents good ink application. Parkinson suggests using a modified single-fluid ink obtained by using an additive comprising a resin treated with a concentrated mineral acid and a selective poly- or mono-M-based alcohol. Polyols are preferably glycerol, ethylene glycol and propylene glycol. Desanto, Jr. 4 people in US Patent No. 4,981,517 (the entire contents of which are specified here. This paper size is applicable to the Chinese National Standard (CNS) M specification (2K) x 297 mm). (Please read the precautions on the back before (Fill in this page) Order 1239988 Inventively incorporated for reference) Describe a printing ink, which is an emulsion of oil-based phase and water-miscible phase. The patent owner insists that it contains a significant portion of water (10% to 21%) and an emulsion using phosphoric acid as an important component has improved stability for phase separation and can be used as a single fluid lithographic ink. The composition of De Snato, Jr. further includes oils and polyol emulsifiers with properties of No. 1 and No. 2 fuel oils as diluents and emulsion stabilizers, and glycerol and ethylene glycol are the only examples provided. However, due to the various shortcomings of the single lithographic ink previously proposed, which include the limited stability and poor clarity and hue already mentioned, the industry standard is to continue a solution containing ink components and individual ink reservoirs Two-component lithographic ink. SUMMARY OF THE INVENTION The present invention provides a single fluid lithographic printing ink composition comprising a hydrophobic phase and an emulsified hydrophilic fluid phase. The hydrophobic phase contains a hydrogen-bonded vinyl-based resin. "Vinyl resin, and, vinyl polymer, etc. are used synonymously in the description of the present invention and refer to the use of ethylene via a carbon-carbon double bond via a chain-reaction polymerization or addition polymerization. Monomers (such as acrylic and methacrylic monomers, other vinyl monomers including vinyl esters and vinyl aromatic monomers (including ethylene)) and other ethylenic monomers copolymerizable therewith Polymers prepared by saturating monomers. ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,-,,,,,-,,-,-,-,-the vinyl-polymer? The base polymer is preferably because the polymerization reaction includes monomers having two or more (preferably two) reaction positions or because the polymerization is based on the Chinese paper standard (CNS) A4 (210X297 mm). ----------—… Fees: (Please read the notes on the back before filling out this page). 、 可 | Fortunately 1239988 A7 B7 V. Description of the invention (4) Make the polymer during or after the reaction Branched in reaction with a limited amount of crosslinker. "Branched "Vinyl polymers are polymers that remain useful in organic solvents, rather than polymers that are cross-linked into an insoluble three-dimensional network structure (which can be expanded only by solvents). A branch of the invention The acetonitrile-based polymer unexpectedly maintains solubility, even if it has a significant branch. The present invention further provides a hydrophobicity for preparing a vinyl resin organic solution having a hydrophilic fluid phase and containing a hydrogen bonding interaction with the hydrophilic fluid phase. Method for the composition of phases. In another aspect of the present invention, the hydrophobic phase contains one or more other additional resins or polymers. The present invention also provides a printing method using the single fluid ink for lithography of the present invention. The invention unexpectedly provides a stable ink that can be used as an ink reservoir with excellent stability and resistance to color tone. Detailed description of preferred specific examples The ink for lithography according to the present invention is a single-fluid ink having hydrogen-containing bonds Hydrophobic continuous phase of vinyl polymer and emulsified phase containing water, liquid polyol or water and liquid polyol. The hydrophobic phase may further contain Polymers and / or resins in ink vehicles and colorants, and the hydrophilic fluid phase may contain additional materials and additives (such as weak acids or bases) to promote the hydrogen bonding strength of the fluid. Composition for lithographic inks There is a sufficient amount of hydrogen bonding between the hydrophobic phase and the hydrophilic phase, so that a single fluid ink does not separate in the ink reservoir, and a sufficiently limited amount of hydrogen bonding between the hydrophobic phase and the hydrophilic phase. Emulsify and rupture during the application of ink and water and / or polyol to the surface, wet the areas where the printing plate does not receive the ink. The ink that is stable in the ink reservoir but quickly breaks apart on the printing plate can clear the printing without color. And provide consistent transfer characteristics. This paper size applies Chinese National Standard (CNS) A4 specifications (210X297 mm) ..... Yes (please read the precautions on the back before filling this page) 1239988 A7 _ B7_ V. Description of the Invention (5) (Please read the notes on the back before filling out this page) The appropriate stability depends on the selected special hydrogen-bonded vinyl polymer and special polyol. The content of the hydrogen-bonded group and the molecular weight of the polymer in the ink and the amount of the hydrogen-bonded vinyl polymer can be adjusted to provide the desired stability. It is generally believed that an increase in the hydrogen bonding group on the vinyl resin will be accompanied by a decrease in the content of the resin contained in the hydrophobic phase. The hydrophilic fluid phase comprises water, one or more liquid polyols, or water and one or more liquid polyols. The liquid polyol is an organic liquid having at least two hydroxyl groups. Polyethylene glycol oligomers (such as diethylene glycol, triethylene glycol, and tetraethylene glycol) and ethylene glycol, propylene glycol, 1,3-propanediol, dipropylene glycol, 1,4-butanediol Alcohols and glycerol are examples of preferred liquid polyols for the hydrophilic fluid phase of the single fluid ink of the present invention. Of course, the emulsified phase may comprise a mixture of different liquid polyols or a mixture of water and one or more liquid polyols. In general, higher molecular weight liquid polyols are preferred when the vinyl polymer of the hydrophobic phase has a higher equivalent of hydrogen bonding groups. The emulsified phase may contain further materials. In a specific example, the emulsified phase may also contain one or more solid polyols. The solid polyol may be selected from the group consisting of a solid alcohol compound and a solid polyol polymer. Examples include, without limitation, 2,3-butanediol, 1,6-hexanediol and other hexanediols, pentaerythritol, dipentaerythritol, highly branched dendrimers of hydroxy groups, trimethylolethane, Trimethyl alcohol propane, neopentyl glycol, 2,2,4-trimethylol; ι, 3-pyridine glycol, M · cyclohexyldimethanol, and hydrogenated bis-A. Compounds having one radical and up to about 8 carbon atoms (preferably up to about 8 carbon atoms) may also be contained, such as cyclohexanol and stearyl alcohol. The emulsified phase can also contain weak acids (such as citric acid, tartaric acid or tannic acid), or weak bases (such as triethanolamine). The paper size applies the Chinese National Standard (CNS) M specification (210X297 mm). 5. Invention Explanation (6) It may be contained in an amount of about 0.01% by weight to up to about 2% by weight of the ink composition. Some tests (such as magnesium nitrate) may be in an amount of about 0.01% to about 0.5% by weight (preferably about 0.08 to about 15% by weight) (based on the weight of the ink composition) Included to help protect plates and extend plate life. Water-soluble polymers such as poly (vinylpyrrolidone), poly (vinyl alcohol), and poly (ethylene glycol) can be added to the emulsion. About 0.5% by weight to about 1.5% by weight of a water-soluble polymer is included, based on the weight of the ink composition. A single fluid ink for lithography can be about 5% to up to about 50% (preferably about 10% to about 35%, and particularly preferably about 20% to about 30% of an emulsified liquid phase (by weight ) Preparation, which is based on the total weight of the ink composition. Unless another cooling device is provided, the ink composition preferably has a sufficient amount of emulsified fluid to keep the printing plate at an operable cooling temperature, preferably At least about 5% by weight, more preferably at least about 10% by weight, and more preferably at least about 15% by weight, and up to about 50% by weight, more preferably up to about 35% by weight, and more preferably Up to about 30% by weight. The content of the emulsified fluid phase required to achieve good printing results and no color tone depends on the type of printing plate to be used, and can be determined by direct testing. Continuous phase containing vinyl polymer Stabilize the emulsified fluid phase. Stability is such that the two phases are not separated in the ink reservoir. However, during the application of the ink, the emulsion breaks and polyhydric alcohols reach the surface, and the areas of the printing plate that do not receive the ink are wet. τ Ink is stable but fast to rupture and separate on the printing plate. Printed in Zhejiang and provide consistent transfer characteristics. Appropriate stability also depends on the selected special hydrogen-bonded vinyl polymer and the special components of the emulsified phase. Hydrogen bond 1239988 A7 B7 V. Description of the invention (7) Junction content The molecular weight of the vinyl polymer and the vinyl polymer concentration in the continuous phase can be adjusted to provide the desired stability. Ethyl-based polymers with higher levels of hydrogen bonding groups (lower equivalents) can generally be Use low content, but generally the concentration of hydrogen bonding groups should not be too high, otherwise the vinyl polymer cannot be fully dissolved in the continuous phase. Destabilizing interactions (such as other polymers, resins or other materials in the continuous phase) And emulsified fluid phase) are avoided. In general, other materials that are more hydrophilic than hydrogen-bonded vinyl polymers are avoided. The hydrophobic phase of a single fluid ink contains at least one A multi-component hydrogen-bonded vinyl polymer. The hydrogen-bonded vinyl polymer of the present invention is polymerized by a monomer mixture containing one or more monomers containing hydrogen-bonded groups. The reaction is prepared by adding a hydrogen-bonded polymer or converting other groups into a desired hydrogen-bonded group after the polymerization reaction. The vinyl polymer of the present invention is prepared by including two reaction sites in the polymerization reaction. The monomers are advantageously branched by reacting the polymer with a material having a plurality of groups capable of reacting with the polymer. When a vinyl polymer is branched, it still retains useful solubility. "Solubility" refers to the polymer It can be diluted with one or more solvents. (Conversely, the polymer can be cross-linked into a gel, which is an insoluble three-dimensional spatial network that can only be expanded by the solvent.) Even with a large number of branches, the branched vinyl resin of the present invention cannot be The solvent-dilutable properties are pre-preserved. The hydrogen-bonded vinyl polymer of the present invention can be converted to a hydrogen-bonded group or a group added thereto by containing at least one hydrogen-containing group or after polymerization. A monomer mixture of monomers is prepared by polymerization. Better Hydrogen Bonding Group -------------------------- Volume ―:-This paper size applies to China National Standard (CNS) A4 specification (210X297 Mm) tr (Please read the notes on the back before filling this page) 1239988 A7 ---------- B7__ _ V. Description of the invention (8) Carboxyl SSL base, slow acid liver base, primary amine Or an amine having an alkyl substituent having three or fewer carbon atoms on the nitrogen atom, a primary amidine, or an amine having an alkyl substituent having two or less carbon atoms on the nitrogen atom, Vinegar, pendant ester, pendant, or sulfur-containing group with three or more anti-atom pendant groups. The carboxy-functional vinyl polymer of the present invention can be obtained by a monomer mixture comprising at least one acid-functional monomer and at least one monomer having a group (such as an anhydride group) which is converted into an acid group after the polymerization reaction. Prepared by polymerization. Examples of acid- or anhydride-functional monomers include without limitation ethylene unsaturated monocarboxylic acids containing 3 to 5 carbon atoms, such as acrylic acid, methacrylic acid, and butenoic acid; containing 4 to 6 carbons Atomic ethylene unsaturated dicarboxylic acids and anhydrides and monoesters of these acids, such as maleic anhydride, monomethyl maleate, and fumaric acid; and functional derivatives of copolymerizable monomers, such as, A hydroxyethyl acrylate half ester of succinic acid. Acid functionality can be provided by other known means, such as by reacting a hydroxyl group with an anhydride or by a hydrolysis reaction of an ester, such as a hydrolysis reaction of a third butyl methacrylate monomer unit. It preferably contains an acid-functional monomer (such as acrylic acid, methacrylic acid, or butenoic acid), or an anhydride monomer (such as maleic anhydride or itaconic anhydride), which can be hydrated to generate an acid group after the polymerization reaction. . The acid-functional vinyl polymer preferably has an acid number of at least about 3 mg of KOH per gram of non-volatile matter, more preferably about 6 to about 30 mg of KOH, per gram of non-volatile matter, and More preferably, the acid number is about 8 to about 25 milligrams of KOH per gram of nonvolatile matter, which is based on the weight of the nonvolatile matter of the vinyl polymer. Examples of amines and amido groups include, without limitation, a class of amidines, of which N_ this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -----------... meal ... : (Please read the precautions on the back before filling out this page). 、 可 | 1239988 A7 B7 V. Description of the invention (9) N-Hexyl amines with three or less carbon atoms, each N · N, N with alkyl groups having three or less carbon atoms, dialkyl amines, primary amines, where N-alkyl groups have three or less atomic interfering N-alkyl groups, where N-alkyl groups N, N having three or less carbon atoms, dialkylamine, amines and sulfonamide. Examples of suitable amine- and amine-functional ethylenically unsaturated monomers include without limitation propylamine, methacrylamidine, p-dimethylaminostyrene, N-dimethylaminoethyl Methyl methacrylate, aminopropyl methacrylate, aminoethyl acrylate, aminopropyl acrylate, aminoethylfluorenyl acrylate, 1-vinylpyrrolidone, N-benzene Allyl acrylamide, N-alkyl amidyl acrylamide, N, N'-dialkyl acrylamide, and N, N, -dialkyl acrylamide, wherein the alkyl group has 3 or less Carbon atoms. Specific examples include N-fluorenylacrylamide, N-methylmethacrylamide, N-isopropylacrylamide, N-isopropylmethacrylamine, N, N-dimethylacrylamide Amine, N, N'-dimethylamidinoacrylamide, N, N'-diisopropylmethacrylamide, N-vinylamidamine, and mixtures thereof. Examples of sulfur-containing groups include sulfonic acid, sulfonamide, sulfur oxides, sulfonium, and mercaptans. Thiols can be included as a chain transfer agent. Examples of suitable monomers include, without limitation, 2-propenylamino-2-methylpropanesulfonic acid, methylvinylfluorene, methylethylene sulfide, and sodium ethylene lutein. Copolymers of ethylene sodium lutein can be acidified and then treated with dialkylamines to produce sulfonamide. Examples of providing a phosphorus group-containing monomer include without limitation vinyl phosphoric acid, which can be esterified to produce a phosphate or amidated with a dialkylamine to produce amidamine. Examples of suitable ethylenically unsaturated hydroxy monomers include without limitation hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, methacrylic. This paper applies Chinese national standards (⑽) A4 specifications (2) 0X297 mm ) (Please read the precautions on the back before filling out this page) ， 可 | 1239988 A7 p .____ —_ B7_ V. Description of the invention (10) Acid ethyl ester, hydroxypropyl methacrylate and hydroxybutyl methacrylate vinegar. Hydroxyl functional groups can also be obtained on vinyl polymers, for example, by hydrolysis of ester groups (eg, hydrolysis of ethyl acetate monomer units to vinyl alcohol), or by acid groups with ethylene oxide. Alkyl reaction (for example, glycidyl methacrylate monomer units react with acetic acid or fluorenyl acrylic monomer units react with ethylene oxide). It is preferred to add a weakly alkaline material to the hydrophilic fluid phase to enhance the hydrogen bonding between the hydroxyl functionality of the vinyl polymer and the components of the hydrophilic fluid phase. Suitable esters include fluorenyl, ethyl, n-propyl, and isopropyl esters of polymerizable acids, such as methyl methacrylate, ethyl acrylate, monomethyl maleate, diethyl maleate, and the like 'And ethylenically unsaturated esters of saturated acids with up to four carbon atoms, such as ethyl acetate, ethyl acetate, propionate and butyrate, Or vinyl formate, vinyl acetate, vinyl propionate and vinyl butyrate. Ethyl acetate can also be used for hydrogen bonding, and monomers containing acetamidine g can produce allyl ions by treating the allyl halide with a strong base (eg, Koh). 4-pentanedione is obtained by reaction. The formed acetoacetate functional monomer is copolymerized to provide an acetoacetate functional ethynyl polymer. Another acetoacetate functional monosystem, acetoacetoxyethyl acetopropionate. The hydrogen-bonded ethylene-based polymer of the present invention may also contain a mixture of the above-mentioned functional groups capable of forming a hydrogen-bonding interaction. Vinyl polymers preferably have at least about 1800 g / equivalent (more preferably at least about 2200 g / equivalent) and more preferably up to about 20,000 g / equivalent (more preferably up to about 7200 g / equivalent). This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the precautions on the back before filling this page), τ. • Aw.! 239988 A7 r ^ --_ JZ___ 5. Description of the invention (11 ) G / equivalent) (which is based on hydrogen bonding). Hydrogen-bonding groups of vinyl polymers can be species that supply hydrogen and species that receive hydrogen. It is to be understood that vinyl polymer hydrophilic fluids may have the same chemical functional groups as the donor species and acceptor species involved as hydrogen bonding pairs. For example, a hydroxyl group on a vinyl polymer can interact with a hydroxyl group of a hydrophilic phase. In addition, donor and acceptor species can be distinct chemical groups. For example, amidino may be hydrogen bonded to a hydroxyl group. In addition, some functional groups on the hydrogen-bonded vinyl polymer can be used as donor species, others as donor species, and others as both. Generally, water and / or polyols of the hydrophilic fluid phase can be used as acceptors and I donors. The strength of hydrogen bonding is related to the relative acidity and basicity of the donor and acceptor species. If it is desired to strengthen the hydrogen bond formed between the donor and acceptor with weakly acidic hydrogen, it can add an acidic material to the donor species to increase its hydrogen bonding affinity. In addition, weaker materials can be added to the hydrogen acceptor to increase the strength of the hydrogen bond. In some cases, ionic interactions can be mitigated and controlled by proper addition of weak acids and bases to donors and acceptors. Hydrogen-bonded vinyl polymers are branched. In a specific example, hydrogen-bonded vinyl polymers are significantly branched. The branched vinyl polymer is still soluble. The branched vinyl polymer of the present invention is diluted 'by adding a solvent instead of being swollen or dispersed. Branching can be accomplished in several ways. In the first method, a monomer having two or more polymerizable double bonds is included in the polymerization reaction. In the second method, a pair of ethylenically unsaturated monomers (each having at least one additional functionality that reacts with additional functionality on another monomer in addition to the polymerizable double bond) is included in the polymer to be polymerized. The size of the monomer mixture is suitable for the paper _ 准 准 (CNS) M specifications (2 to 297), ^ ---------------- Γ -... 囔 ----- ------------- tr ---------------- Meal · (Please read the precautions on the back before filling this page) 1239988

DESCRIPTION OF THE INVENTION Within. The second method consists of cross-linking a polymer with a crosslinking agent having at least two functional groups capable of reacting with functional groups on the polymer. (Please read the notes on the back before filling this page)

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Meeting I Preferably, the vinyl resin of the present invention is polymerized using at least one monomer having two or more polymerizable ethylene unsaturated bonds. Examples of monomers having two or more ethylene unsaturated moieties include, without limitation, (meth) acrylates of polyhydric alcohols such as 1,4-butanediol di (meth) acrylate, 1,6-Hexanediol di (methyl) propionate, neopentyl glycol di (methyl) propionate, dimethyl alcohol propane tris (methyl) propionate g Purpose, tetramethyl alcohol methane tetrakis (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (fluorenyl) acrylate, elongation glycol Di (meth) propanoate and poly (ethylene) glycol di (meth) acrylates, such as ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, diethyl Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and polyethylene glycol di (meth) acrylate; divinylbenzene, methacrylic acid methyl ester, Di-dipropyl acid, diallyl terephthalate, etc., which may be a single or a mixture of two or more. Among them, divinylbenzene, butanediol dimethacrylate, butanediol dimethacrylate, dimethyl alcohol propylene dipropionate, and pentaerythritol tetrapropionate are preferred, and Divinylbenzene is more preferred. Preferably, the branched vinyl polymer is polymerized by polymerizing at least one monomer with at least two ethylenically unsaturated polymerizable bonds using at least about 0.008 gram / 100 grams of monomer, or 0.004 Equivalents / ιιοg of monomer are polymerized by polymerizing each of two monomers which have a reactive group in addition to ethylene unsaturated polymerizable bonds. Preferably, the branched vinyl polymer is about the size of the paper and is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1239988 A7 I ---- ~ — 57 ____ 5. Description of the invention (13) " 0 012 to about 0,08 equivalents / 100 grams (more preferably about 0.016 to about 0.064 equivalents / 100 grams) of monomers with functional monomers having at least two ethylene unsaturated polymerizable bonds < I has a -polymerized bond and-an additional mutual reactive t monomer pair polymerizes to polymerize. The polyfunctional monomer preferably has two to four ethylene unsaturated polymerizable bonds, and more preferably two ethylene unsaturated polymerizable bonds. In a specific example, the branched ethylene resin is preferably about 0.5% to about 6% (more preferably about 1.2% to about 6%) by polymerization based on the total weight of the monomers to be polymerized. More preferably, it is about 1.2% to about 4%, and more preferably about 15% I to about 3.25 / i). The monomer mixture of ethynylbenzene is prepared. Commercial grade divinylbenzene includes monofunctional and / or non-functional materials. The amount of commercial material needed to provide the percentages shown needs to be calculated. For example, 5% by weight of 80% by weight of divinylbenzene / 20% of monofunctional monomer material will provide a 4% by weight divinylbenzene fraction. The optimum amount of divinylbenzene or other monomer having at least two polymerizable ethylene unsaturated bonds contained in the polymerization reaction mixture is to some extent dependent on special reaction conditions such as the rate of monomer addition during the polymerization reaction ), The solubility of the polymer to be formed in the selected reaction medium, the monomer content relative to the reaction medium, the half-life of the selected starter at the reaction temperature, and the starting dose based on the weight of the monomer and It can be determined by direct testing. In addition, the polymer may be crosslinked by including at least one pair of monomers having at least one functional group that reacts with the functionality of other monomers in the monomer mixture. Preferably, the reaction of the additional functional group occurs during the polymerization reaction, even if it is not important when forming the polymer according to the present invention, and the additional official is ----------- = ~~ — This paper size is applicable China National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page), ^ τ— 0, 1239988 A7 ____ £ 7_ V. Description of the invention (14) The reaction of the energy base can be found in The polymerization is partially or completely completed before or after. A variety of these mutually reactive groups are possible. Examples of such reactive group pairs include, without limitation, epoxides and carboxyl groups, amines and carboxyl groups, epoxides and amine groups, epoxides and anhydride groups, amines and anhydride groups, hydroxyl groups and carboxyl groups or anhydride groups, and amines. And acid gas group, alkylene imine and carboxyl group, organic alkoxysilane and carboxyl group, isocyanate and hydroxyl group, cyclic carbonate and amine group, isocyanate and amine group, etc. When a hydrogen bonding group is included as a reactive group, it is used in a sufficient excess to provide a desired hydrogen bonding functionality in a vinyl resin. Specific examples of these monomers include without limitation glycidyl (meth) acrylate (meth) acrylic acid, N-alkoxyfluorinated acrylamide (reacting with itself), such as N- Isobutoxylated acrylamide, rmethacryloxytrialkoxysilane (reacts with itself), and mixtures thereof. With regard to the description of the present invention, the term "(meth) acrylate," is used to refer to acrylates and fluorenyl acrylates, and "(meth) propylene," is used to refer to propylene compounds, methacrylic compounds, and the like. The polymers of the present invention can also branch by reacting the polymer with a limited amount of cross-linking compounds after polymerization. The amount of cross-linking is limited to keep the vinyl compound soluble in the continuous phase. These cross-linking agents contain at least two Functional groups that react with functional groups on the polymer. The reactive groups on the cross-linking agent can be the same or different, and the cross-linking agent will be selected based on the functional groups present on the polymer. Note that the hydrogen-bonded vinyl group Many hydrogen-bonding functional groups on polymers can be cross-linked. Generally, this cross-linking occurs at a low stoichiometric ratio, so that after this cross-linking, hydrogen-bonding groups can be obtained to be hydrophilic as described above. The components of the fluid phase form hydrogen bonds. Examples of cross-linking agents include, without limitation, polycarboxyl paper. Applicable to China National Standard (CNS) A4 (210X297 mm) ----- τ ...- meal- ----------------- Order -------------- --... (Please read the precautions on the back before filling this page) 1239988 V. Description of the invention (15 j (Please read the precautions on the back before filling out this page) Acids, Polyamines, Polyisocyanates and Polyesters Non-limiting examples of cross-linking agents include diethylene glycol, triethylene glycol, hexanediamine, adipic acid, neopentyl glycol, dipropylene glycol, tripropylene glycol, 1,4-cyclohexane Dimethyl alcohol, 1,6-hexanediol, 1,3-butanediol, hydrogenated bisphenol a, 2,2,4_trimethylsulfonium dioxin, etc. Ming gelling agent can also be used as a diplomatic association These aluminum gelling agents can be aluminum, organic complexes, or aluminum alkoxides. Aluminum gelling agents crosslink hydrogen-bonded vinyl groups due to the formation of aluminum alkoxide bridges between reactive groups on the polymer. Polymers. Specific examples of the aluminum gelling agent used in the present invention include, without limitation, acetoacetone, triisopropyl aluminum oxide, tri-n-butyl aluminum oxide, aluminum diisopropoxide ethyl acetate, oxygen Acetate (0A0 of Chattem Chemicals), and mixtures thereof. In addition, alkanoates and hammer salts can be used without limitation, for example, two ( Based) phenyloxyethylene titanate, bis (dioctyl) phosphoethylene titanate, diisopropyl distearylfluorenyl titanate, the corresponding zirconium salt, and mixtures thereof. Aluminum gelation Mixtures of agents, alkoxides and alkanoates can also be used. Other monomers that can be polymerized with monomers containing hydrogen bonding groups include, without limitation, ethylenic unsaturation containing 3 to 5 carbon atoms Higher esters of monocarboxylic acids, such as butanols and higher alcohols of acrylic acid, methacrylic acid and butenoic acid; butanes of α, / 3 -ethylene unsaturated dicarboxylic acids containing 4 to 6 carbon atoms Alcohol and higher diesters; butyl and higher vinyl esters, vinyl ethers, vinyls (such as vinyl ethyl ketones), and aromatic or heterocyclic aliphatic ethynyl compounds. Representative examples of suitable esters of acrylic acid, methacrylic acid, and butenoic acid. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 1239988 A7 I -------- B7 _ V. Description of the invention ( 16) " ~~ 一 — + Limited to include esters that react with saturated aliphatic and cycloaliphatic alcohols containing 4 to 2G carbon atoms, such as n-butyl, isobutyl, third butyl, fluorene Ethylhexyl, lauryl, stearyl, cyclohexyl, trimethylcyclohexyl, tetrahydrofuranyl, stearyl, sulfoethyl and isobornyl acrylates, methacrylates and butenoates; and Acrylates and methacrylates of polyalkylene glycols. Representative examples of other ethylene unsaturated polymerizable monomers include, without limitation, diesters such as fumaric acid, maleic acid, and itaconic acid with alcohols such as butanol, isobutanol, and tertiary butanol. Representative examples of aromatic or heterocyclic aliphatic vinyl compounds include, without limitation, compounds such as styrene, "-methylstyrene, ethynyltoluene, third butylstyrene, and the like. Monomer selection system Based on various factors commonly considered in the preparation of ink paints, including the desired glass transition temperature and the desired dilution of the polymer to form the solvent or solvent system of the ink composition. The preferred vinyl polymer can be borrowed Prepared by traditional techniques (preferably a semi-batch process of free radical polymerization). For example, in a semi-batch process, monomers, starters and any chain transfer agents can be supplied to the injections at a controlled rate. Properly heat the reactor with solvents. Typical free radical sources are organic peroxides, including dialkyl peroxides, such as di-third butyl peroxide and dicumyl peroxide, peroxyesters, such as , Third butyl peroxy 2-ethylhexanoate and third butyl peroxyvaleric acid vinegar; peroxy carbonate and peroxy dicarbonate, such as third butyl peroxy isopropyl carbonate Di_2_ethylhexylperoxydicarbon Esters and dicyclohexylperoxydicarbonates; difluorenyl peroxides, such as diphenylfluorenyl peroxide and dilaurylfluorenyl peroxide; hydrogen peroxide, such as dry paper, applicable to China Standard (CNS) Α4 Specification (21〇χ297 公 爱)-_

Order — (Please read the notes on the back before filling this page) ▼ 1239988 A7 ________B7_ V. Description of the invention (17) Hydrogen peroxide and tertiary butyl hydrogen peroxide; Ketone peroxides, such as cyclohexyl Oxides and methyl isobutyl ketone peroxides; and peroxyketals such as 1,1-bis (third butylperoxy) -3,5,5-trimethylcyclohexane and bis ( Second butyl peroxy) cyclohexane; and azo compounds such as 2,2'-azobis (2-methylbutanenitrile), 2,2'-azobis (2-methyl) Propionitrile, and azobis (cyclohexanecarbonitrile). Organic peroxides are preferred. Particularly preferred is third butylperoxy isopropyl carbonate. The particular initiator and the starting dose used depend on factors known to those skilled in the art, such as the reaction temperature, the content and type of solvent (in the case of solution polymerization), the half-life of the initiator, etc. Chain transfer agents can also be used in the polymerization. Typical chain transfer agents are mercaptans such as octyl mercaptan, n- or tertiary dodecyl mercaptan, thiosalicylic acid, thiol carboxylic acids such as thiol acetic acid and thiol Propanoic acid and its esters' and thiol ethanol; halogenated compounds; and dimer α-methylstyrene. Preferably, no chain transfer agent is included because of odor and other known disadvantages. Addition polymerization such as radical polymerization is generally performed at a temperature of about 20 ° C to about 300 ° C (preferably about 150 ° C to about 200. (:, more preferably about 160 ° C to about 165 ° C)). Completed in solution. Preferably, the polymerization is completed at about the same temperature and using the same initiator throughout the process. The initiator must be selected so that its half-life at the reaction temperature is preferably no more than about 30 minutes Especially preferred is no more than about 5 minutes, and more preferred is no more than about 2 minutes. Particularly preferred is at about 150 ° C to about 200. (: A temperature starting agent with a half-life of less than about 1 minute In general, when the half-life of the initiator is short and / or more initiators are used, more branched monomers can be included. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 public love)

1239988 V. Description of the invention (18) The vinyl polymer vehicle of the present invention preferably has a monomer content with little or no residue (unreacted). In particular, the B County vehicle is preferably substantially free of residual monomers, that is, having less than about 0.5% residual monomers, and more preferably less than about 0.1% residual monomers (by weight). , Which is based on the total weight of the monomers to be polymerized). In a semi-batch process, the monomers and initiators are added to the polymerization reactor over a period of time and preferably at a fixed rate. Typically, the addition time is about 1 to about 10 hours, and the addition time is about 3 to about 5 hours. Larger addition times typically result in lower number average molecular weights. A lower number average molecule 1 can also be produced by increasing the solvent to monomer ratio or by using a stronger solvent for the polymer formed. Generally, the branched vinyl polymer of the present invention has a low number average molecular weight and a wide polydispersity. The number-average molecular S Mη and weight-average molecular weight Mw of the vinyl resin according to the present invention can be obtained by gel permeation chromatography using polystyrene standards (which can be up to 6 million weight-average molecular weight according to acceptable methods Gain). Polydispersity is defined as the Mw / Mn ratio. In a specific example, the vinyl polymer has a number average molecular weight of less than 1,000 (more preferably at least about 2000). The number average molecular weight is also preferably less than about 15,000, more preferably less than about 500,000, and more preferably less than about 8,500. A preferred range of Mη is from about 1,000 to about 10,000, a more preferred range of Mη is from about 2000 to about 8500, and a more preferred range is from about 4000 to about 8,000. The weight average molecular weight needs to be at least about 30,000, preferably at least about 100,000. The weight average molecular weight is preferably up to about 60 million, which can be obtained by using a weight average molecular weight of 6 million. This paper size is applicable to China National Standard (CNS) A4 specifications (210X297 mm) 1239988 A7 B7 V. Description of the invention (19) The GPC decision of the standard. A preferred range of Mw is about 30,000 to about 55 million, a more preferred range of Mw is about 100,000 to about 1 million, and a more preferred range is about 100,000 to about 300,000. Resins with ultra-high molecular weight shoulders (visible by GPC) are preferably avoided for Mw ranges of about 100,000 to about 300,000. The polydispersity (or Mw / Mn ratio) can be up to about 10,000, and preferably up to about 1,000. The polydispersity is preferably at least about 15, especially at least about 50. The polydispersity is preferably in the range of about 15 to about 1000, and more preferably, it is in the range of about 50 to about 800. The theoretical glass transition temperature (Tg) can be adjusted by selecting and distributing co-monomers according to methods known in the art. In a preferred embodiment, the theoretical Tg is higher than room temperature, and preferably, the theoretical Tg is at least about 60 ° C, and more preferably at least about 70t. The method and composition of the present invention are preferably those having a temperature of about 5 ° C. to about 125 ° C. (more preferably about 60 ° C. to about 100 ° C., and more preferably about 70 ° C. to about 90 ° C.). ) Vinyl polymer. The theoretical glass transition temperature can be determined using the Fox equation. In a specific example of the present invention, a hydrogen-bonded vinyl polymer (which may be a branched vinyl polymer) and ink Other resins of the composition are mixed. Examples of suitable other resins that can be mixed with the hydrogen-bonded vinyl polymer include, without limitation, polyesters and alkyd resins, phenolic resins, turpentine, cellulose, and derivatives thereof such as Turpentine-modified phenolic resin, phenolic-modified turpentine, hydrocarbon-modified turpentine, maleic-modified turpentine, fumaric-modified turpentine; hydrocarbon resins, other propylene or vinyl resins, polymer Phenylamine resin, etc. For each part of the present invention, the hydrogen-bonded vinyl polymer of the present invention is polymerized ----- This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) (please read the note on the back first) (Fill in this page again)

• 、 Can I Φ 1239988 A7 _B7_ 905. Description of the invention () (Please read the precautions on the back before filling in this page), these resins or polymers can be about 1 part by weight up to 100 parts by weight (compared to Preferably, it is included in an amount of about 3 to about 50 parts by weight, based on the weight of the resin's nonvolatile matter. In addition to the hydrogen-bonded vinyl resin and any optional second resin, the ink composition of the present invention preferably contains one or more organic solvents. In a preferred embodiment of the present invention, the branched vinyl resin is formed in a solution or an apparent solution having no apparent turbidity in the organic solvent of the ink composition. The specific organic solvent and the amount of solvent included are determined by the desired ink viscosity, body, and tackiness. Generally, a non-oxidizing solvent with a low shell pinol butanol (KB) value is used for inks that will come into contact with rubber parts such as rubber rollers during the lithography process to avoid affecting rubber. Appropriate solvents for inks that may come into contact with rubber parts include, without limitation, normal and isoparaffin solvents of aliphatic hydrocarbons (such as crude oil distillation fractions) with limited aromatic characteristics. For example, crude oil middle distillates (such as those available from Magie Bros. Oil Company (Pennsylvania Refining Company, Franklin Pakr, a subsidiary of IL) under the trade name Magie Sol are available from Exxon Chemical Co., Houston, TX ExxPriny, and available from Golden Bear Oil Specialties, Oildale, CA, Total Petroleum Inc., Denver, CO and Calumet Lubricants Co. 5 Indianapolis, IN) can be used. In addition or in addition, soybean oil or other vegetable oils may be included. When a non-oxidizing solvent such as these is used, it is generally necessary to include a sufficient amount of at least one pair of aliphatic solvents having a large affinity for the monomer to obtain the desired solubility of the preferred branched vinyl polymer. Generally, in the alcohol part of ester or styrene or alkyl styrene (such as tertiary butyl styrene), there is ― 1 ------ This paper size applies to China National Standard (CNS) A4 specification (210X297 (Public love) 1239988 A7 ___B7 V. Description of the invention (21) At least 6 carbon propylene ester monomers can be included in the polymerized monomer for this purpose. In a preferred embodiment, the ink composition with a non-oxidizing solvent includes a self-promoting lipid comprising at least about 20% (preferably about 20% to about 40%, and more preferably about 20% to about 25%). A branched vinyl resin in which a monomer mixture of a family-soluble monomer (such as stearyl methacrylate or tertiary butyl styrene, and stearyl methacrylate is a preferred such monomer) is polymerized. It is also preferred that it contains at least about 55% styrene, more preferably about 55% to about 80% phenethylfluorene 'and more preferably at least about 60% to about 70% styrene. If desired, 'other monomers can also be used to reduce the solvent tolerance in aliphatic solvents. All percentages are by weight, based on the total weight of the polymerized monomer mixture. The preferred monomer composition of the ethylene-based polymer for lithographic inks includes (meth) acrylic esters of alcohols having 8-20 carbon atoms, such as stearyl methacrylate, styrene, Vinylbenzene, and monomers containing hydrogen bonding groups. In a preferred embodiment, the branched vinyl resin of the lithographic printing ink is from about 15 (preferably about 20) to about 30 (preferably about 25) by weight of an alcohol having 8-20 carbon atoms. (Meth) acrylic ester (especially stearyl methacrylate); about 50 (preferably about 60) to about 80 (preferably about 75)% by weight of a styrene monomer (especially styrene itself) . Preferably, the organic solvent or solvent mixture will have a boiling point of at least about 10 ° C and preferably no more than about 550 ° C. Offset printing inks may use solvents having a boiling point above about 200 ° C. Newspaper inks are generally It is composed of about 20 to about 85% by weight of solvents such as mineral oil, vegetable oil, and high boiling point crude oil distillates. The solvent content also depends on the type of ink composition (that is, ink is used for newspaper printing, heat setting, Sheets, etc.), the special solvents used, and the paper size of this technical institute are applicable to the Chinese National Standard (CNS) A4 specification (2〗 0 > < 297 public love) (Please read the precautions on the back before filling this page)

I 1239988 A7 B7 V. Invention description (22) Other factors known. Typically, the lithographic ink has a solvent content of up to about 60%, which may include oil as part of the solvent packaging. Generally, at least about 35% of the solvent is present in the lithographic ink. When used to formulate the preferred ink composition of the present invention, these paints or vehicles (including branched vinyl resins) are typically clear, apparent solutions. The ink composition of the present invention generally contains one or more colorants in a hydrophobic phase. The number and type of colorants depend on the type of ink to be formulated. Newspaper ink, cold set, and book black compositions typically contain only one or more colorants (such as carbon black), while commonly used color inks can include more complex colorant packages that include special functions (Such as pearl luster or metallic effect). The lithographic printing inks for full-color printing are typically used in four colors-magenta, yellow, black, and cyan, and the customary colors can be included as desired. Any conventional inorganic and organic colorants can be included in the ink composition of the present invention. In addition, the composition of the present invention can be used as an overprint primer or varnish. Overprint primer (air-dried) or varnish (cured) is intended to be clear or transparent, and therefore opaque pigments are not included. It has been observed that the print quality using the lithographic ink composition of the present invention may be a function of pH under certain conditions. As shown above, a wide variety of chemically functional groups in hydrogen-bonded vinyl resins are suitable for providing a single fluid ink composition for lithography, which is stable in the ink reservoir and breaks when applied to a printing plate To provide high-quality printing materials. It is believed that the present invention operates in part on the principle of the balance between hydrogen-providing capacity and hydrogen-accepting capacity between the hydrogen-bonding group of the vinyl resin and the components of the hydrophilic fluid phase. The component of the hydrophilic fluid phase contains a hydroxyl group having hydrogen supplying ability and hydrogen receiving ability. According to the choice ......... 丨 丨 丨 丨 丨, 丨 丨 丨, 丨 丨 丨 丨 丨 —.M.,, ^ _ This paper size applies to Chinese national standards ( CNS) A4 specification (210X297 mm) ------ 1 ----..... (Please read the precautions on the back before filling this page)

• 、 I 1239988 A7 B7 V. Description of the invention (23) Depending on the mouse bonding of the ethylene-based resin of the ink composition of the present invention, the hydrogen-bonding group on the ethyl-based resin may have relatively high or low hydrogen Provide or accept capacity. If the hydrogen bonding capacity of the polymer is relatively low based on hydrogen supply capacity, it is preferred to place a component in the hydrophilic fluid phase to increase its relative hydrogen acceptance capacity to provide a proper balance. For example, when hydrogen-bonding a base alcohol on a polymer, it has been found useful to add a weak base to the hydrophilic fluid phase. On the other hand, when the nitrogen-bonding functional group on the ethyl resin is a particularly strong nitrogen acceptor, care must be taken not to place additives into the hydrophilic fluid phase, which will increase the hydrogen supply ability of the hydrophilic fluid phase. For example, when the hydrogen-bonding group on the vinyl resin is an amine group, it is preferred that a strong acid cannot be placed in the hydrophilic fluid phase. This weak acid in the hydrophilic fluid phase can easily form a salt with the amine on the vinyl resin, resulting in poor performance of the ink composition, and the composition may be too stable to crack when applied to a printing plate. Ink containing an amine-functional vinyl resin as described above is most effective at about neutral pH. When the hydrogen-bonding functional group on vinyl resin is fluorene or N-alkyl fluoramine, it has been observed that the proper functionality of the ink composition is almost independent of pH. It is believed that the amidine functional group has an appropriate balance of hydrogen accepting properties to allow low pH, high pH, or neutrality within the hydrophilic fluid phase. In contrast, for a hydrogen-bonded vinyl resin containing an alcohol-hydrogen-bonded group, the performance of the ink composition depends on the pH value. Preferably, the hydrophilic fluid phase has Hansen solubility parameters having these values: a dispersion parameter value of at least about 6, a polarity parameter value of at least about 4, and a hydrogen bonding parameter value of at least about 10. Preferably, the hydrophilic fluid phase has Hansen's solvent parameters with these values: at least about-^-plus ·-=-This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) --- ------------------------- 、 耵 ---------------- 鮝. (Please read the back first Please note this page and fill in this page again) 1239988 A7 r___ __ B7 P V. Description of the invention (24) Dispersion parameter values from 8.0 to about 9.0, Polarity parameter values from about 50 to about 80, and about 12 to about 20 Hydrogen bonding parameter value. Generally, at least a small amount of water is desired to help dissolve or homogenize the components of the hydrophilic fluid phase. Generally, about 4 or 5% by weight of water can be included in the hydrophilic fluid phase rain for this purpose. When water is present at higher levels, and especially when the hydrophilic fluid phase is more than 50% water, adjustments are generally required to obtain a satisfactory ink. For example, organic or inorganic salts need to be added to the hydrophilic fluid phase to maintain the integrity of the emulsion. These salts include, without limitation, monovalent or divalent salts that are at least partially soluble in the hydrophilic fluid phase. Examples of such salts include, without limitation, salts of lithium, sodium, potassium, magnesium, calcium, iron (II), manganese (II), copper (II), and zinc, and especially the metals such as these. "Πα · & Acetate, Nitrate, Sulfate, Diprate, Hydrogenate, Hydrosulfate, Gas Salt, Chloride, Bromide and Iodide. These salts may be contained in the hydrophilic fluid phase up to about 5% by weight (preferably about 0.001% to about 5% by weight, and more preferably about 0.1% to about 15% by weight). In addition, when the hydrophilic fluid phase contains more than about 5% of water, any chemical group that can be precipitated by hydrogen bonding in an ink vehicle (such as a conventional acid-functional alkyd vehicle) needs to be compared with Use less. Humidifying agents (such as polyvinylpyrrolidone) can be added to help the plate wet. About 0.5% by weight to about 1.5% by weight of polyvinylpyrrolidone is included, based on the weight of the ink composition. I Those skilled in the art need to understand that other additives known in the art may be included in the ink composition of the present invention, as long as these additives do not significantly detract from the benefits of the present invention. Examples of these examples include, without limitation, the pour point suppression paper size (CNS) Α4 size (210X297 mm) " ^ 27-(Please read the precautions on the back before filling this page) • Order · 1239988 A7 ______B7 V. Description of the invention (25) '~ ^ Preparations, surfactants, wetting agents, soils, emulsifiers and dispersants, agents, antioxidants, UV absorbers, desiccants (for example, Vegetable oil composition), flow agent and other rheology modifiers, gloss promoters and anti-settling agents. When included, the additives are typically included in an amount of at least about 0.001% of the ink composition, and may be included in an amount of about 7% by weight or more of the ink composition. The composition of the present invention is suitable for any lithographic composition, which includes, without limitation, heat-setting ink, newspaper ink, and cut sheet ink. The offset printing method in which the ink of the present invention can be used is known in the art and described in many documents. The invention is illustrated by the following examples. These examples are illustrative only and do not in any way limit the scope of the invention as described and defined. Unless otherwise indicated ' all parts are parts by weight. Example In the example, t-BICM75 is a 75% solution of the third butylperoxy isopropyl carbonate in mineral spirits. Example- · 1. Hydrogen-bonded vinyl / carbon grease with carboxyl group was injected with 44.19 parts by weight of Total 200 (the crude middle distillate available from Total Crude Oil Company) into a stirrer and nitrogen inlet. Glass reactor with total reflux condenser and monomer inlet. The solvent was stirred under a blanket of nitrogen and heated to 160.degree. Monomer mixture of 36.01 parts by weight of styrene, 12.27 parts by weight of stearyl methacrylate, 2.62 parts by weight of divinylbenzene, K89 parts by weight of methacrylic acid and 2.79 parts by weight of t-BICM75 in 3 hours Added to the reactor during this period. After the monomers are completely added, the paper size is compliant with China National Standard (CNS) A4 (210X297 mm).

1239988 A7 B7 V. Description of the invention (26) (Please read the notes on the back before filling out this page) The t-BICM75 part weight is added in 15 minutes. The temperature was maintained at 160 ° C for another 2 hours to allow complete conversion of the monomer to polymer. The measured content of non-volatile materials (NVM) is 55%. The percent conversion (measured as NVM divided by the total weight of monomers) is 100.0. The acid number of the solution was 12.0 mg KOH / g. Viscosity is 30 Stokes (bubble tube, 54.4 ° C). Solvent tolerance is 230% and NVM at cloud point is 16.7%. Example 2. Preparation of a hydrogen-bonded vinyl resin with a carboxyl group 44.22 parts by weight of Golden Bear 1108 (crude crude oil available from Golden Bear Oil Specialties) is injected into a blender, nitrogen inlet, and total reflux Reaction flask with condenser and monomer inlet. The solvent was heated to 145 ° C with stirring. 33.86 parts by weight styrene, 12.6 parts by weight stearyl acrylate, 3.1 parts by weight n-butyl acrylate, 1.31 parts by weight divinylbenzene HP (80% divinylbenzene), 1.89 parts by weight methacrylic acid and 2.89 parts A monomer mixture by weight t-BICM75 was added to the reaction flask over a period of 3 hours. After monomer addition was complete, 0.23 parts by weight of t-BICM75 was added to the flask over a period of 15 minutes. The temperature was maintained at 145 ° C for another 2 hours to allow complete conversion of the monomer to polymer. The measured content of non-volatile materials (NVM) is 56%. The conversion percentage (measured as the percentage of the total weight of the monomers converted to non-volatile materials) is 101.5. The acid number of the solution was 12.0 mg KOH / g. The viscosity is 47 Stokes (bubble tube, 54.4t). The solvent tolerance is greater than 1400% and the NVM at the cloud point is less than 3.7% (ie, no cloud point has been observed at this dilution). Example 3. Preparation of a hydrogen-bonded vinyl resin having a carboxyl group. Calumet 600 (available from Calumet-^ -------): 461.2 parts by weight (applicable to China National Standard (CNS) A4 (210X297 mm)) 1239988 A7 B7 97 V. Description of the invention ()

Lubricants Co.'s crude oil middle point) was injected into a glass reactor equipped with a stirrer, nitrogen inlet, total reflux condenser and monomer inlet. The solvent was heated to 145 ° C with stirring under a blanket of nitrogen. 350.1 parts by weight of styrene, 131.3 parts by weight of stearyl methacrylate, 4.21 parts by weight of n-butyl acrylate, 17.1 parts by weight of divinylbenzene HP, 9.8 parts by weight of methacrylic acid, and 29.2 parts by weight of t-BICM75 monomer mixture Add to reactor during 3 hours. After monomer addition was complete, 2.4 parts by weight of t-BICM75 was added over a period of 15 minutes. The temperature was maintained at 145 ° C for another 2 hours to allow complete conversion of the monomer to polymer. The measured content of non-volatile materials (NVM) is 56%. The percent conversion (measured by dividing NVM by the total weight percent of monomer) is 101.6. The acid number of the solution was 6.3 mg KOH / g. Viscosity is 35 Stokes (bubble tube, 54.4 ° C). The solvent tolerance is greater than 80% and the NVM at the cloud point is 31.0%. Example 4. Production of a vinyl resin without hydrogen bonding as a comparative test

iJL 1548.1 parts by weight of ExxPrint 283D (crude crude oil obtained from Exxon Chemical Co.) was injected into a glass reactor equipped with a mixer, a nitrogen inlet, a total reflux condenser, and a monomer inlet. The solvent was heated to 145 ° C with stirring under a nitrogen blanket. 1248.5 parts by weight of styrene, 429.6 parts by weight of stearyl methacrylate, 102.8 parts by weight of n-butyl acrylate, 68.9 parts by weight of divinylbenzene HP, and 85.7 parts by weight of t-BICM75 monomer mixture were added to the reaction over a period of 3 hours Device. After monomer addition was complete, 16.4 parts by weight of t-BICM75 was added over a period of 15 minutes. The temperature is 145 ° (: keep for another 2 hours to fully convert the monomer into polymer. Non-volatile paper size applies Chinese National Standard (CNS) A4 specifications (210X297 mm) ---------- ------------------ # ---------------- 0 (Please read the notes on the back before filling this page) 1239988 A7 ___ B7 5. Description of the invention (28) The measured content of the material (NVM) is 56%. The conversion percentage (measured by dividing the NVM by the total weight percentage of the monomer) is 101.4. The viscosity is 26 Stokes (bubble tube , 54.4 ° C. The solvent tolerance is 160% and the NVM at the cloud point is 21.5% 〇 Fantu! 5. According to the present invention, the preparation of a single inkjet printing ink 58.0 g of the following mixture 5A is added to 142.0 Grams of the following mixture 5B and stirred. The ink composition was mixed on a disperser maintained at a vortex and maintained at a temperature of 14 ° C for 20 minutes. The ink composition had a single fall time of 14 to 17 seconds for 500 grams of the system at 30 ° C. Laray. When used in the single-fluid heat-setting lithographic printing method, the ink system is printed without color tone. Mixture 5A: 181.0 g of diethylene glycol, 8.0 g of deionized water, 0.4 g Citric acid and 0.4 g of magnesium nitrate were mixed in a glass beaker until clear. 191.2 g of diethylene glycol was added and mixed until homogeneous. Mixture 5B: Using a high-speed mixer, 46.0 g of the vinyl vehicle of Example 1 and 4.0 g of Blue Flush 12-FH-320 (available from CDR Corporation, Elizabethtown, KY), 1.0 g of technical grade soybean oil (available from Cargill, Chicago, IL) and 0.6 g of antioxidant. 34.4 grams of a hydrocarbon resin solution (60% LX-2600 in ExxPrint 283D, available from Neville), 27.0 grams of carbon black (CSX-156, available from Cabot Corp.), and 1.0 grams of polytetrafluoroethylene rhenium ( Pinnacle 9500D, available from Carrol Scientific). Mix at high speed for 30 minutes at 300 ° F. Slow down the mixing rate and add 27.0 grams of ExxPrint 588D (this paper size can apply Chinese National Standard (CNS) A4 specifications (210X297 mm) • ... : Meal ------------------ 、 Yes ............. 0 (Please read the precautions on the back before filling this page) 1239988 A7 B7

OQ 5. Description of the invention () from Exxon). The premix is ground in a granulating mill to the appropriate size. Mixture B has a Rayleigh viscosity of 180 to 240 poise and a Rayleigh yield of 800 to 1200 (according to ASTM D4040 method: power law-3k, 1.5k, 0.7k, 0.3k). Mixture B was tested on a Neem J ink layer thickness measuring instrument (Inkometer) at 1200 rpm for 25 to 29 units for 1 minute. Example 6. Preparation of a single fluid printing ink for a newspaper ink according to the present invention 6A: 87.0 g of diethylene glycol, 12.7 g of glycerol, 0.15 g of citric acid monohydrate and 0. 15 g of citric acid hexahydrate The mixture was heated (130-140 ° F) and stirred until homogeneous. Mixture 6B: Blend of 40.2 grams of hard asphalt varnish, 0.8 grams of refined oronite, 17.9 grams of MSO solvent (available from Calumet), and 41.1 grams of carbon black (CSX-320 from Cabot Corp.) The material was shear mixed to a Hegman grinding size of 4.0, then ground in a granulating mill to a size of at least 0/10 of a 2 mil size. The Rayleigh viscosity at 30 ° C was measured at 296 poise for 2000 grams of drop weight, and for a 200 grams drop of 1332 poise (± 25% accuracy), at 90 ° F (32 ° C) ) At 400 rpm for 1 minute and immediately thereafter at 1200 rpm for 1 minute to produce 5-10 units of printing ink layer thickness meter readings. Newspaper inks: Newspaper inks were obtained by mixing 32.4 grams of Mixture B and 37.6 grams of Example 2 together to obtain a temperature of 90 ° F (321) for 1 minute at 400 rpm and immediately after 1 minute at 1200 rpm. The paper size of 18.8 units applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) ---------- 1: ...... · --------------- --- 、 Can ---------------- Generation (Please read the precautions on the back before filling this page) 1239988 A7 B7 30 _ V. Printing ink layer of the invention description () Thickness meter reading, 375 poise for 2000 g added weight drop system at 30 ° C and 200 g added drop system (please read the precautions on the back before filling in this page) Lai Lei viscosity of 565 poise (± 25% accuracy) and a mixture of 6C with a viscosity of 285 poise measured at 2500 s · 1 according to ASTM D4040 (Power Law 2000, 1500, 1000, 500) and a planned output of 1709 dyne / cm 2. To obtain this ink, 30.0 g of mixture 6A was added to mixture 6C and mixed at 3000 rpm for 10 minutes. The formed ink has a single landing time of 21 seconds for 500 grams at 30 ° C. This ink does not exhibit hue when used in a single fluid lithographic printing method. Example 7. Synthesis of hydroxyl-bonded hydrogen-bonded vinyl resin ExxPdnt 274A (461 · 5 g) was injected into a reactor equipped with a stirrer, a nitrogen inlet, a total condenser, and an inlet. 371.5 g of styrene, 126.5 g of stearyl methacrylate, 23.9 g of divinylbenzene HP, 29.8 g of hydroxypropyl methacrylate and 27.7 g of t-BICM75 monomer / starter blend over 2 hours 15 The reactor was injected via the inlet during the minutes. During the addition, the temperature was maintained at 160 ° C and the reactor was covered with nitrogen. After the addition, 2.5 g of t-BICM75 was added, and the reaction was performed for an additional 2 hours. The reaction product was poured into a storage container through a fine filter. The measured content of non-volatile materials (NVM) is 56.2%. The conversion percentage (measured as the percentage of the total weight of monomers converted to non-volatile materials) is 102.2. Viscosity is 12.0 Stokes (bubble tube, 54.4 ° C). Solvent tolerance is 380% and NVM at cloud point is 11.7%. Example 8. ExxPdnt 274A (461 · 5g), a synthetic solvent containing a hydrogenated vinyl resin containing amido groups, was injected into a stirrer and nitrogen. The paper size was in accordance with Chinese National Standard (CNS) A4 (210X297 mm) ) 1239988 A7 B7 — V. Description of the invention () Gas inlet, main condenser and inlet reactor, and stir to 160 ° c. 376.8 g of styrene, 128.3 g of stearyl acrylate, 23.9 g of divinylbenzene HP, 22.7 g of N, N-dimethylacrylamide, and 27.7 g of t-BICM75 monomer initiator blend It was injected through the inlet during 2 hours and 15 minutes, during which the temperature was kept at 160 ° C with stirring and the reactor was covered with nitrogen. After the addition was complete, 2.5 grams of t-BICM75 was added and the reaction continued for another 2 hours. The measured content of non-volatile materials (NVM) was 56.6%. The percent conversion is 103.0. The viscosity is 23.5 Stokes at 54.4 ° C. Solvent tolerance is 688%, NVM at cloud point is less than 8.2%. Example 9 Using a high-speed mixer, 118 grams of the hydrogen-bonded vinyl resin of Example 8 and 102.5 grams of Lanxiaguang 15FQ-308 (containing phthalocyanine blue, Available from CDR Corporation, Elizabethtown, Kentucky), 16.5 grams of burnt-based refined linseed oil and 5 grams of Teflon wax blend. While mixing, 116.5 grams of a hydrocarbon resin solution (60% Lx-2600, at ExxPrint 283D, available from Neville) was added and mixed at 160 ° F for 30 minutes at high speed to form mixture 9b. The mixing rate is slowed and 28.3 parts by weight of mixture 5a is added to 71.7 parts by weight of mixture 9b. The finished viscosity of the ink at 30 ° C (cone-plate rheometer) is 178.3Pa s. This ink was tested for stability and hue in lithographic printing methods. The stability of the ink reservoir of this ink is greater than 900 seconds, and the ink is printed with no tone. Example 10. Preparation of ink containing fluoramine functional vinyl resin-M- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) --------------- Γ —… Meals -....... 、 玎 --------------- (Please read the notes on the back before filling in this Page) 1239988 A7 B7 V. Description of the invention () (Please read the notes on the back before filling this page) Mixture 10a is obtained by mixing 181 g of diethylene glycol, 8 g of deionized water, 0.4 g of triethanolamine in a glass beaker. And 0.4 g of magnesium nitrate to form a homogeneous. Add 191.2 grams of ethylene glycol and mix until homogeneous. Using a high-speed mixer, 118 grams of hydrogen-bonded vinyl resin of Example 7 and 102.5 grams of Lanxiaguang 15FQ-308 (containing phthalocyanine blue, available from CDR Corporation, Elizabethtown, Kentucky), 16.5 grams of burnt-based refined linen Mix seed oil with 5 grams of Teflon wax. By mixing, 116.5 grams of a hydrocarbon resin solution (60% Lx_2600, at ExxPrint 283D, available from Neville) was added and mixed at 160 ° F for 30 minutes at high speed to form mixture 10b. To prepare this ink, 28.3 parts by weight of a mixture 10a and 71.7 parts of a mixture 10b were mixed. The finished product viscosity (cone-plate rheometer) of this ink at 30 ° C is 101.8 Pa s. This ink was tested for stability and hue in lithographic printing methods. The stability of the ink reservoir of this ink is greater than 900 seconds, and the ink is printed with no tone.

Examples 11-16 and Comparative Examples A-D Examples 11-16 and Comparative Examples A-D were prepared by a method similar to that of Example 5 and the components and component contents listed in the following table. These examples were tested for stability in ink reservoirs and for color tones in lithographic printing methods. Examples 11-13 were prepared from the acid-functional vinyl resin of Example 1, and Examples 14-16 were prepared from the acid-functional vinyl resin of Example 3. The hydrophilic phases of all Examples 11-16 contained a mixture of diethylene glycol, ethylene glycol and water of Example 5A, and further contained citric acid and magnesium nitrate. In comparing the paper size to the Chinese National Standard (CNS) A4 (210X297 mm) 1239988 A7 ____B7 V. Description of the Invention (33) In the example, the ink is a lithographic printing method that does not contain the hydrogen-bonded vinyl resin of the present invention. Operation. Comparative Examples A-C contained the vinyl resin of Example 4, which did not contain a functional group capable of forming a hydrogen bond of a component bonded to a hydrophilic phase. Comparative Example D was operated on an ink prepared from a conventional turpentine-modified hydrocarbon solution. In the case of Comparative Examples A-C, the ink was unstable in the ink reservoir and was not stable enough for operation in the printing method. Comparative Example D had a son-in-law character sufficient for operation in a printing method, but exhibited an excellent tone on the first sheet to be printed. Material Comparative Example A Comparative Example B Comparative Example C Comparative Example D The vinyl resin of Example 4 8 18 37 ~~ Hydrocarbon solution modified by turpentine 4 (number of acids in solution system 4.8) 37 Hydrocarbon varnish solution 1 32.5 22.5 Coated black bottom 2 30 30 30 ~ " 30 ~ 'Total 220 0.5 0.5 4'-Diethylene glycol mixture 3 29 29 29 29 Ink container rupture time (seconds) 200 60 5 'Η > 600 ~ Hue ( Insufficient stability for operation) Insufficient stability for operation) (Instable stability for operation) Immediately (^ 1: Sheet produces color tone) 4. 55% RP 369 (available from Westvaco , St. Louis, MO), in ExxPrim 283D. Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Acid-functional vinyl resin 8 in watt example 8 Τδ " Acid-functional vinyl resin in watt 3 example 8 ~~ 18 37 Hydrocarbon varnish solution 1 32.5 22.5 32.5 ~ 22.5 Uncoated black background 2 30 30 30 30 30 30 Total 220 0.5 0.5 4 0.5 0.5 4 Diethylene glycol mixture 3 29 29 29 29-29 29 Ink reservoir rupture time (seconds) > 600 > 600 > 600 > 600 > 600 > 600 Hue clarification clarification clarification clarification clarification 1. LX2600 (available from Neville Chemical Co., Pittsbm ^ h: PA) »60% ^ MExxPrint 283D 2.45% carbon black material ( In 51% hydrocarbon varnish solution), 3% soybean oil, 1% anti-oxidative cutting 3. Example 5 mixture 5A ', one = mouth (please read the precautions on the back before filling out this page) Best specific examples are described in detail. However, it should be understood that various changes and improvements can be made within the spirit and scope of the present invention and the scope of the following patent applications. This paper size applies to China National Standard A4 (210X297 mm)

Claims (1)

Six: Application for the protection of the scope of each 1J patent application No. 91116043 Patent Application Amendment 9307728 1 · A lithographic ink composition comprising a continuous phase comprising a hydrogen-bonded vinyl polymer, and an emulsified phase, It contains water. 2. The lithographic ink composition according to item 1 of the application, wherein the emulsified phase further comprises a member selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, glycerol, and monopropylene glycol. Liquid polyols of the group consisting of 1,3-propanediol, dipropylene glycol, butanediol, glycerol and mixtures thereof. 3. The lithographic ink composition according to item 丨 of the patent application scope, wherein the ink composition contains 5% to 50% by weight of the emulsified phase. 4. The lithographic ink composition according to item 1 of the patent application scope, wherein the ink composition contains the emulsified phase in an amount of 0% to 35% by weight. 5. The lithographic ink composition according to item 丨 of the application, wherein the ink composition contains 20% to 30% by weight of the emulsified phase. 6. The lithographic ink composition according to item 1 of the patent application scope, wherein the emulsified phase contains a weak acid or weak acid. Consumption cooperation stamps of employees of the Intellectual Property Bureau of the Ministry of Economic Affairs have cracked into the lithographic ink composition as described in the first patent application scope, wherein the emulsified phase contains a member selected from lithium, sodium, potassium, magnesium, calcium, iron, and n), copper (π) and zinc acetates. Glycolates, nitrates, sulfates, phosphates, hydrosulfates, hydrosulfates, chlorates, chlorides, bromides, iodides, and A member of a community of mixtures. 8. The lithographic ink composition according to item 1 of the application, wherein the emulsified phase comprises water and a liquid polyol. 9. If the lithographic ink composition of item 1 of the patent application scope, wherein the emulsification 37 1239988 A8 B8 C8 D8 VI. Apply for the seal of consumption cooperation of employees of the Intellectual Property Bureau of the Ministry of Economic Affairs of the patent scope of the patent application and further include at least one Solid polyol. A The micro-continuous ink composition according to item 1 of the patent application scope, wherein the emulsified phase comprises 2,3-butanediol, hexanediol, pentaerythritol, dipentaerythritol, a highly functional branched dendrimer with hydroxyl functionality, and three Methyl alcohol ethane, dimethyl alcohol propionate, Xinyi Qiyihui 4 ammonium chloride, 2,2,4-trimethyl-1,3-pentane dioxin, H bad One of the members of the group consisting of dimethyl alcohol, gasified difluorene, A, compounds with a single radical, and up to 18 stone anatomic atoms, and mixtures thereof. η. The lithographic ink composition according to item 1 of the patent application, wherein the emulsified phase comprises one member of the group consisting of «acid, tartaric acid, tannic acid, and mixtures thereof. 12. The lithographic ink composition according to item 1 of the patent application, wherein the emulsified phase contains triethanolamine. ... Shen. The lithographic ink composition according to item 1 of the monthly patent, wherein the emulsified phase contains a weak acid or a strong base of from 0. 0% by weight to 2% by weight. 14 · If the scope of patent application is the first! The lithography of item. The ink composition, wherein the emulsified phase contains 0.01% by weight to 0.5% by weight of magnesium nitrate. 15. The lithographic ink composition according to item 1 of the scope of the patent application. The chemical phase contains a water-soluble polymer. 16. For the lithographic ink composition according to item 丨 of the scope of patent application ... The chemical phase contains a material selected from the group consisting of poly (vinyl alcohol), poly (ethylene alcohol), poly (ethylene glycol), and the like. A member of a community of mixtures. A lithographic ink composition comprising: a continuous phase comprising a hydrogen-bonded vinyl polymer, the hydrogen-bonded vinyl polymer comprising a group selected from a carboxylic anhydride group, a primary amine group, and a tri-38- Where the milk among the milk «! Installed -------- order -------- tj (Jing first read the phonetic of the song δ? Please fill out this page again) 17. 1239988 6. Apply for a patent Ammonium substituents with a range of or less carbon atoms, amine groups of primary ammonium groups, amidine groups of cylic alkyl substituents with three or less carbon atoms, groups with three or less carbon atoms A hydrogen bonding group of a group consisting of an ester group, an isocyanate group, a hydroxyl group, a sulfur-containing group, a phosphorus-containing group, an ethyl acetate group, and a mixture thereof; , Including one member of the group consisting of water, liquid polyols, and mixtures thereof. 18. The lithographic ink composition according to claim n, wherein the air-bonded vinyl polymer comprises a primary amine group, an amine having an N-alkyl substituent of three or less carbon atoms Or a mixture thereof. 19. The lithographic ink composition according to item 17 of the application, wherein the air-bonded vinyl polymer comprises a primary fluorenyl group, and fluorenamine having an N-alkyl substituent of three or less carbon atoms. Or a mixture thereof. 20. The lithographic ink composition according to claim 1 in the scope of the patent application, wherein the nitrogen-bonded ethylenimine-based polymer contains a warp group. 21 · The lithographic ink composition according to claim 17 of the patent scope, wherein the hydrogen-bonded vinyl polymer includes a carboxylic acid anhydride group. 22. The lithographic ink composition as claimed in claim π, wherein the hydrogen-bonded vinyl polymer comprises an alkyl group having a pendant alkyl group having three or less carbon atoms, a / 3-hydroxyester group, or Its mixture. 23. The lithographic ink composition according to item 17 of the patent, wherein the hydrogen-bonded vinyl polymer contains a sulfur-containing group. 24. The lithographic ink composition according to item 17 in the scope of the patent application, wherein the hydrogen-bonded, fluorene ethylenic polymer comprises a member selected from the group consisting of a continuous acid group, a continuous amine group, a sulfur oxide group, a fluorene group, Thiol, Phosphate, Phosphate, Phosphoamidine, and f% (Min ^ on the back of the letter before filling out this page)-Binding. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ 39 [239988 A8 B8 C8 D8 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and the Consumer Cooperatives. Scope of patent application. Hydrogen bonding of ethnic groups composed of mixtures. 25. The lithographic ink composition according to claim 17, wherein the hydrogen-bonded vinyl polymer comprises a vinyl alcohol monomer unit. 26. The lithographic ink composition according to claim 20, wherein the emulsified phase includes a weak test. 27. The lithographic ink composition according to claim 17, wherein the hydrogen-bonded vinyl polymer comprises a mixture of different hydrogen-bonded groups. 28. The lithographic ink composition according to item 17 of the application, wherein the hydrogen-bonding group of the hydrogen-bonded vinyl polymer serves as a hydrogen-donating group. 29. The lithographic ink composition according to item 17 of the application, wherein the hydrogen-bonding group of the hydrogen-bonded vinyl polymer serves as a hydrogen-accepting group. 30. The lithographic ink composition according to item 17 of the application, wherein the hydrogen-bonding group of the hydrogen-bonded vinyl polymer serves as a hydrogen-donating group and a hydrogen-accepting group. 31. The lithographic ink composition according to claim 28, wherein the emulsified phase includes a weak test. 32. The lithographic ink composition according to claim 29, wherein the emulsified phase contains a weak acid. 33. The lithographic ink composition according to claim 17, wherein the hydrogen-bonded vinyl polymer has an equivalent weight of at least 1,800 g / equivalent based on the hydrogen-bonded group. 34. The lithographic ink composition according to item 17 of the application, wherein the hydrogen-bonded vinyl polymer has an equivalent weight of up to 20,000 g / equivalent based on the hydrogen-bonded group. 3 5. The lithographic ink composition according to item 17 of the scope of the patent application, wherein the hydrogen is 40 sheets of paper, which is used in the Chinese standard iMCNS) A4 specification (2) 0 > 297. (Notes for v8, please fill out this page) 1239988 A8 B8 C8 D8 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ¾ Application for patents-. Bonded ethylene-based polymers have 2200 g / equivalent to 7200 g / equivalent, which is based on hydrogen bonding meter. 36. The lithographic ink composition according to claim 1 in the patent application range, wherein the nitrogen-bonded vinyl polymer includes an ethyl acetate group. 37. A lithographic ink composition comprising: a hydrophobic continuous phase comprising a solution of a branched hydrogen-bonded vinyl polymer, and an emulsified phase comprising water. '38. The lithographic ink composition according to item 37 of the application, wherein the emulsified phase further comprises a member selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, A liquid polyol of the group consisting of 13-propanediol, 4 -butanediol, glycerin and mixtures thereof. 39. The lithographic ink composition according to item 37 of the application, wherein the ink composition comprises 5% to 50% by weight of the emulsified phase. 40. The lithographic ink composition according to claim 37, wherein the ink composition comprises 10% to 35% by weight of the emulsified phase. 41. The lithographic ink composition according to item 37 of the scope of the patent application, wherein the emulsified phase comprises a member selected from the group consisting of lithium, sodium, potassium, magnesium, iron, iron, manganese, copper (Π), and zinc. A member of the group consisting of acetate, triacetate, salts, sulfates, onates, hydrophosphates, hydrosulfates' chlorates, vapors, deserts, iodides, and mixtures thereof. 42. The micro ink composition according to item 37 of the application, wherein the emulsified phase comprises water and a liquid polyol. 43. According to the U.K. shadow ink composition of Tulebe in the scope of patent application, the size of the milk paper is 41-. -Jn! (Notes on the back of Zhu Xianxian 15 before filling out this page) 1239988 6. Scope of patent application ‘Chemical phase further includes at least one solid polyol. 44. The lithographic ink composition according to item 37 of the application, wherein the emulsified phase further comprises 2,3-butanediol, hexanediol, pentaerythritol, and dipentaerythritol. Compounds, trimethyl alcohol ethyl ^, dimethyl alcohol propane, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-cyclohexanedimethanol, Member of the group consisting of hydrogenated bisphenol A, compounds having one hydroxyl group and up to 18 carbon atoms, and mixtures thereof. 45. The lithographic ink composition according to claim 37, wherein the emulsified phase contains from 0.01 to 2% by weight of a weak acid or a strong base. 46. The lithographic ink composition according to claim 37, wherein the emulsified phase contains a wetting agent. 47 · An ink composition for lithography, comprising: a hydrophobic continuous phase of a hydrogen-bonded, ethylenically-based polymer solution containing a branched chain, the hydrogen-bonded vinyl polymer comprising a carboxylic anhydride group , Primary amine groups, amine groups with N-alkyl substituents having three or fewer stone anatomic atoms, primary amine groups, N-:!: End-group substituents with three or less $ anion atoms Amino groups, ester groups with pendant alkyl groups of three or fewer carbon atoms, non-hydroxy ester groups, hydroxyl groups, employees of the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumption Co., Ltd., phosphorus-containing groups, ethyl acetate The ΐ bond group of the group consisting of the ester group and the mixture thereof. 48. The lithographic ink composition according to item 47 of the application, wherein the chlorine-bonded vinyl polymer comprises a primary amine group, an amine group having N-alkyl substituents having three or less carbon atoms, or Its mixture. 49. The lithographic ink composition according to item 47 of the patent application scope, wherein the chlorine-42-.---------------- This paper standard uses the Chinese standard Half (CNS) A4 specification (?) 0. χ297 publicly issued 1239988 consumer cooperation soil seal of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ ^ N ^ / Patent scope '. Bonded vinyl group: The polymer contains a fluorenyl group, a fluorenyl group having a three or atom N-alkyl substituent, or a mixture thereof.乂 衩 50. The lithographic ink composition according to item 47 of the patent application, wherein the hydrogen bond B :): the sternyl polymer contains a warp group. 51. The lithographic ink composition according to claim 47, wherein the bonded vinyl polymer contains a carboxylic acid anhydride group. Bond: The lithographic ink composition of item 47, wherein the base polymer contains a fluorenyl group having a pendant group of three or less carbon atoms, an rhydroxyester group, or a mixture thereof. 53. The ink composition according to item U of the scope of the patent application, wherein the hydrogen, vinyl, and " vinyl polymer contains a sulfur-containing group. 54. If the chemical phase of item 47 in the scope of patent application includes weak inspection. Ink composition, which is the ink composition for lithography in which the milk 5X is applied for in the scope of patent application No. 47, wherein the nitrogen, ethyl ether polymer includes a mixture of different hydrogen bonding groups. 56. = Patent No. 47 of the _ ink group silk, wherein the hydrogen bonding group of the gas ethylene silk compound is used as a hydrogen donor group. 57. The lithographic ink composition according to item 47 of the patent application, wherein a hydrogen-bonding group bonded to an ethylene-based polymer is used as a hydrogen-accepting group. 58. For example, the lithographic ink composition according to item 47 of the patent, wherein the hydrogen bonding group of the ethylene silk compound is used as a hydrogen donor group and a chlorine acceptor group. For example, the lithographic ink composition of the 56th aspect of the patent application, wherein the emulsified phase contains a weak base. 6〇_If the lithographic ink composition of the 57th scope of the application for a patent, wherein the lactate ------------ ^^ 丨 installed ---- (^ First Mif back Please pay attention to this page and fill in this page again) I Iτ, · ". 1" I i where the hydrogen and the hydrogen φ -------43 1239988 A8 B8 C8 D8 6. The scope of patent application phase contains weak acid. 61. For example, the lithographic ink composition of item 47 of the patent application, wherein the hydrogen-bonded vinyl polymer has an equivalent weight of at least 1,800 g / equivalent, which is based on the hydrogen-bonded group. The lithographic ink composition of item 47, wherein the hydrogen-bonded vinyl polymer has an equivalent weight of up to 20,000 g / equivalent, which is based on the hydrogen-bonded group. 63. If the scope of patent application is 47 The lithographic ink composition, wherein the hydrogen-bonded vinyl polymer has an equivalent of 2200 g / equivalent to 7200 g / equivalent, which is based on the hydrogen-bonded group. Lithographic ink composition, wherein the hydrogen-bonded vinyl polymer uses at least one polymerizable ethylenic unsaturated 65. For example, the lithographic ink composition according to item 47 of the patent application, wherein the hydrogen-bonded vinyl polymer is polymerized using divinylbenzene. 66. As described in item 47 of the patent application, Lithographic ink composition, wherein the hydrogen-bonded vinyl polymer is polymerized using at least 0.008 equivalents / 100 grams of a monomer polymerized with at least one monomer having two or more polymerizable ethylenically unsaturated bonds. 67 . For example, the lithographic ink composition according to item 47 of the patent application, wherein the hydrogen-bonded vinyl polymer uses 0.012 to 0.08 equivalents per 100 grams of at least one polymerizable ethylenically unsaturated bond. 68. For example, the lithographic ink composition of item 47 in the scope of patent application, wherein the hydrogen -44-the standard of this paper is S 舀 house standard ai (CNS) A4 set grid m 〇 > ^ 97) (Please fill in the notes on the back of 3 before filling out this page) Binding 4 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1239988 AS B8 __ C8 ^ __ — _ ™ / 、、 Scope of Patent Application Bonded vinyl polymers use 0.016 to 0.064 # / 100g is polymerized with at least one monomer having two or more polymerizable ethylenically unsaturated bonds. 69. The lithographic ink composition according to item 47 of the patent application, wherein the hydrogen bond is Vinyl polymers are polymerized using at least 0.004 equivalents / 100 grams of two monomers that polymerize each of the monomers having a reactive group in addition to the ethylenically unsaturated polymerizable bond. 70. The lithographic ink composition of the 47th member of the scope of application for a patent, wherein the hydrogen-bonded vinyl polymer has been selected from the group consisting of an aluminum gelling agent, an alkoxide, an aluminate, and a mixture thereof. One of the branches. 71. The lithographic ink composition according to item 47 of the patent application, wherein the hydrogen-bonded vinyl polymer has been selected from the group consisting of acetoacetone aluminum, triisopropyl aluminum oxide, di-second butyl aluminum oxide, and aluminum. One branch of acetamyl diisopropoxide, aluminum oxyacetylate, and mixtures thereof. 72. The lithographic ink composition according to claim 47, wherein the hydrogen-bonded vinyl polymer has a number average molecular weight of at least 1,000 and a weight average molecular weight of at least 30,000. 73. The lithographic ink composition according to claim 47, wherein the hydrogen-bonded vinyl polymer has a weight-average molecular weight of at least 100,000. 74. The lithographic ink composition according to claim 47, wherein the hydrogen-bonded vinyl polymer has a polydispersity of at least 15. 75. The lithographic ink composition according to claim 47, wherein the hydrogen-bonded vinyl polymer has a polydispersity of at least 50. Used this paper size?舀 舀 Home Brown Soap (CNS) A4 Specification (2) 0_ > 297 Public Transport) (Notes on the back of ifiLMts, please fill in this page again) Binding. Printed by the Staff Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs-f. 45 1239988 AS B8 C8 D8 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ^: Application for Profit Scope _ ~ 76 · If the lithographic ink composition of item 47 of the patent scope is applied, the hydrogen-bonded vinyl polymer has 15 to 100. 〇The degree of dispersion. 77. The lithographic ink composition according to claim 47, wherein the hydrogen-bonded vinyl polymer has a polydispersity of 50 to 800. 78. The lithographic ink composition according to claim 47, wherein the hydrogen-bonded ethylene-based polymer has a theoretical glass transition temperature higher than room temperature. 79. The lithographic ink composition according to item 47 of the patent application, wherein the bonded vinyl polymer has a theoretical glass transition temperature of at least 600 ° C. 80. The lithographic ink according to item 47 of the patent application A composition wherein the milk-bonded vinyl polymer has ^. (Theoretical glass transition temperature of 125 to 125 t. 'Panel M. For example, the lithographic ink composition of item 47 of the patent application range, wherein the chain,', and shell phase comprise a member selected from the group consisting of polyester, alkyd, phenolic, turpentine, Cellulose, turpentine 2M, mysterious modified turpentine, hydrocarbon modified turpentine, malay ^ pine turpentine, formalin modified turpentine, hydrocarbon resin, polyamide, not hydrogenated with this etiquette phase Further materials of the group consisting of vinyl polymers and mixtures thereof. 82. The lithographic ink composition according to item 81 of the patent application scope, wherein the further materials are based on the hydrogen-bonded ethylene for each part by weight. The base polymer is included in an amount of up to 100 parts by weight. 83. The lithographic ink composition as described in item 81 of the patent application scope, wherein the further material is based on Hydrogen-bonded ethyl polymer is included in an amount of 3 parts by weight to 50 parts by weight. 84. The lithographic ink composition according to item 47 of the patent application scope, wherein the hydrogen-hydrogen group For the matters needing attention, please fill in this page again) Install J ^ T. T 46 297 male) A8 B8 C8 D8 Heavy Hydrogen B Subsidiary Intellectual Property Bureau of the Ministry of Economic Affairs Employee Consumption Cooperative Indo-Pacific 1239988 Scope of Patent Application ... Bonding B, dilute polymer based system uses at least 15 weight. /. The propylene polymerization having π in the alcohol portion is based on the total monomer weight. 85. If applying for the lithography I! Composition of Item 47, the chlorine-bonded ethyl-based polymer uses 15% to 30% by weight of the alcohol portion having 8 to 20 shilus. Shao & γ a stone in contrast to C fine S purpose polymerization, which is based on the total monomer amount. 86. For example, the lithographic ink composition according to item 47 of the application, wherein the bonded ethylene polymer is polymerized using 50 to 80% by weight of styrene, which is based on the total monomer weight. . 87 · —A lithographic ink composition comprising: a hydrophobic continuous phase comprising a solution of a branched hydrogen-bonded ethylene-based polymer, and a etiquette phase having a policy of at least 6 as a Hansen solubility parameter Cang value, a polarity parameter value of at least 4, and a nitrogen bond parameter value of at least iq. 8 8 · If the scope of patent application is 帛 8 7 for workers 'lithography, the composition, where the dispersion parameter value is 8 to 9' the polarity parameter value is 5 to 8, and the hydrogen bonding parameter value is 12 to 2 0. 89 · —A lithographic ink composition comprising: a continuous phase, a vinyl polymer containing a fluorenyl group containing a primary fluorenyl group, an N-alkyl substituent having 3 or less carbon atoms, or a mixture thereof Materials, in which the vinyl polymer has a polydispersity of at least 15; and no. A sheet of scale which uses the Chinese family standard half (eight 4 47 7¾¾ (210 > 297 (please read the phonetic notation of 15 back ¾? (Fill in this page again) 1239988 A8 B8 C8 D8 Patent application scope. ‘Emulsified phase, the inclusion of which is selected from the group consisting of water, liquid polyols and mixtures thereof. 9 0 · The lithographic ink composition according to the scope of application for patent item No. 9, wherein the emulsified phase contains a member selected from the group consisting of ethanediase, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, 1, 3 _ Liquid polyols of the group consisting of propane dicasein, dipropylene glycol and mixtures thereof. 91. The lithographic ink composition according to claim 89, wherein the ink composition contains 5% to 50% by weight of the emulsified phase. 92. The lithographic ink composition according to claim 89, wherein the ink composition contains 10% to 35% by weight of the emulsified phase. 93. The lithographic ink composition according to claim 89, wherein the ink composition contains 20% to 30% by weight of the emulsified phase. 94. The lithographic ink composition according to claim 89, wherein the emulsified phase contains a weak acid or a weak base. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 95. For example, the lithographic ink composition of the 89th scope of the patent application, wherein the emulsified phase contains a member selected from lithium, sodium, potassium, magnesium, calcium, iron (11), Manganese (π), copper (Π) and zinc acetates, glycolates, nitrates, sulfates, tank salts, hydrophosphates, hydrosulfates, chlorates, chlorides, bromides, stone compounds And one of its members. 96. The lithographic ink composition according to claim 89, wherein the emulsified phase is non-aqueous. 97. The lithographic ink composition according to item (1) of the patent application scope, wherein the B and H x χκ mouthpieces further comprise an ester group having a pendant group having 3 or less carbon atoms, and a / 9-hydrocarbon ester group Or a mixture thereof. 48 # (CNS) A4 (2) 〇: < 297 1239988 A8 B8 C8 D8 Consumption cooperation between employees of Intellectual Property Bureau of the Ministry of Economic Affairs of the People's Republic of China for the scope of patent application, such as the composition of lithographic ink for the 97th scope of the patent application in May Material, wherein the vinyl polymer has an equivalent weight of 2200 g / equivalent to 72,000 g / equivalent, which is based on the total amidine and ester groups. &Quot; The ink composition for film, wherein the amido group is obtained by copolymerizing N, N-dimethylacrylamide, and the ester group is obtained by copolymerizing methyl methacrylate. 100. If applied The lithographic ink composition of item 89 of the patent, wherein the vinyl polymer has a number average molecular weight between 10,000 and 15,000, and a weight average molecular weight of at least 100,000. 101. The lithographic ink composition as described in claim 89, wherein the continuous phase comprises a resin selected from the group consisting of polyester resin, hydrocarbon resin, alkyd resin, phenolic resin, turpentine, cellulose turpentine, and modification thereof. Further materials of the group consisting of the mixture and its mixture. An ink composition for lithography according to item 1, wherein the further material is less hydrophilic than the acid-functional ethylene-based polymer. 103.-A method for preparing a printing ink for lithography, comprising making amine containing fermented amine The step of mixing the first composition of the official hydrogen-bonded vinyl polymer with a second group comprising one member selected from the group consisting of water, polyhydric alcohols, and mixtures thereof, thereby forming an ink, which has The first composition as the continuous phase and the second composition as the discontinuous phase. 104. h The lithographic ink composition for patent application No. 89, whose emulsified phase contains water. 105. μPlease patent scope The lithographic ink composition of item 89 can be made into this medium—φ! Μ (^ Notes on the back side before filling out this page) J-ξτ · • t 49 1239988 A8 B8 C8 D8 Patent application scope: Viewing further-further comprising a member selected from the group consisting of solid polyol compounds' solid polyvalent sulfonate polymers and compounds having-hydroxyl groups and compounds up to 18 carbon atoms. P brushing method, including the use of such as application Ink of item i of patent scope as a single fluid micro Step of printing a substrate by photolithography of a shadow ink. 10 = a printing method including the use of photolithography of a photolithography ink using a single fluid as described in Patent Application No. 89. Steps for printing. «! Packing (please fill in the notes on the reverse side before filling out this page) Order · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. S k • T- A 5) N (c iii.Ibid Ijiacb— rr) / rl one ix rule paper I book one S one eight two 7/9 50