WO2018133213A1

WO2018133213A1 - Modified polyvinyl alcohol and synthesis method therefor, hydrophilic plate for printing and application thereof, and printing plate

Info

Publication number: WO2018133213A1
Application number: PCT/CN2017/079564
Authority: WO
Inventors: 沙栩正; 宋延林; 杨明; 吴为; 秦明明
Original assignee: 中国科学院化学研究所
Priority date: 2017-01-20
Filing date: 2017-04-06
Publication date: 2018-07-26

Abstract

The present invention relates to the field of printing plates, and discloses a modified polyvinyl alcohol and a synthesis method therefor, a hydrophilic plate for printing and an application thereof, and a printing plate. The modified polyvinyl alcohol is polyvinyl alcohol sulfonate, polyvinyl alcohol ester benzene sulfonate or polyvinyl alcohol ester sulfonate. Said type of hydrophilic high molecular compound may greatly increase the hydrophilicity of a coating and improve the printing suitability of a hydrophilic plate.

Description

Modified polyvinyl alcohol and synthesis method thereof, hydrophilic plate and application for printing and printing plate

Technical field

The present invention relates to the field of printing plates, and in particular to a modified polyvinyl alcohol and a synthetic method thereof, comprising a hydrophilic plate for printing a hydrophilic layer formed of the modified polyvinyl alcohol, the hydrophilic plate being in a printing plate Applications, as well as ink jet printing plates, photosensitive photographic printing plates and thermal printing plates formed from the hydrophilic plate.

Background technique

The printing industry is one of the industries that have an important impact on China's national economy. Preparing a printing plate is an important technical step. In modern printing plate preparation, a hydrophilic plate is usually prepared first, and an ink jet printing plate, a photosensitive photosensitive printing plate or a thermal printing plate or the like can be further prepared on the basis of the hydrophilic plate. Therefore, obtaining a high quality hydrophilic plate is a top priority.

CN103587273A discloses a photosensitive, non-sanding plate comprising a plate, a hydrophilic layer and a photosensitive layer, the hydrophilic layer and the photosensitive layer being sequentially coated on the substrate. The hydrophilic layer contains nano-sized and/or micro-sized particles and a resin. The coated hydrophilic layer has hydrophilic properties and water retention properties similar to those after electrolytic sanding and anodizing, and can replace the plate after electrolytic sanding and anodizing, thereby greatly avoiding the waste acid generated by anodizing. And the purpose of waste alkali pollution of the environment.

CN103937303A discloses a cationically polymerized hydrophilic coating material comprising from 15 to 45% of a vinyl ether monomer or a prepolymer thereof, from 1 to 5% of a cationic initiator, and from 50 to 80% by mass. Composition of nano- or micro-scale hydrophilic particles. The hydrophilic coating material is coated on the substrate and cured by ultraviolet light to obtain a sand-free printing plate. The method adds hydrophilic particles to the coating forming the hydrophilic layer to provide the finally obtained printing plate material, which can save the sanding treatment on the plate base, simplify the process and improve the viscosity and surface tension of the plate material.

CN102407653A discloses an environmentally friendly lithographic printing plate base comprising a metal or non-metal plate base, wherein an adhesive layer and a hydrophilic layer are sequentially adhered to the plate base, and the adhesive layer is cured by a coating liquid of the adhesive layer. The hydrophilic layer is formed by curing a hydrophilic layer coating liquid, and the hydrophilic layer coating liquid is composed of 5%-10% hydrophilic polymer resin, 10%-30% nanometer or micron metal. Or a non-metal oxide, 0.5%-5% curing agent and 0.05%-3% surfactant and 60%-80% water; the substrate is a metal material, and the bonding layer coating liquid is 10% -40% thermosetting resin, 3%-20% curing agent and 50%-80% aqueous solvent; the substrate is a non-metallic material, and the bonding layer coating liquid is 5%-50% solvent resin , 0-25% corrosive agent and 30%-95% aqueous solvent. However, this method requires nano or micro-scale metal or non-metal oxides to help improve the hydrophilic properties of the hydrophilic layer and requires an additional tie layer to provide adhesion.

In the prior art, nano- or micro-sized hydrophilic particles are often used to form a hydrophilic layer, which is likely to cause dirty and flawed printed products.

Summary of the invention

The object of the present invention is to solve the problem of how to improve the printing performance of a hydrophilic plate for printing, and to provide a modified polyvinyl alcohol and a synthetic method thereof, a hydrophilic plate and application for printing, and a printing plate. A clean printed product can be obtained and the printing plate has a high printing durability.

In order to achieve the above object, the present invention provides a modified polyvinyl alcohol, which is a polyvinyl alcohol sulfonate, a polyvinyl alcohol benzene sulfonate or a polyvinyl alcohol sulfonate;

The polyvinyl alcohol sulfonate contains a chemical structure represented by the formula (1),

Formula (1) wherein m + n = a positive integer of 400 to 5000, n / (m + n) = 0.05 to 1, x is a positive integer of 1 to 3; and A ₁ to A ₄ are each independently hydrogen or a C ₁ -C ₆ alkyl group;

The polyvinyl alcohol sulfonate contains a chemical structure represented by the formula (2).

Formula (2), wherein p + q = a positive integer of 400 to 5000, p / (p + q) = 0.05 to 1, y is a positive integer of 1 to 3; and A ₅ to A ₈ are each independently hydrogen, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ alkenyl group;

The polyvinyl alcohol benzene sulfonate contains a chemical structure represented by the formula (3),

Formula (3), wherein g + h = a positive integer of 400 to 5000, g / (g + h) = 0.05 ~ 1; A ₉ - A ₁₂ are each independently hydrogen, C ₁ - C ₆ alkoxy Or a halogen element; wherein M is Li, Na, K or NH ₄ .

The present invention also provides a method for synthesizing the modified polyvinyl alcohol of the present invention, which comprises: in the presence of a solvent and an activator,

Esterification of polyvinyl alcohol and sulfopropionic anhydride represented by formula (4),

Formula (4), wherein x is a positive integer of 1 to 3, and A ₁ to A ₄ are each independently hydrogen or a C ₁ -C ₆ alkyl group; or

The polyvinyl alcohol and the sultone lactone represented by the formula (5) are subjected to etherification reaction,

Formula (5), wherein y is a positive integer of 1 to 3; and A ₅ to A ₈ are each independently hydrogen, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ alkenyl group;

Esterification of polyvinyl alcohol and sulfobenzoic anhydride represented by formula (6),

The formula (6), wherein each of A ₉ to A _{12 is} independently hydrogen, a C ₁ -C ₆ alkoxy group or a halogen element.

The present invention also provides a hydrophilic plate for printing, comprising: a substrate, and a hydrophilic layer formed on the substrate; wherein, in the infrared absorption spectrum of the hydrophilic layer, the wave number is 3340 cm ^-1 The absorption peak of the polyvinyl alcohol hydroxyl group, the wave number is 1740 cm ^-1 is the absorption peak of the ester carbonyl group, and the wave number is 1240 cm ^-1 and 1120 cm ^-1 is the absorption peak of the sulfonic acid group;

Alternatively, the infrared absorption spectrum of the hydrophilic layer, at the wavenumber 3340cm ^-1 absorption peak of hydroxyl groups of polyvinyl alcohol, at the wavenumber 1120cm ^-1 ether bond absorption peak wavenumber of 1240cm ^-1 and 1090cm ^{- 1} is the absorption peak of the sulfonic acid group;

Alternatively, in the infrared absorption spectrum of the hydrophilic layer, the wave number is 3340 cm ^-1 , which is the absorption peak of the polyvinyl alcohol hydroxyl group, and the wave number is 1720 cm ^-1 , which is the absorption peak of the ester carbonyl group, and the wave number is 1500 cm ^-1 and 1450 cm ^- an absorption peak at ^a benzene ring, at the wavenumber 1110cm ^-1 to 1220cm ^-1 and an absorption peak of a sulfonic acid group.

The invention also provides the use of a hydrophilic version of the invention in a printing plate.

The present invention also provides a printing plate comprising: a hydrophilic plate of the present invention, and a graphic information layer formed on the hydrophilic layer in the hydrophilic plate.

The present invention also provides an ink jet printing plate comprising: the hydrophilic plate of the present invention, and a graphic information layer formed on the hydrophilic layer in the hydrophilic plate, wherein the graphic information layer passes through The hydrophilic layer is sprayed with ink and dried to form.

The present invention also provides a photosensitive photosensitive printing plate comprising: a hydrophilic plate of the present invention, and a photosensitive photosensitive adhesive on a hydrophilic layer in a hydrophilic plate, the photosensitive photosensitive adhesive forming a graphic information layer.

The present invention also provides a thermal printing plate comprising: a hydrophilic plate of the present invention, and a thermographic layer on a hydrophilic layer in the hydrophilic plate, the thermographic layer forming a graphic information layer.

According to the above technical solution, a polyvinyl alcohol sulfonate is provided, and the hydrophilic plate for printing prepared by using the polyvinyl alcohol sulfonate can obtain very good hydrophilic effect, water resistance and print resistance without additional Add nano- or micro-scale hydrophilic particles. Qualified printed products can be obtained, the surface is clean and flawless, and the printing plate has a high printing durability.

Other features and technical effects of the present invention will be described in detail in the detailed description that follows.

detailed description

Specific embodiments of the present invention will be described in detail below. It is to be understood that the specific embodiments described herein are merely illustrative and not restrictive.

The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to include values that are close to the ranges or values. For numerical ranges, the endpoint values of the various ranges, the endpoint values of the various ranges and the individual point values, and the individual point values can be combined with one another to yield one or more new ranges of values. The scope should be considered as specifically disclosed herein.

A first object of the present invention provides a modified polyvinyl alcohol, the modified polyvinyl alcohol sulfonate being a polyvinyl alcohol sulfonate, a polyvinyl alcohol benzene sulfonate or a polyvinyl alcohol sulfonate;

Formula (1) wherein m + n = a positive integer of 400 to 5000, n / (m + n) = 0.05 to 1, x is a positive integer of 1 to 3; and A ₁ to A ₄ are each independently hydrogen or a C ₁ -C ₆ alkyl group; M is Li, Na, K or NH ₄ ;

Formula (2), wherein p + q = a positive integer of 400 to 5000, p / (p + q) = 0.05 to 1, y is a positive integer of 1 to 3; and A ₅ to A ₈ are each independently hydrogen, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ alkenyl group; M is Li, Na, K or NH ₄ ;

Formula (3), wherein g + h = a positive integer of 400 to 5000, g / (g + h) = 0.05 ~ 1; A ₉ - A ₁₂ are each independently hydrogen, C ₁ - C ₆ alkoxy Or a halogen element; M is Li, Na, K or NH ₄ .

In the present invention, in the polyvinyl alcohol sulfonate, a partial hydroxyl group of polyvinyl alcohol may be substituted with a sulfonate salt, such as a structural unit of the formula (1) with a lower corner labeled n (denoted as a structural unit - 1); may also be partially a polyvinyl alcohol, such as a structural unit of the formula (1) with a lower corner labeled m (denoted as structural unit-2). Formula (1) is used to illustrate the chemical structure of the polyvinyl alcohol sulfonate, wherein the connection manner of the structural unit-1 and the structural unit-2 in the polyvinyl alcohol sulfonate is not limited, and It is random or block. Further, the structural unit-2 of the chemical structure of the polyvinyl alcohol sulfonate may or may not be. The content of the structural unit-1 in the polyvinyl alcohol sulfonate can be represented by n/(m+n). Preferably, n/(m+n) is 0.2 to 0.95, preferably 0.2 to 0.8, and more preferably 0.4 to 0.6. When the content relationship of the structural unit-1 and the structural unit-2 satisfies the above range in the chemical structure of the polyvinyl alcohol sulfonate, the polyvinyl alcohol ester sulfonate may be further prepared as a hydrophilic version for printing. Provides better printing properties such as hydrophilicity, water resistance, print durability and the like.

In the present invention, in the chemical structure of the polyvinyl alcohol sulfonate, a part of the hydroxyl group of the polyvinyl alcohol may be substituted with a sulfonate, such as a structural unit in the lower formula of the formula (2), which is designated as p. -3); may also be partially a polyvinyl alcohol, such as a structural unit of the formula (2) with a lower corner labeled q (denoted as structural unit-4). Formula (2) is used to illustrate the chemical structure of the polyvinyl alcohol sulfonate, wherein the connection manner of the structural unit-3 and the structural unit-4 in the polyvinyl alcohol sulfonate is not limited and may be none Gauge or block. Further, the structural unit-3 may or may not be present in the chemical structure of the polyvinyl alcohol sulfonate. The content of the structural unit-3 in the polyvinyl alcohol sulfonate can be represented by p/(p+q). Preferably, p/(p+q) is from 0.2 to 0.95, preferably from 0.2 to 0.8, more preferably from 0.4 to 0.6. When the content relationship of the structural unit-3 and the structural unit-4 satisfies the above range in the chemical structure of the polyvinyl alcohol sulfonate, the polyvinyl alcohol sulfonate may be provided as a further prepared hydrophilic version for printing. Better printing properties such as hydrophilicity, water resistance, print durability, etc.

In the present invention, in the chemical structure of the polyvinyl alcohol benzene sulfonate, a partial hydroxyl group of the polyvinyl alcohol may be substituted with a benzenesulfonate salt, such as a structural unit having a lower corner of the formula (3) (Remarked as structural unit-5); it may also be partially polyvinyl alcohol, such as a structural unit (indicated as structural unit-6) with a lower corner in the formula (3). Formula (3) is used to illustrate the chemical structure of the polyvinyl alcohol benzene sulfonate, wherein the connection manner of the structural unit-5 and the structural unit-6 in the polyvinyl alcohol benzene sulfonate is not limited. Can be random or block. Further, the structural unit-6 of the polyvinyl alcohol benzene sulfonate may or may not be present in the chemical structure. Can be expressed by g/(g+h) The content of the structural unit-5 in the polyvinyl alcohol benzene sulfonate is out. Preferably, g/(g+h) is from 0.2 to 0.95, preferably from 0.2 to 0.8, more preferably from 0.4 to 0.6. When the content relationship of the structural unit-5 and the structural unit-6 satisfies the above range in the chemical structure of the polyvinyl alcohol benzene sulfonate, the polyvinyl alcohol benzene sulfonate may be used for further printing. The hydrophilic version provides better printing properties such as hydrophilicity, water resistance, print durability and the like.

The chemical structure of the polyvinyl alcohol sulfonate, polyvinyl alcohol benzene sulfonate or polyvinyl alcohol sulfonate in the present invention can be determined by an infrared spectrum method. The content of the hydroxyl-substituted portion of the polyvinyl alcohol can be determined by potentiometric titration.

According to the present invention, in the infrared spectrum of the polyvinyl alcohol sulfonate, the absorption peak of the polyvinyl alcohol hydroxyl group at a wave number of 3340 cm ^-1 and the absorption of the ester carbonyl group at a wave number of 1740 cm ^-1 are preferably used. The peak, the wave number is 1240 cm ^-1 and 1120 cm ^-1 is the absorption peak of the sulfonic acid group.

According to the present invention, preferably, the polyvinyl sulfonate IR spectra, at the wavenumber 3340cm ^-1 absorption peak of hydroxyl groups of polyvinyl alcohol, at the wavenumber 1120cm ^-1 ether bond absorption peak wavenumber 1090cm ^-1 to 1240cm ^-1 and an absorption peak at a sulfonic acid group.

According to the invention, Preferably, the polyvinyl ester salt of the IR spectra, at the wavenumber 3340cm ^-1 polyvinyl alcohol hydroxyl absorption peak, at a wave number of 1720cm ^-1 to the ester carbonyl absorption peak at a wave number of 1450cm ^-1 and a benzene ring absorption peak 1500cm ^-1, 1220cm ^-1 and a wavenumber of the absorption peak at 1110cm ^-1 sulfonic acid group.

According to a preferred embodiment of the present invention, the polyvinyl alcohol sulfonate can be synthesized by the following method: The polyvinyl alcohol sulfonate is an esterification product of polyvinyl alcohol and sulfopropionic anhydride.

Preferably, the sulfopropanhydride is selected from the group consisting of 3-sulfopropionic anhydride, 4-methyl-3-sulfopropionic anhydride, 5-methyl-3-sulfopropionic anhydride, 4,4-dimethyl- 3-sulfopropionic anhydride, 5,5-dimethyl-3-sulfopropionic anhydride, 4,5-dimethyl-3-sulfopropionic anhydride, 4-propyl-3-sulfopropionic anhydride and 5 At least one of isopropyl-3-sulfopropionic anhydride.

In the present invention, polyvinyl alcohol and sulfopropionic anhydride are subjected to an esterification reaction in the presence of an activator and a solvent. The activator is preferably a basic compound, for example, the activator may be selected from the group consisting of tetramethylammonium hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydride, potassium hydride, sodium hydride, and lithium metal. At least one of sodium and potassium. The metal element in the activator may be left in the polyvinyl alcohol ester sulfonate to obtain sodium polyvinyl alcohol sulfonate, potassium polyvinyl alcohol sulfonate, lithium polyvinyl alcohol sulfonate or polyvinyl alcohol. Amine sulfonate amine.

According to another preferred embodiment of the present invention, the polyvinyl alcohol sulfonate can be synthesized by the following method: The polyvinyl alcohol sulfonate is an etherification product of polyvinyl alcohol and sultone.

Preferably, the sultone is selected from the group consisting of 1,3-propane sultone, 1,4-propane sultone, 1-methyl-1,3-propane sultone, 1,1- Dimethyl-1,3-propane sultone, 1-ethyl-1,3-propane sultone, 1,2-dimethyl-1,3-propane sultone, 1,3 - dimethyl-1,3-propane sultone, 1-propenyl-1,3-propane sultone, 1-methyl-2-ethyl-1,3-propane sultone, 1-methyl-1,4-butane sultone, 1-methyl-1,4-butane sultone, 1-propenyl-1,4-butane sultone and 1,5-pentyl At least one of sultone. More preferably, the sultone is selected from the group consisting of 1,3-propane sultone and 1-methyl-1,3-propane sulfonic acid. Ester, 1,1-dimethyl-1,3-propane sultone, 1-ethyl-1,3-propane sultone, 1,2-dimethyl-1,3-propane sulfonic acid At least one of a lactone and 1,4-propane sultone.

In the present invention, the polyvinyl alcohol and the sultone are subjected to an etherification reaction in the presence of a basic compound and a solvent. The basic compound may be selected from at least one of tetramethylammonium hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydride, potassium hydride, sodium hydride, and lithium metal, sodium, and potassium. A metal element in the basic compound may be left in the polyvinyl alcohol sulfonate to obtain sodium polyvinyl alkoxide, potassium polyvinyl alkoxide, lithium polyvinyl alcohol sulfonate or a polyvinyl alcohol sulfonate.

According to still another preferred embodiment of the present invention, the polyvinyl alcohol benzene sulfonate can be synthesized by the following method: the polyvinyl alcohol benzene sulfonate is a polyvinyl alcohol and a sulfobenzoic anhydride. Esterification product.

Preferably, the sulfobenzoic anhydride is selected from the group consisting of 2-sulfobenzoic anhydride, 5-fluoro-2-sulfobenzoic anhydride, 5-iodo-2-sulfobenzoic anhydride, 5-methoxy- At least one of 2-sulfobenzoic anhydride, 5-ethoxy-2-sulfobenzoic anhydride, tetrabromo-2-sulfobenzoic acid cyclic anhydride, and tetraiodo-2-sulfonic acid benzoic anhydride. It is preferably at least one selected from the group consisting of 2-sulfobenzoic anhydride, 5-fluoro-2-sulfobenzoic anhydride, and tetraiodo-2-sulfonic acid benzoic anhydride.

In the present invention, polyvinyl alcohol and sulfobenzoic anhydride are subjected to an esterification reaction in the presence of a basic compound and a solvent. The basic compound may be selected from at least one of tetramethylammonium hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydride, potassium hydride, sodium hydride, and lithium metal, sodium, and potassium. The metal element in the basic compound may be left in the polyvinyl alcohol benzene sulfonate to obtain sodium polyvinyl alcohol benzene sulfonate, potassium polyvinyl alcohol benzene sulfonate, lithium polyvinyl alcohol benzene sulfonate or Polyvinyl alcohol benzene sulfonate amine.

A second object of the present invention is to provide a method for synthesizing the modified polyvinyl alcohol of the present invention, which comprises: in the presence of a solvent and an activator,

According to the present invention, the selected sulfopropionic acid anhydride of the formula (4) can promote the improvement of the performance of the polyvinyl alcohol as a hydrophilic layer of the printing plate, and improve the printing property of the further obtained hydrophilic plate, such as hydrophilicity, The polyvinyl alcohol ester sulfonate having a chemical structure represented by the formula (1) may be used for water resistance, print durability, and the like. Preferably, the sulfopropanhydride is selected from the group consisting of 3-sulfopropionic anhydride (CAS No. 5961-88-6), 4-methyl-3-sulfopropionic anhydride (CAS No. 1058711-91-3) , 5-methyl-3-sulfopropionic anhydride (CAS No. 21010-17-3), 4,4-dimethyl-3-sulfopropionic anhydride (CAS No. 35638-12-1), 5, 5-dimethyl-3-sulfopropionic anhydride (CAS No. 5927-70-8), 4,5-dimethyl-3-sulfopropionic anhydride (CAS No. 1234622-75-3), 4- At least one of propyl-3-sulfopropionic anhydride (CAS No. 42228-01-3) and 5-isopropyl-3-sulfopropionic anhydride (CAS No. 4374-76-9).

According to the present invention, the sulfopropionic anhydride is commercially available or can be prepared. When prepared, the method of preparation may include, for example,

The brominated carboxylic acid is dissolved in acetone, and after heating to 50 ° C, a 10% aqueous solution of sodium sulfite is added dropwise, and the molar ratio of sodium sulfite to bromocarboxylic acid is at least 1:1, and the temperature is raised to 75- after completion of the dropwise addition. The reaction was carried out at 80 ° C for 5 hours or more, and the structural formula was

The intermediate product is then subjected to an esterification reaction in the presence of SOCl ₂ to give a compound of the formula (4). The reaction equation for this preparation process is as follows:

In the above production method, each of A ₁ to A _{4 is} independently hydrogen or a C ₁ -C ₆ alkyl group, and x is a positive integer of 1 to 3. The obtained product can be determined by infrared analysis to have a structure represented by the formula (4).

According to the present invention, the selected sultone lactone of the formula (5) can promote the improvement of the performance of the polyvinyl alcohol as a hydrophilic layer of the printing plate, and improve the printing property of the further obtained hydrophilic plate, such as hydrophilicity, The polyvinyl alcohol sulfonate having a chemical structure represented by the formula (2) may be used for water resistance, print durability, and the like. Preferably, the sultone is selected from the group consisting of 1,3-propane sultone, 1-methyl-1,3-propane sultone, 1,1-dimethyl-1,3-propane Sulfonate, 1-ethyl-1,3- Propane sultone, 1,2-dimethyl-1,3-propane sultone, 1,3-dimethyl-1,3-propane sultone, 1-propenyl-1,3 -propane sultone, 1-methyl-2-ethyl-1,3-propane sultone, 1-methyl-1,4-butane sultone, 1-methyl-1,4 At least one of butane sultone, 1-propenyl-1,4-butane sultone, and 1,5-pentane sultone.

According to the present invention, the selected sulfobenzoic anhydride represented by the formula (6) can promote the improvement of the performance of the polyvinyl alcohol as a hydrophilic layer of the printing plate, and improve the printing property of the further obtained hydrophilic plate, such as hydrophilicity. The polyvinyl alcohol benzene sulfonate having a chemical structure represented by the formula (3) may be satisfied, such as water resistance and printing durability. Preferably, the sulfobenzoic anhydride is selected from the group consisting of sulfobenzoic anhydride selected from the group consisting of 2-sulfobenzoic anhydride, 5-fluoro-2-sulfobenzoic anhydride, 5-iodo-2-sulfobenzoic acid Anhydride, 5-methoxy-2-sulfobenzoic anhydride, 5-ethoxy-2-sulfobenzoic anhydride, tetrabromo-2-sulfobenzoic acid cyclic anhydride and tetraiodo-2-sulfonic acid benzene At least one of the anhydrides.

According to the present invention, the polyvinyl alcohol may provide a base material used as a hydrophilic layer of a printing plate, and may have a structural unit as shown in the formula (7)

Formula (7). The polyvinyl alcohol is selected from the group consisting of a polyvinyl alcohol sulfonate having a chemical structure represented by the formula (1), a polyvinyl alcohol sulfonate having a chemical structure represented by the formula (2), or a chemical represented by the formula (3). The structure of polyvinyl alcohol benzene sulfonate can be used. Preferably, the polyvinyl alcohol has a degree of polymerization of from 400 to 5,000. It may correspond to the value of m+n in the chemical structure represented by the formula (1), the value of p+q in the chemical structure represented by the formula (2), or the value of g+h in the chemical structure represented by the formula (3). . The degree of polymerization is preferably from 1,500 to 3,000, more preferably from 1,700 to 2,600. At the same time, the degree of alcoholysis of the polyvinyl alcohol may be 99%. The polyvinyl alcohol may be a known substance, and PVA1799 (degree of polymerization: 1700, degree of alcoholysis of 99%) of Sinopec Shanghai Petrochemical Co., Ltd., PVA1799, PVA1899 of Ningxia Dadi Chemical Co., Ltd. (degree of polymerization) may be commercially available. 1800, the degree of alcoholysis is 99%), PVA2099 (degree of polymerization is 2000, degree of alcoholysis is 99%), PVA2499 (degree of polymerization is 2400, degree of alcoholysis is 99%), PVA2699 (degree of polymerization is 2600, alcoholysis) Degree is 99%).

According to the present invention, the solvent may be used in the etherification reaction process so that the reactant polyvinyl alcohol and sultone are better subjected to an etherification reaction; or used in the esterification reaction process so that the reactant polyethylene The alcohol and sultone or sulfobenzoic anhydride are better subjected to esterification. Preferably, the solvent may be water or an organic solvent which can dissolve polyvinyl alcohol. Preferably, the organic solvent is at least one selected from the group consisting of dimethylformamide, r-butyrolactone, N-methylpyrrolidone, N-ethylpyrrolidone, tetrahydrofuran, ethanol, and dioxane.

According to the invention, the activator may be used to effect the etherification reaction or the esterification reaction. Preferably, the activator is a basic compound; preferably the activator is selected from the group consisting of tetramethylammonium hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydride, potassium hydride, sodium hydride and lithium metal At least one of sodium, potassium.

According to the present invention, the polyvinyl alcohol ester sulfonate of the above formula (1) can be obtained by synthesizing the conditions of the esterification reaction of the polyvinyl alcohol sulfonate. Preferably, the weight ratio of the polyvinyl alcohol to the sulfopropionic anhydride is (0.1 to 20): 1, preferably (0.1 to 10): 1, more preferably (0.2 to 5): 1. The amount of the polyvinyl alcohol and the sulfopropionic acid anhydride can be such that the obtained polyvinyl alcohol ester sulfonate has n, m in the structure represented by the formula (1).

According to the present invention, preferably, the molar ratio of the sulfopropionic anhydride to the activator is 1: (1 to 1.1).

According to the present invention, preferably, the esterification reaction temperature is from 40 ° C to 120 ° C, preferably from 60 ° C to 100 ° C; and the esterification reaction time is from 1 to 10 h, preferably from 3 to 5 h.

In the present invention, the polyvinyl alcohol and the sulfopropanic anhydride may be separately dissolved in the solvent to prepare a solution, and then contacted to carry out the esterification reaction.

In the present invention, in particular, polyvinyl alcohol may be dissolved in the solvent, and then the activator may be added; and the solution in which the sulfopropionic anhydride is dissolved in the solvent is further added dropwise at room temperature; Thereafter, the formed reaction solution is pre-reacted at room temperature for 1 to 2 hours, and then heated to 60 ° C to 80 ° C for esterification reaction for 2 to 4 hours. The product obtained by the reaction was spray-dried to obtain a solid powder. The obtained solid powder was subjected to infrared spectroscopy to determine the polyvinyl alcohol sulfonate containing the chemical structure represented by the formula (1). In the infrared absorption spectrum, the wave number is 3340 cm ^-1 at the absorption peak of the polyvinyl alcohol hydroxyl group, the wave number is 1740 cm ^-1 at the absorption peak of the ester carbonyl group, and the wave number is 1240 cm ^-1 and the sulfonic acid group at 1120 cm ^-1 Absorption peak. And further determine the specific structural parameters in combination with the feed.

According to the present invention, the conditions of the etherification reaction can give the aforementioned polyvinyl alcohol sulfonate. A polyvinyl alcohol sulfonate represented by the formula (2) is preferred. Preferably, the weight ratio of the polyvinyl alcohol to the sultone is (0.1 to 4): 1, preferably (0.1 to 1): 1. The amount of the polyvinyl alcohol and the sultone may be such that the obtained polyvinyl alcohol sulfonate has p, q in the structure represented by the formula (2).

According to the present invention, preferably, the molar ratio of the sultone to the activator is 1: (1 to 1.2).

According to the present invention, preferably, the etherification reaction temperature is from 40 ° C to 120 ° C, preferably from 60 ° C to 100 ° C; and the etherification reaction time is from 1 to 10 h, preferably from 3 to 5 h.

In the present invention, the polyvinyl alcohol and the sultone may be separately dissolved in the solvent, and after being formulated into a solution, the etherification reaction may be carried out by contacting.

In the present invention, in particular, polyvinyl alcohol may be dissolved in the solvent, and then the activator may be added; and the solution in which the sulfonate is dissolved in the solvent is further added dropwise at room temperature; Thereafter, the formed reaction solution is pre-reacted at room temperature for 1 to 2 hours, and then heated to 60 ° C to 80 ° C for etherification reaction for 2 to 4 hours. The product obtained by the reaction was spray-dried to obtain a solid powder. The obtained solid powder was subjected to infrared spectroscopy to determine a polyvinyl alcohol sulfonate having a chemical structure represented by the formula (2). IR spectra, at the wavenumber 3340cm ^-1 polyvinyl alcohol hydroxyl absorption peak, at a wave number of 1120cm ^-1 is an ether bond absorption peak wave number of 1240cm ^-1 and 1090cm ^-1 of the sulfonic acid group Absorption peak. And further determine the specific structural parameters in combination with the feed.

According to the present invention, the conditions for the esterification reaction of the polyvinyl alcohol benzene sulfonate can be synthesized to obtain the above polyvinyl alcohol benzene sulfonate, preferably the polyvinyl alcohol benzene sulfonate represented by the formula (3). . Preferably, the weight ratio of the polyvinyl alcohol to the sulfobenzoic anhydride is (0.05-10):1, preferably (0.1-5):1. The amount of the polyvinyl alcohol and the sulfobenzoic anhydride to be supplied may be such that the obtained polyvinyl alcohol benzenesulfonate has g, h in the structure represented by the formula (3).

According to the present invention, preferably, the molar ratio of the sulfobenzoic anhydride to the activator is 1: (1 to 1.1).

In the present invention, the polyvinyl alcohol and the sulfobenzoic anhydride may be separately dissolved in the solvent to prepare a solution, and then contacted to carry out the esterification reaction.

In the present invention, in particular, polyvinyl alcohol may be dissolved in the solvent, and then the activator may be added; and the solution of the sulfobenzoic anhydride dissolved in the solvent may be added dropwise at room temperature; After completion, the formed reaction solution is pre-reacted at room temperature for 1 to 2 hours, and then heated to 60 ° C to 80 ° C for esterification reaction for 2 to 4 hours. The product obtained by the reaction was spray-dried to obtain a solid powder. The obtained solid powder was subjected to infrared spectroscopy to determine the polyvinyl alcohol benzene sulfonate containing the chemical structure represented by the formula (3). Infrared absorption spectrum wavenumber of the absorption peak at 3340cm ^-1 for the hydroxyl group of polyvinyl alcohol, at the wavenumber 1720cm ^-1 ester carbonyl absorption peak of wavenumber 1500cm ^-1 and 1450cm ^-1 of the absorption peak of the benzene ring wavenumber 1110cm ^-1 to 1220cm ^-1 and an absorption peak at a sulfonic acid group. And further determine the specific structural parameters in combination with the feed.

A third object of the present invention provides a printed hydrophilic plate comprising: a substrate, and a hydrophilic layer formed on the substrate; wherein, in the infrared absorption spectrum of the hydrophilic layer, the wave number is 3340 cm ^-1 The absorption peak of the polyvinyl alcohol hydroxyl group, the wave number is 1740 cm ^-1 is the absorption peak of the ester carbonyl group, and the wave number is 1240 cm ^-1 and 1120 cm ^-1 is the absorption peak of the sulfonic acid group;

According to the present invention, the provided hydrophilic layer of the hydrophilic layer having the above chemical structure can provide better printing performance. Preferably, the contact angle of the hydrophilic plate is less than 10°; the water resistance of the hydrophilic plate is such that it does not fall off after being immersed in water for 3 hours, and the printing durability of the hydrophilic plate is not less than 5000 parts. Wherein, determining the contact angle of the hydrophilic layer can indicate the hydrophilicity of the hydrophilic layer, and the smaller the value of the contact angle, the better the hydrophilicity. The water resistance of the hydrophilic plate is related to the printing durability, and the stronger the water resistance, the higher the printing durability of the hydrophilic plate.

Preferably, the hydrophilic layer has a thickness of 0.5 to 10 μm.

According to the present invention, preferably, the hydrophilic layer is obtained by coating the modified polyvinyl alcohol of the present invention on the substrate. The modified polyvinyl alcohol can be obtained by the modified polyvinyl alcohol synthesis method provided by the present invention.

According to a preferred embodiment of the present invention, the coating process comprises: dissolving the modified polyvinyl alcohol in water to obtain a water-soluble coating liquid; and performing the coating liquid on the surface of the substrate. Coating, baking at 100 ° C ~ 200 ° C for 1 ~ 10 min, and then cooling to obtain the hydrophilic layer.

Preferably, in the water-soluble paint, the content of the modified polyvinyl alcohol is 5 to 30% by weight.

Preferably, the coating is by extrusion, spraying or roller coating.

According to the present invention, preferably, the water-soluble paint further contains a curing agent.

Preferably, in the water-soluble paint, the curing agent is contained in an amount of 1 to 10% by weight.

Preferably, the curing agent is selected from the group consisting of isocyanates, aziridines or compounds containing a plurality of epoxy groups. The isocyanate may be a blocked isocyanate, and may be obtained by commercially available reagent companies such as Belling, Sinopharm Group, and the like. The compound containing a plurality of epoxy groups may have at least two epoxy groups in the structure of the compound, such as a diepoxide, a triepoxy compound, or the like. Specifically, for example, 3,4-epoxycyclohexylcarboxylic acid-3',4'-epoxycyclohexylmethyl ester, tris(epoxypropyl)isocyanurate, glycidyl ether, novolac epoxy resin, etc. The compound containing a plurality of epoxy groups is a known substance, and is commercially available from a reagent company such as Belling, Sinopharm Group, and the like.

In the present invention, preferably, the substrate is selected from a plastic sheet base, an aluminum substrate or an aluminum alloy substrate; and the substrate has a thickness of 0.1 mm to 0.4 mm.

In the present invention, preferably, the plastic base may be a polypropylene base, a PET base or a nylon base, which is commercially available.

In the present invention, preferably, the aluminum alloy may be an alloy of aluminum and magnesium, copper, carbon, iron, zinc or silicon, wherein the aluminum content is not less than 90%, which is commercially available.

A fourth object of the present invention is to provide an application of the hydrophilic plate of the present invention to a printing plate.

A fifth object of the present invention is to provide a printing plate comprising: the hydrophilic plate of the present invention, and a graphic information layer formed on the hydrophilic layer in the hydrophilic plate.

A sixth object of the present invention is to provide an ink jet printing plate comprising: the hydrophilic plate of the present invention, and a graphic information layer formed on the hydrophilic layer in the hydrophilic plate, wherein the graphic information layer It is formed by spraying ink on the hydrophilic layer and drying.

In the inkjet printing plate provided by the present invention, the ink used to form the graphic information layer may be inkjet plate-making ink or ink used in the art, and is commercially available, for example, Beijing Zhongkena New Printing Technology Co., Ltd. K series plate ink.

In the present invention, the thickness of the graphic information layer may be from 0.5 μm to 10 μm.

In the present invention, the method and conditions for spraying the ink may be conventional techniques in the art, and will not be described herein.

A seventh object of the present invention is to provide a photosensitive photosensitive printing plate comprising: a hydrophilic plate of the present invention, and a photosensitive photosensitive adhesive on a hydrophilic layer in a hydrophilic plate, wherein the photosensitive photosensitive adhesive forms a graphic information layer .

In the present invention, the graphic information layer can be formed by applying the photosensitive photosensitive adhesive.

In the present invention, the photosensitive photosensitive adhesive of one embodiment contains 2 to 12 parts by mass of a photoactive compound, 0.1 to 0.5 part by mass of a background dye, 10 to 25 parts by mass of a film-forming resin, and 60 to 80 parts by mass of a solvent. .

In the present invention, preferably, the photoactive compound is selected from the group consisting of 2-diazo-1-naphthol-4-sulfonyl chloride or 2-diazo-1-naphthol-5-sulfonyl chloride and a hydroxyl group-containing compound. a product; the hydroxyl-containing compound is selected from the group consisting of an alcohol, a phenol, or a hydroxyl group The base polymer, such as a hydroxyl group-containing polymer and/or a phenolic hydroxyl group-containing polymer.

In the present invention, preferably, the molar ratio of the 2-diazo-1-naphthol-4-sulfonyl chloride or 2-diazo-1-naphthol-5-sulfonyl chloride to the hydroxyl group in the hydroxyl group-containing compound is 1: (1 ~ 20).

In the present invention, preferably, the background dye is at least one selected from the group consisting of basic brilliant blue, crystal violet, Victoria blue, indigo, methyl violet, malachite green, and oil-soluble blue.

In the present invention, preferably, the film-forming resin is selected from the group consisting of a water-insoluble polymer, and specifically one or more of an epoxy resin, a phenol resin, a polyvinyl acetal resin, and a polyurethane resin. The epoxy resin, phenolic resin, polyvinyl acetal resin and polyurethane resin are all known materials, and are commercially available, for example, Dow DOW solid DER671 epoxy resin, Weihai Economic and Technological Development Zone Tiancheng Chemical Co., Ltd. BTB Series of phenolic resin, Sekisui BL-1H, Sekisui S-LEC BL-1 grade polyvinyl acetal resin, or PU408 grade polyurethane resin of Guangzhou Xieyu Chemical Co., Ltd.

In the present invention, preferably, the solvent is selected from the group consisting of propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, methyl ethyl ketone, butyl acetate, dioxane, N-methyl At least one of pyrrolidone, methanol, and tetrahydrofuran.

In the present invention, the photosensitive photosensitive adhesive is a known substance, and a PS version photosensitive liquid or a CTcP photosensitive liquid of Taixing Dongfang Industrial Co., Ltd. can be commercially available.

In the present invention, the photosensitive photoresist may be applied by extrusion, spraying or roll coating. The conditions for carrying out the coating may be conventional techniques in the art and will not be described herein.

An eighth object of the present invention is to provide a thermal printing plate comprising: a hydrophilic plate of the present invention, and a thermographic layer on a hydrophilic layer in a hydrophilic plate, the thermographic layer forming a graphic Information layer.

In the present invention, the graphic information layer can be formed by applying a thermographic composition.

In the present invention, the thermographic composition of one embodiment contains 0.1 to 2 parts by mass of a photothermal conversion material, 0.1 to 0.5 part by mass of a background dye, 10 to 25 parts by mass of a film-forming resin, and 60 to 85 masses. Parts of solvent.

In the present invention, preferably, the photothermal converter is at least one selected from the group consisting of a benzofluorene cyanine dye, a cyanine dye, and various infrared absorbing dyes having a maximum wavelength (λ _max ) of 780 to 840 nm. The photothermal converter is a known substance, and the benzofluorene cyanine dye can be commercially available from Jingmen City Kui Kui Chemical Co., Ltd., and the step flower cyanine dye can be purchased from Hubei Jusheng Technology Co., Ltd. Infrared absorbing dyes having a maximum wavelength (λ _max ) of 780 to 840 nm are commercially available as infrared dyes of the development zone Liye Chemical Co., Ltd.

In the present invention, preferably, the film-forming resin may be selected from the group consisting of novolacs, poly-p-hydroxystyrene and modified products thereof, poly-o-hydroxystyrene and modified products thereof, phenol-formaldehyde resin, m-cresol - Formaldehyde resin, o-cresol-formaldehyde resin, phenol-m-cresol-formaldehyde resin, phenol-o-cresol-formaldehyde resin, phenol-p-cresol-formaldehyde resin, phenol-tert-butylphenol-formaldehyde resin, phenol- M-cresol-p-cresol-formaldehyde resin, m-cresol-p-cresol-formaldehyde resin and One or more of cresol-tert-butylphenol-formaldehyde resins.

The solvent is selected from the group consisting of cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, γ-butyrolactone, ethyl lactate, butyl acetate, dioxane, tetrahydrofuran, trichloroethylene, chloroform. One or several of dichloromethane.

In the present invention, the thermographic composition may be applied by extrusion, spray coating or roll coating. The conditions for carrying out the coating may be conventional techniques in the art and will not be described herein.

In the present invention, the thermographic composition is a known substance, and a thermographic composition of Taixing Dongfang Industrial Co., Ltd. is commercially available.

The invention will be described in detail below by way of examples.

In the following examples, the hydrophilicity of the hydrophilic plate can be measured by a contact angle meter (Crussian Scientific Instruments (Shanghai) Co., Ltd., DSA100);

The method for determining the water resistance of the hydrophilic plate may be as follows: the sample plate is cut into 10 cm × 10 cm (accurate to 1 mm), and weighed with a balance (accurate to 0.1 mg). Then, it was placed in water at a temperature of 25±2° C., soaked for 12 hours, and then placed in an oven at 100° C. for 15 minutes, and then cooled to room temperature and weighed. The hydrophilic layer was removed, rinsed with water, dried in an oven at 100 ° C for 15 min, cooled to room temperature and weighed. Water resistance is calculated as follows:

% water resistance = [(m _{1 -} m ₂ ) / (m _{1 -} m ₃ )] × 100%, where m ₁ is the mass (g) before immersion, and m ₂ is the mass after soaking (g), m ₃ is the mass (g) after removing the hydrophilic layer;

The printing durability of the hydrophilic version can be measured by the printing durability simulator (Beijing Longruida Technology Co., Ltd. LR-1 model) by: fixing the prepared coating substrate in the printing durability simulator. 15 ml of phosphoric acid, 75 ml of isopropanol, 225 ml of water, 75 g of quartz sand, and 15 rubber stoppers were added. Then add a special aqueous solution (isopropyl alcohol 15%, 3% phosphoric acid), rubber stopper (10% of special aqueous solution), 100 mesh silicon carbide (10% of special aqueous solution); rotation resistance at 20 rpm After 0.5 h, 1 h, 2 h, and 3 h of the simulator, the loss of the hydrophilic layer was observed, and the hydrophilic layer was required to have no apparent change. The printing durability (parts) corresponding to 0.5h, 1h, 2h, and 3h rotation is about 5,000, 10,000, 30,000, and 50,000.

In the following examples, the parameters of the obtained product were determined based on the feed.

Example 1

This example illustrates the preparation of the polyvinyl alcohol sulfonate of the present invention.

22g of polyvinyl alcohol (Ningxia Dadi Chemical Co., Ltd. 1799) was dissolved in 200mL of dimethylformamide (DMF), 5.7g of sodium metal was chopped and added, mixed at room temperature for 0.5h;

Then, 3-sulfopropionic anhydride (formula (4), wherein A ₁ , A ₂ , A ₃ and A ₄ are H, x=1; purchased from Shanghai Sanmu Chemical Technology Co., Ltd.) is added dropwise. Formamide solution (3-sulfopropionic anhydride 34.03g, dimethylformamide 300mL), polyvinyl alcohol: 3-sulfopropionic anhydride weight ratio of 0.65:1, about 1h, to obtain a reaction mixture;

The reaction mixture was pre-reacted at room temperature for 1 h, and then heated to 70 ° C for etherification reaction for 3 h;

The product obtained after completion of the etherification reaction was spray-dried to obtain a solid powder.

The solid powder was analyzed by infrared spectroscopy. The wave number of the spectrum was 3340 cm ^-1 , which is the absorption peak of the polyvinyl alcohol hydroxyl group. The wave number is 1740 cm ^-1 , which is the absorption peak of the ester carbonyl group. The wave number is 1240 cm ^-1 and 1120 cm ^-1 . The absorption peak of the sulfonic acid group. Using sodium as an activator, sodium polyvinyl alcohol sulfonate is obtained.

According to the ratio of the polyvinyl alcohol and 3-sulfopropionic anhydride, the sodium polyvinyl alcohol sulfonate corresponds to the structure represented by the formula (1), n = 850, m = 850, and n / (m + n) = 0.5. Recorded as PSL-1.

Example 2

11g of polyvinyl alcohol (Ningxia Dadi Chemical Co., Ltd. 1899) was dissolved in 100mL of dioxane, and a total of 3.6g of sodium hydride (distributed in mineral oil, wherein the concentration of sodium hydride was 60% by weight) was slowly added in three batches. ), mixed at room temperature for 1 h;

Then 4-methyl-3-sulfopropionic anhydride was added dropwise (the structural formula is as shown in formula (4), wherein A ₁ is methyl, A ₂ , A ₃ and A ₄ are both H, x = 1; purchased from BEHRINGER) The dioxane solution (4-methyl-3-sulfopropionic acid 22.52g, dioxane 20mL), polyvinyl alcohol: 4-methyl-3-sulfopropionic anhydride in a weight ratio of 0.49:1 , about 1 hour, to obtain a reaction mixture;

The reaction mixture was pre-reacted at room temperature for 1.2 h, and then heated to 75 ° C for etherification reaction for 2 h;

The solid powder was analyzed by infrared spectroscopy. The wave number of the spectrum was 3340 cm ^-1 , which is the absorption peak of the polyvinyl alcohol hydroxyl group. The wave number is 1740 cm ^-1 , which is the absorption peak of the ester carbonyl group. The wave number is 1240 cm ^-1 and 1120 cm ^-1 . The absorption peak of the sulfonic acid group. Sodium hydride sulfonate was obtained using sodium hydride as an activator.

According to the ratio of the polyvinyl alcohol and 4-methyl-3-sulfopropionic anhydride, the sodium polyvinyl alcohol sulfonate corresponds to the structure represented by the formula (1), n = 1080, m = 720, n / (m + n) = 0.6. Recorded as PSL-2.

Example 3

22g of polyvinyl alcohol (Ningxia Dadi Chemical Co., Ltd. 2099) was dissolved in 20mL of dimethylformamide (DMF), 7.8g of potassium metal was chopped, added, and mixed at room temperature for 0.5h;

Then, 4,4-dimethyl-3-sulfopropionic anhydride was added dropwise (the structural formula is as shown in formula (4), wherein A ₁ and A ₂ are methyl groups, A ₃ and A ₄ are H, x=1; purchased from sigma Aldrich) dimethylformamide solution (4,4-dimethyl-3-sulfopropionic anhydride 32.84 g, dimethylformamide 40 mL), polyvinyl alcohol: 4,4-dimethyl-3- The weight ratio of sulfopropionic anhydride is 0.67:1, about 1 hour, to obtain a reaction mixture;

The reaction mixture was pre-reacted at room temperature for 0.8 h, and then heated to 65 ° C for etherification reaction for 3.5 h;

The solid powder IR spectroscopy, spectra at a wave number of 3340cm ^-1 of polyvinyl alcohol hydroxyl absorption peak, at a wave number of 1740cm ^-1 to the absorption peak of the ester carbonyl, the wave number of 1240cm ^-1 and 1120cm ^-1 of at The absorption peak of the sulfonic acid group. Using potassium as an activator, potassium polyvinyl alcohol sulfonate is obtained.

According to the ratio of the polyvinyl alcohol and the 4,4-dimethyl-3-sulfopropionic anhydride, the potassium polyvinyl alcohol sulfonate corresponds to the structure represented by the formula (1), n = 800, m = 1,200, n / (m+n) = 0.4. Recorded as PSL-3.

Example 4

11g of polyvinyl alcohol (Ningxia Dadi Chemical Co., Ltd. 2499) was dissolved in 200mL of tetrahydrofuran (THF), 1.6g of lithium hydride was added, mixed at room temperature for 0.5h;

Then 5-methyl-3-sulfopropionic anhydride was added dropwise (the structural formula is as shown in formula (4), wherein A ₃ is methyl, A ₁ , A ₂ and A ₄ are H, x = 1; purchased from sigma aldrich) a tetrahydrofuran solution (5-methyl-3-sulfopropionic anhydride 30.03 g, tetrahydrofuran 200 mL), a weight ratio of polyvinyl alcohol: 5-methyl-3-sulfopropionic anhydride of 0.37:1, about 1 h, obtained Reaction mixture

The reaction mixture was pre-reacted at room temperature for 1 h, and then heated to 70 ° C for etherification reaction for 4 h;

The solid powder was analyzed by infrared spectroscopy. The wave number of the spectrum was 3340 cm ^-1 , which is the absorption peak of the polyvinyl alcohol hydroxyl group. The wave number is 1740 cm ^-1 , which is the absorption peak of the ester carbonyl group. The wave number is 1240 cm ^-1 and 1120 cm ^-1 . The absorption peak of the sulfonic acid group. Using lithium hydride as an activator, lithium polyvinyl alcohol sulfonate was obtained.

According to the ratio of the polyvinyl alcohol and 5-methyl-3-sulfopropionic anhydride, the lithium polyvinyl alcohol sulfonate corresponds to the structure represented by the formula (1), n = 1920, m = 480, n / (m + n) = 0.8. Recorded as PSL-4.

Example 5

44g of polyvinyl alcohol (Ningxia Dadi Chemical Co., Ltd. 1799) was dissolved in 100mL of tetrahydrofuran, and a total of 4.8g of sodium hydride (dispersed in mineral oil, wherein the concentration of sodium hydride was 60% by weight) was added slowly in three batches. Mix 1h;

Then, 5,5-dimethyl-3-sulfopropionic anhydride was added dropwise (the structural formula is as shown in formula (4), wherein A ₃ and A ₄ are methyl groups, A ₁ and A ₂ are H, x=1; purchased from Shanghai Tetrahydrofuran solution (3,5-dimethyl-3-sulfopropionic anhydride 32.84 g, tetrahydrofuran 200 mL), polyvinyl alcohol: 5,5-dimethyl-3-sulfopropanic anhydride The weight ratio is 1.34:1, about 1 hour, to obtain a reaction mixture;

The reaction mixture was pre-reacted at room temperature for 1 h, and then heated to 75 ° C for etherification reaction for 3 h;

According to the ratio of the polyvinyl alcohol and 5,5-dimethyl-3-sulfopropionic anhydride, the sodium polyvinyl alcohol sulfonate corresponds to the structure represented by the formula (1), n = 340, m = 1360, n / (m+n) = 0.2. Recorded as PSL-5.

Example 6

11g of polyvinyl alcohol (Ningxia Dadi Chemical Co., Ltd. 1799) was dissolved in 100mL of dioxane, slowly added 1.9g of lithium hydride, mixed at room temperature for 1h;

Then, 4-propyl-3-sulfopropionic anhydride was added dropwise (the structural formula is as shown in formula (4), wherein A ₁ is a propyl group, A ₂ , A ₃ and A ₄ are H, x = 1; purchased from Sigma Co., Ltd.) The dioxane solution (4-propyl-3-sulfopropionic acid 42.32g, dioxane 200mL), polyvinyl alcohol: 4-propyl-3-sulfopropionic anhydride in a weight ratio of 0.26:1 , about 1 hour, to obtain a reaction mixture;

The reaction mixture is pre-reacted at room temperature for 1 h, and then heated to 75 ° C for etherification reaction for 2 h;

According to the ratio of the polyvinyl alcohol and 4-propyl-3-sulfopropionic anhydride, the lithium polyvinyl alcohol sulfonate corresponds to the structure represented by the formula (1), n=1615, m=85, n/(m+ n) = 0.95. Recorded as PSL-6.

Example 7

44g of polyvinyl alcohol (Sinopec Shanghai Petrochemical Co., Ltd. 1799) was dissolved in 300mL of dimethyl sulfoxide, 1.95g of potassium metal was cut into pieces and slowly added, mixed at room temperature for 0.5h;

Then 5-isopropyl-3-sulfopropionic anhydride was added dropwise (the structural formula is as in formula (4), wherein A ₃ is isopropyl, A ₁ , A ₂ and A ₄ are H, x=1; purchased from sigma aldrich Company) dimethyl sulfoxide solution (8.91 g of 5-isopropyl-3-sulfopropanhydride, 40 mL of dimethyl sulfoxide), polyvinyl alcohol: 5-isopropyl-3-sulfopropionic anhydride The weight ratio is 4.94:1, and the reaction mixture is obtained after about 1 hour;

The reaction mixture is pre-reacted at room temperature for 0.5 h, and then heated to 80 ° C for etherification reaction for 2 h;

The solid powder was analyzed by infrared spectroscopy. The wave number of the spectrum was 3340 cm ^-1 , which is the absorption peak of the polyvinyl alcohol hydroxyl group. The wave number is 1740 cm ^-1 , which is the absorption peak of the ester carbonyl group. The wave number is 1240 cm ^-1 and 1120 cm ^-1 . The absorption peak of the sulfonic acid group. Using potassium as an activator, potassium polyvinyl alcohol sulfonate is obtained.

According to the ratio of the polyvinyl alcohol and 5-isopropyl-3-sulfopropionic anhydride, the potassium polyvinyl alcohol sulfonate corresponds to the structure represented by the formula (1), n = 85, m = 1,615, n / (m +n) = 0.05. Recorded as PSL-7.

Example 8

11g of polyvinyl alcohol (Ningxia Dadi Chemical Co., Ltd. 1899) was dissolved in 200mL of N-methylpyrrolidone, 1.75g of lithium metal was cut into pieces and slowly added, mixed at room temperature for 0.5h;

Then, 4,5-dimethyl-3-sulfopropionic anhydride was added dropwise (the structural formula is as shown in formula (4), wherein A ₁ and A ₃ are methyl groups, A ₂ and A ₄ are H, x=1; purchased from sigma Nd-methylpyrrolidone solution (4,5-dimethyl-3-sulfopropanhydride 41.05 g, N-methylpyrrolidone 100 mL), polyvinyl alcohol: 4,5-dimethyl-3- The weight ratio of sulfopropionic anhydride is 0.27:1, and the reaction mixture is obtained after about 1 hour;

The reaction mixture was pre-reacted at room temperature for 1 h, and then heated to 120 ° C for etherification reaction for 3 h;

The solid powder was analyzed by infrared spectroscopy. The wave number of the spectrum was 3340 cm ^-1 , which is the absorption peak of the polyvinyl alcohol hydroxyl group. The wave number is 1740 cm ^-1 , which is the absorption peak of the ester carbonyl group. The wave number is 1240 cm ^-1 and 1120 cm ^-1 . The absorption peak of the sulfonic acid group. Using lithium as an activator, lithium polyvinyl alcohol sulfonate is obtained.

According to the ratio of the polyvinyl alcohol and the 4,5-dimethyl-3-sulfopropionic anhydride, the lithium polyvinyl alcohol sulfonate corresponds to the structure represented by the formula (1), n=1800, m=0, n/ (m+n)=1. Recorded as PSL-8.

Example 9

This example illustrates the preparation of an ink jet printing plate of the present invention.

PSL-1 prepared in Example 1 and aziridine (XAMA-7 of Bayer, Germany) were dissolved in water to prepare an aqueous solution having a PSL-1 concentration of 11% by weight and an aziridine concentration of 2% by weight;

The aqueous solution was coated on the surface of an aluminum substrate (thickness 0.27 mm, Chengde Tiancheng Printing Technology Co., Ltd.), and then baked at 160 ° C for 5 min, and cooled to obtain a hydrophilic plate formed with a hydrophilic layer; a hydrophilic layer The thickness is 2 μm;

According to the required graphic information, inkjet plate making (Beijing Zhongkena New Printing Technology Co., Ltd., inkjet plate-making machine 116C, K-series inkjet plate-making ink) was baked by inkjet plate-making machine and baked at 180 ° C for 3 min to form a thickness of A 3 μm image information layer was obtained to obtain an inkjet printing plate.

The ink jet printing plate was subjected to contact angle, water resistance, and print durability test, and the results are shown in Table 1.

Example 10

This example illustrates the preparation of the photosensitive photosensitive printing plate of the present invention.

The PSL-2 and KL-1202 aqueous non-ion-blocking cross-linking agent prepared in Example 2 (Jiangsu Kangle New Material Technology Co., Ltd., blocked isocyanate) was dissolved in water to prepare a PSL-2 concentration of 10% by weight, isocyanate. An aqueous solution having a concentration of 3% by weight;

The aqueous solution was coated on the surface of an aluminum substrate (thickness 0.15 mm, Chengde Tiancheng Printing Technology Co., Ltd.), and then baked at 100 ° C for 3 min, and cooled to obtain a hydrophilic plate formed with a hydrophilic layer; a hydrophilic layer Thickness 3μm;

Spraying PS version photosensitive photosensitive adhesive (Taixing Oriental Industrial Co., Ltd.) to the hydrophilic plate and drying at 130 ° C for 5 min to form a photosensitive photosensitive layer with a thickness of 2 μm, and obtaining a photosensitive photosensitive printing plate after plate making;

The photosensitive photosensitive printing plate was tested for contact angle, water resistance, and print durability, and the results are shown in Table 1.

Example 11

This example illustrates the preparation of the thermal printing plate of the present invention.

PSL-3 prepared in Example 3 and epoxy resin GE-95 (Shanghai Run Carbon New Material Technology Co., Ltd.) were dissolved in water to prepare a PSL-3 concentration of 12% by weight and an epoxy resin GE-95 concentration of 1 % by weight aqueous solution;

The aqueous solution is coated on the surface of a 0.25 mm aluminum substrate, and then baked at 180 ° C for 4 min, after cooling to obtain a hydrophilic plate formed with a hydrophilic layer; the hydrophilic layer has a thickness of 2 μm;

Spraying the thermosensitive image on the hydrophilic plate (Taixing Dongfang Industrial Co., Ltd.) and performing at 130 ° C for 10 min. Drying, forming a thermosensitive imaging layer having a thickness of 1.8 μm, and obtaining a thermal printing plate after plate making;

The thermal printing plate was tested for contact angle, water resistance, and print durability. The results are shown in Table 1.

Example 12

PSL-4 prepared in Example 4 and epoxy resin GE-51 (Shanghai Run Carbon New Material Technology Co., Ltd.) were dissolved in water to prepare a PSL-4 concentration of 9% by weight and an aziridine concentration of 4% by weight. Aqueous solution

The aqueous solution was coated on the surface of a PET film (thickness 0.25 mm, Hai'an Jintong Adhesive Technology Co., Ltd.), and then baked at 130 ° C for 10 min, and cooled to obtain a hydrophilic plate formed with a hydrophilic layer; a hydrophilic layer The thickness is 2 μm;

According to the required graphic information, inkjet plate making with inkjet plate-making machine, (Beijing Zhongkena New Printing Technology Co., Ltd., inkjet plate-making machine 116C, K-series inkjet plate-making ink) and baked at 140 ° C for 10 min to form thickness An inkjet printing plate was obtained as a 3 μm graphic information layer.

Example 13

The PSL-5 and HD-115 trifunctional aziridine crosslinker prepared by the method of Example 5 (Jiangsu Kangle New Material Technology Co., Ltd.) were dissolved in water to prepare a PSL-5 concentration of 12% by weight, and the aziridine concentration was 1% by weight aqueous solution;

The aqueous solution was coated on the surface of a PET film (thickness 0.25 mm, Hai'an Jintong Adhesive Technology Co., Ltd.), and then baked at 140 ° C for 10 min, and cooled to obtain a hydrophilic plate formed with a hydrophilic layer; a hydrophilic layer The thickness is 2 μm;

According to the required graphic information, inkjet plate making (Beijing Zhongkena New Printing Technology Co., Ltd., inkjet plate making machine 116C, K series inkjet plate making ink) was baked by inkjet plate-making machine and baked at 140 ° C for 10 min to form a thickness of A 3 μm image information layer was obtained to obtain an inkjet printing plate.

Example 14

The PSL-6 and HD-110 trifunctional aziridine crosslinker prepared by the method of Example 6 (Jiangsu Kangle New Material Technology Co., Ltd.) were dissolved in water to prepare a PSL-6 concentration of 8% by weight, and the aziridine concentration was 5% by weight aqueous solution;

The aqueous solution was coated on the surface of a PET film (thickness 0.25 mm, Hai'an Jintong Adhesive Technology Co., Ltd.), and then baked at 140 ° C for 10 min, and cooled to obtain a hydrophilic plate formed with a hydrophilic layer; a hydrophilic layer The thickness is 3 μm;

The hydrophilic plate was sprayed with CTcP photosensitive photosensitive adhesive (Taixing Oriental Industrial Co., Ltd.) and dried at 130 ° C for 10 min to form a photosensitive photosensitive adhesive layer having a thickness of 1.8 μm, and a photosensitive photosensitive printing plate was obtained after the plate making;

Example 15

The PSL-7 and HD-110 trifunctional aziridine crosslinker prepared by the method of Example 7 (Jiangsu Kangle New Material Technology Co., Ltd.) were dissolved in water to prepare a PSL-7 concentration of 13% by weight, and the aziridine concentration was 0.5% by weight aqueous solution;

The aqueous solution was coated on the surface of a PET film (thickness 0.15 mm, Hai'an Jintong Adhesive Technology Co., Ltd.), and then baked at 140 ° C for 10 min. After cooling, a hydrophilic plate having a hydrophilic layer was formed, and a hydrophilic layer was obtained. The thickness is 2 μm;

According to the required graphic information, inkjet plate making with inkjet plate making machine, (Beijing Zhongkena New Printing Technology Co., Ltd., The ink jet plate making machine 116C, K series inkjet plate ink) was baked at 140 ° C for 10 min to form a graphic information layer having a thickness of 3 μm to obtain an ink jet printing plate.

Example 16

The PSL-8 prepared in Example 8 was formulated into an aqueous solution having a PSL-8 concentration of 13% by weight and coated on the surface of a PET film (thickness 0.25 mm, Shenzhen Hongda Technology Applied Materials Co., Ltd.), and then baked at 140 ° C. Bake for 10 min, after cooling, a hydrophilic plate with a hydrophilic layer is formed, and the hydrophilic layer has a thickness of 3 μm;

Example 17

Then, 1,3-propane sultone (Belling Technology Co., Ltd.) in dimethylformamide solution (1,3-propane lactone 30.5 g, dimethylformamide 300 mL) was added dropwise, polyvinyl alcohol: The weight ratio of 1,3-propane sultone is 0.72:1, and the reaction mixture is obtained after about 1 hour;

The solid powder was analyzed by infrared spectroscopy. The wave number of the spectrum was 3340 cm ^-1 , which is the absorption peak of the polyvinyl alcohol hydroxyl group. The wave number is 1120 cm ^-1 , which is the absorption peak of the ether bond. The wave number is 1240 cm ^-1 and 1090 cm ^-1 . The absorption peak of the sulfonic acid group. Sodium is used as the activator to obtain sodium polyvinyl alcohol sulfonate.

According to the ratio of the polyvinyl alcohol and the 1,3-propane sultone, the sodium polyvinyl alcohol sulfonate corresponds to the structure represented by the formula (2), p = 850, q = 850, p / (p + q) = 0.5. Recorded as PSL-9.

Example 18

11 g of polyvinyl alcohol (Ningxia Dadi Chemical Co., Ltd. 1899) was dissolved in 100 mL of dioxane, and a total of 6 g of sodium hydride (dispersed in mineral oil, wherein the concentration of sodium hydride was 60% by weight) was slowly added in three batches. , mixed at room temperature for 1 h;

Then, 1-methyl-1,3-propane sultone (Sigma-Aldrich) dioxane solution (1-methyl-1,3-propane sultone 20.4 g, dioxane) was added dropwise. 20mL), polyvinyl alcohol: 1-methyl-1,3-propane sultone weight ratio of 0.54:1, about 1h, to obtain a reaction mixture;

The solid powder was analyzed by infrared spectroscopy. The wave number of the spectrum was 3340 cm ^-1 , which is the absorption peak of the polyvinyl alcohol hydroxyl group. The wave number is 1120 cm ^-1 , which is the absorption peak of the ether bond. The wave number is 1240 cm ^-1 and 1090 cm ^-1 . The absorption peak of the sulfonic acid group; using sodium hydride as an activator to obtain sodium polyvinyl alcohol sulfonate.

According to the ratio of the polyvinyl alcohol and 1-methyl-1,3-propane sultone, the sodium polyvinyl alcohol sulfonate corresponds to the structure represented by the formula (2), p = 1080, q = 720, p / ( p+q)=0.6. Recorded as PSL-10.

Example 19

Then, a solution of 1,1-dimethyl-1,3-propane sultone (Billing) in dimethylformamide (1,1-dimethyl-1,3-propane sultone 30 g, Dimethylformamide 40mL), polyvinyl alcohol: 1,1-methyl-1,3-propane sultone weight ratio of 0.73:1, about 1h, to obtain a reaction mixture;

The solid powder was analyzed by infrared spectroscopy. The wave number of the spectrum was 3340 cm ^-1 , which is the absorption peak of the polyvinyl alcohol hydroxyl group. The wave number is 1120 cm ^-1 , which is the absorption peak of the ether bond. The wave number is 1240 cm ^-1 and 1090 cm ^-1 . The absorption peak of the sulfonic acid group; potassium is used as an activator to obtain potassium polyvinyl alcohol sulfonate.

According to the ratio of the polyvinyl alcohol and the 1,1-methyl-1,3-propane sultone, the potassium polyvinyl polyvinyl sulfonate corresponds to the structure represented by the formula (2), p=800, q=1200, p /(p+q)=0.4. Recorded as PSL-11.

Example 20

Then, a solution of 1-ethyl-1,3-propane sultone (Belling Technology Co., Ltd.) in tetrahydrofuran (30 g of 1-ethyl-1,3-propane sultone, 200 mL of tetrahydrofuran) was added dropwise, and polyvinyl alcohol was added. : a weight ratio of 1-ethyl-1,3-propane sultone of 0.37:1, about 1 hour, to obtain a reaction mixture;

The solid powder was analyzed by infrared spectroscopy. The wave number of the spectrum was 3340 cm ^-1 , which is the absorption peak of the polyvinyl alcohol hydroxyl group. The wave number is 1120 cm ^-1 , which is the absorption peak of the ether bond. The wave number is 1240 cm ^-1 and 1090 cm ^-1 . An absorption peak of a sulfonic acid group; using lithium hydride as an activator to obtain lithium polyvinyl alcohol sulfonate.

According to the ratio of the polyvinyl alcohol and 1-ethyl-1,3-propane sultone, lithium polyvinyl sulfonate corresponds to the structure represented by the formula (2), p = 1920, q = 480, p / ( p+q)=0.8. Recorded as PSL-12.

Example 21

44g of polyvinyl alcohol (Ningxia Dadi Chemical Co., Ltd. 1799) was dissolved in 100mL of tetrahydrofuran, and 8g of sodium hydride (dispersed in mineral oil, wherein the concentration of sodium hydride was 60% by weight) was slowly added in three batches, and mixed at room temperature for 1 hour. ;

Then, a solution of 1,2-dimethyl-1,3-propane sultone (Belling Technology Co., Ltd.) in tetrahydrofuran (1,2-dimethyl-1,3-propane sultone 30 g, tetrahydrofuran) was added dropwise. 200mL), polyvinyl alcohol: 1,2-dimethyl-1,3-propane sultone weight ratio of 1.47:1, about 1h, to obtain a reaction mixture;

According to the ratio of the polyvinyl alcohol and the 1,2-dimethyl-1,3-propane sultone, the sodium polyvinyl alcohol sulfonate corresponds to the structure represented by the formula (2), p=340, q=1360, p / (p + q) = 0.2. Recorded as PSL-13.

Example 22

Then, a solution of 1,3-propane sultone (Belling Technology Co., Ltd.) in dioxane (29 g of 1,3-propane sultone, 200 mL of dioxane) was added dropwise, and polyvinyl alcohol: 1,3 - the weight ratio of propane sultone is 0.38:1, about 1 hour, to obtain a reaction mixture;

According to the ratio of the polyvinyl alcohol and the 1,3-propane sultone, lithium polyvinyl sulfonate corresponds to the structure represented by the formula (2), p=1615, q=85, p/(p+q)= 0.95. Recorded as PSL-14.

Example 23

44g of polyvinyl alcohol (Sinopec Shanghai Petrochemical Co., Ltd. 1799) was dissolved in 300mL of dimethyl sulfoxide, 3.9g of potassium metal was cut into pieces and slowly added, mixed at room temperature for 0.5h;

Then, a solution of 1,4-propane sultone (Sigma-Aldrich) in dimethyl sulfoxide (13.6 g of 1,4-propane sultone, 40 mL of dimethyl sulfoxide) was added dropwise, and polyvinyl alcohol: 1 , the weight ratio of 4-propane sultone is 3.25:1, about 1 hour, to obtain a reaction mixture;

According to the ratio of the polyvinyl alcohol and the 1,4-propane sultone, the potassium polyvinyl sulfonate corresponds to the structure represented by the formula (2), p=85, q=1615, p/(p+q)= 0.05. Recorded as PSL-15.

Example 24

Then, a solution of 1,3-propane sultone in N-methylpyrrolidone, (1,3-propane sultone 30 g, N-methylpyrrolidone 100 mL), polyvinyl alcohol: 1,3-propane sulfonate was added dropwise. The weight ratio of the acid lactone is 0.37:1, and the reaction mixture is obtained after about 1 hour;

The solid powder was analyzed by infrared spectroscopy. The wave number of the spectrum was 3340 cm ^-1 , which is the absorption peak of the polyvinyl alcohol hydroxyl group. The wave number is 1120 cm ^-1 , which is the absorption peak of the ether bond. The wave number is 1240 cm ^-1 and 1090 cm ^-1 . The absorption peak of the sulfonic acid group; lithium is used as an activator to obtain lithium polyvinyl alcohol sulfonate.

According to the ratio of charge of polyvinyl alcohol and 1,3-propane sultone, lithium polyvinyl sulfonate corresponds to the structure represented by formula (2), p=1800, q=0, p/(p+q)= 1. Recorded as PSL-16.

Example 25

PSL-9 prepared in Example 17 and aziridine (XAMA-7 of Bayer, Germany) were dissolved in water to prepare an aqueous solution having a PSL-9 concentration of 11% by weight and an aziridine concentration of 2% by weight;

Example 26

The PSL-10 and KL-1202 aqueous nonionic blocking cross-linking agent prepared by the method of the present invention (Jiangsu Kangle New Material Technology Co., Ltd., blocked isocyanate) was dissolved in water to prepare a PSL-10 concentration of 10% by weight, isocyanate. An aqueous solution having a concentration of 3% by weight;

The aqueous solution is coated on an aluminum substrate (thickness 0.15 mm, Chengde Tiancheng Printing Technology Co., Ltd.) Surface, then baked at 100 ° C for 3 min, after cooling to obtain a hydrophilic plate formed with a hydrophilic layer; hydrophilic layer thickness of 3 μm;

Example 27

PSL-11 prepared in Example 19 and epoxy resin GE-95 (Shanghai Run Carbon New Material Technology Co., Ltd.) were dissolved in water to prepare a PSL-11 concentration of 12% by weight and an epoxy resin GE-95 concentration of 1 % by weight aqueous solution;

The thermosensitive image was sprayed onto the hydrophilic plate (Taixing Dongfang Industrial Co., Ltd.) and dried at 130 ° C for 10 min to form a thermosensitive imaging layer having a thickness of 1.8 μm, and a thermal printing plate was obtained after the plate making;

Example 28

The PSL-12 prepared in Example 20 and the epoxy resin GE-51 (Shanghai Run Carbon New Material Technology Co., Ltd.) were dissolved in water to prepare a PSL-12 concentration of 9% by weight and an aziridine concentration of 4% by weight. Aqueous solution

Example 29

The PSL-13 and HD-115 trifunctional aziridine crosslinker (Jiangsu Kangle New Material Technology Co., Ltd.) prepared in Example 21 were dissolved in water to prepare a PSL-13 concentration of 12% by weight, and the aziridine concentration was 1% by weight aqueous solution;

Example 30

PSL-14 and HD-110 trifunctional aziridine crosslinker prepared in Example 22 (Jiangsu Leisure New Materials Section) Technology Co., Ltd.) dissolved in water, formulated into an aqueous solution having a PSL-14 concentration of 8% by weight and an aziridine concentration of 5% by weight;

Example 31

The PSL-15 and HD-110 trifunctional aziridine crosslinker (Jiangsu Kangle New Material Technology Co., Ltd.) prepared in Example 23 were dissolved in water to prepare a PSL-15 concentration of 13% by weight, and the aziridine concentration was 0.5% by weight aqueous solution;

Example 32

The PSL-16 prepared in Example 24 was formulated into an aqueous solution having a PSL-8 concentration of 13% by weight and coated on the surface of a PET film (thickness 0.25 mm, Shenzhen Hongda Technology Applied Materials Co., Ltd.), and then baked at 140 ° C. Bake for 10 min, after cooling, a hydrophilic plate with a hydrophilic layer is formed, and the hydrophilic layer has a thickness of 3 μm;

Example 33

This example illustrates the preparation of the polyvinyl alcohol benzene sulfonate of the present invention.

22g of polyvinyl alcohol (Ningxia Dadi Chemical Co., Ltd. 1799) was dissolved in 200mL of dimethylformamide (DMF), 5.75g of sodium metal was chopped and added, mixed at room temperature for 0.5h;

Then, a solution of 2-sulfobenzoic anhydride (Belling Technology Co., Ltd.) in tetrahydrofuran (46.04 g of 2-sulfobenzoic anhydride, 200 mL of tetrahydrofuran) was added dropwise, and the weight ratio of polyvinyl alcohol: 2-sulfobenzoic anhydride was 0.48. :1, about 1 hour, to obtain a reaction mixture;

The reaction mixture was reacted at room temperature for 1 h, and then heated to 70 ° C for esterification reaction for 3 h;

The product obtained after completion of the esterification reaction was spray-dried to obtain a solid powder.

The solid powder IR spectroscopy, spectra at a wave number of 3340cm ^-1 of polyvinyl alcohol hydroxyl absorption peak, at a wave number of 1720cm ^-1 to the absorption peak of the ester carbonyl, the wave number of 1500cm ^-1 and 1450cm ^-1 of at benzene ring absorption peak wavenumber 1110cm ^-1 to 1220cm ^-1 and an absorption peak at a sulfonic acid group. Using sodium as an activator, sodium polyvinyl alcohol benzene sulfonate is obtained.

According to the ratio of the polyvinyl alcohol and the 2-sulfobenzoic anhydride, the sodium polyvinyl alcohol benzene sulfonate corresponds to the structure represented by the formula (3), g = 850, h = 850, g / (g + h) = 0.5. Recorded as PSL-17.

Example 34

11 g of polyvinyl alcohol (Ningxia Dadi Chemical Co., Ltd. 1899) was dissolved in 100 mL of dioxane, and 3.6 g of sodium hydride (dispersed in mineral oil, sodium hydride concentration of 60% by weight) was slowly added in three batches at room temperature. Mix 1h;

Then, a solution of 5-fluoro-2-sulfobenzoic anhydride (Sigma-Aldrich) in dioxane (30.33 g of 5-fluoro-2-sulfobenzoic anhydride, 20 mL of dioxane), and polyvinyl alcohol were added dropwise. : a weight ratio of 5-fluoro-2-sulfobenzoic anhydride of 0.36:1, about 1 hour, to obtain a reaction mixture;

The reaction mixture was pre-reacted at room temperature for 1.2 h, and then heated to 75 ° C for esterification reaction for 2 h;

The solid powder was analyzed by infrared spectroscopy. The absorption number of the polyvinyl alcohol hydroxyl group was 3340 cm ^{-1 in the} spectrum, and the absorption peak of the ester carbonyl group was 1720 cm ^-1 . The wave number was 1500 cm ^-1 and 1450 cm ^-1 . benzene ring absorption peak wavenumber 1110cm ^-1 to 1220cm ^-1 and an absorption peak at a sulfonic acid group. Sodium hydride was used as the activator to obtain sodium polyvinyl alcohol benzene sulfonate.

According to the ratio of the polyvinyl alcohol and the 2-sulfobenzoic anhydride, the sodium polyvinyl alcohol benzene sulfonate corresponds to the structure represented by the formula (3), g = 1080, h = 720, g / (g + h) = 0.6. Recorded as PSL-18.

Example 35

Then, a solution of tetraiodo-2-sulfonic acid benzoic anhydride in dimethylformamide (137.55 g of tetraiodo-2-sulfonic acid benzoic anhydride, 40 mL of dimethylformamide) was added dropwise, and polyvinyl alcohol: tetraiodo-2 was added dropwise. - the weight ratio of sulfonic acid benzoic anhydride is 0.16:1, about 1 hour, to obtain a reaction mixture;

The reaction mixture was pre-reacted at room temperature for 0.8 h, and then heated to 65 ° C for esterification reaction for 3.5 h;

The solid powder IR spectroscopy, spectra at a wave number of 3340cm ^-1 of polyvinyl alcohol hydroxyl absorption peak, at a wave number of 3340cm ^-1 is polyvinyl alcohol hydroxyl absorption peak, at a wave number of 1720cm ^-1 is an ester carbonyl absorption peak wave number of the absorption peak at 1500cm ^-1 and 1450cm ^-1 are benzene rings, at the wavenumber 1110cm ^-1 to 1220cm ^-1 and an absorption peak of a sulfonic acid group. Using potassium as an activator to obtain potassium polyvinyl alkane sulfonate;

According to the ratio of polyvinyl alcohol and tetraiodo-2-sulfonic acid benzoic anhydride, potassium polyvinyl benzene sulfonate corresponds to formula (3) In the structure shown, g = 800, h = 1,200, g / (g + h) = 0.4. Recorded as PSL-19.

Example 36

Then, a solution of 2-sulfobenzoic anhydride (Belling Technology Co., Ltd.) in tetrahydrofuran (36.83 g of 2-sulfobenzoic anhydride, 200 mL of tetrahydrofuran) was added dropwise, and the weight ratio of polyvinyl alcohol: 2-sulfobenzoic anhydride was 0.3. :1, about 1 hour, to obtain a reaction mixture;

The reaction mixture was pre-reacted at room temperature for 1 h, and then heated to 70 ° C for esterification reaction for 4 h;

The solid powder was analyzed by infrared spectroscopy. The absorption number of the polyvinyl alcohol hydroxyl group was 3340 cm ^{-1 in the} spectrum, and the absorption peak of the ester carbonyl group was 1720 cm ^-1 . The wave number was 1500 cm ^-1 and 1450 cm ^-1 . benzene ring absorption peak wavenumber 1110cm ^-1 to 1220cm ^-1 and an absorption peak at a sulfonic acid group. Using lithium hydride as an activator to obtain lithium polyvinyl benzene sulfonate;

According to the ratio of the polyvinyl alcohol and 2-sulfobenzoic anhydride, the lithium polyvinyl alcohol benzene sulfonate corresponds to the structure represented by the formula (3), g = 1920, h = 480, g / (g + h) = 0.8. Recorded as PSL-20.

Example 37

44g of polyvinyl alcohol (Ningxia Dadi Chemical Co., Ltd. 1799) was dissolved in 100mL of tetrahydrofuran, slowly added 4.8g of sodium hydride (dispersed in mineral oil, sodium hydride concentration of 60% by weight) in three batches, mixed at room temperature for 1h;

Then, a solution of 2-sulfobenzoic anhydride (Belling Technology Co., Ltd.) in tetrahydrofuran (36.83 g of 2-sulfobenzoic anhydride, 40 mL of tetrahydrofuran) was added dropwise, and the weight ratio of polyvinyl alcohol: 2-sulfobenzoic anhydride was 1.19. :1, about 1 hour, to obtain a reaction mixture;

The reaction mixture was pre-reacted at room temperature for 1 h, and then heated to 75 ° C for esterification reaction for 3 h;

The solid powder was analyzed by infrared spectroscopy. The absorption number of the polyvinyl alcohol hydroxyl group was 3340 cm ^{-1 in the} spectrum, and the absorption peak of the ester carbonyl group was 1720 cm ^-1 . The wave number was 1500 cm ^-1 and 1450 cm ^-1 . benzene ring absorption peak wavenumber 1110cm ^-1 to 1220cm ^-1 and an absorption peak at a sulfonic acid group. Using sodium hydride as an activator to obtain sodium polyvinyl alcohol benzene sulfonate;

According to the ratio of the polyvinyl alcohol and the 2-sulfobenzoic anhydride, the sodium polyvinyl alcohol benzene sulfonate corresponds to the structure represented by the formula (3), g = 340, h = 1360, g / (g + h) = 0.2. Recorded as PSL-21.

Example 38

Then, a solution of 2-sulfobenzoic anhydride (Belling Technology Co., Ltd.) in dioxane (43.74 g of 2-sulfobenzoic anhydride, 40 mL of dioxane), polyvinyl alcohol: 2-sulfobenzophenone was added dropwise. The anhydride weight ratio is 0.25:1, about 1h, Obtaining a reaction mixture;

The reaction mixture was pre-reacted at room temperature for 1 h, and then heated to 75 ° C for esterification reaction for 2 h;

According to the ratio of the polyvinyl alcohol and the 2-sulfobenzoic anhydride, lithium polyvinyl alcohol benzenesulfonate corresponds to the structure represented by the formula (3), g=1615, h=85, g/(g+h)= 0.95. Recorded as PSL-22.

Example 39

Then, a solution of 5-fluoro-2-sulfobenzoic anhydride (Sigma-Aldrich) in dimethyl sulfoxide (5-fluoro-2-sulfobenzoic anhydride 10.11 g, dimethyl sulfoxide 20 mL) was added dropwise. The weight ratio of vinyl alcohol: 5-fluoro-2-sulfobenzoic anhydride is 4.35:1, and the reaction mixture is obtained after about 1 hour;

The reaction mixture is pre-reacted at room temperature for 0.5 h, and then heated to 80 ° C for esterification reaction for 2 h;

The solid powder was analyzed by infrared spectroscopy. The absorption number of the polyvinyl alcohol hydroxyl group was 3340 cm ^{-1 in the} spectrum, and the absorption peak of the ester carbonyl group was 1720 cm ^-1 . The wave number was 1500 cm ^-1 and 1450 cm ^-1 . benzene ring absorption peak wavenumber 1110cm ^-1 to 1220cm ^-1 and an absorption peak at a sulfonic acid group. Using potassium as an activator to obtain potassium polyvinyl alcohol benzene sulfonate;

According to the ratio of the polyvinyl alcohol and 5-fluoro-2-sulfobenzoic anhydride, the polyvinyl alcohol ester potassium sulfonate corresponds to the structure represented by the formula (3), g = 85, h = 1615, g / (g +h) = 0.05. Recorded as PSL-23.

Example 40

Then, a solution of 5-fluoro-2-sulfobenzoic anhydride (Sigma-Aldrich) in N-methylpyrrolidone (5-fluoro-2-sulfobenzoic anhydride 50.54 g, N-methylpyrrolidone 100 mL) was added dropwise. The vinyl alcohol: 5-fluoro-2-sulfobenzoic anhydride is 0.22:1 by weight, and the reaction mixture is obtained after about 1 hour;

The reaction mixture was pre-reacted at room temperature for 1 h, and then heated to 120 ° C for esterification reaction for 3 h;

The solid powder was analyzed by infrared spectroscopy. The absorption number of the polyvinyl alcohol hydroxyl group was 3340 cm ^{-1 in the} spectrum, and the absorption peak of the ester carbonyl group was 1720 cm ^-1 . The wave number was 1500 cm ^-1 and 1450 cm ^-1 . benzene ring absorption peak wavenumber 1110cm ^-1 to 1220cm ^-1 and an absorption peak at a sulfonic acid group. Using lithium as an activator to obtain lithium polyvinyl alcohol benzene sulfonate;

According to the ratio of the polyvinyl alcohol and the 5-fluoro-2-sulfobenzoic anhydride, lithium polyvinyl alcohol benzenesulfonate corresponds to the structure represented by the formula (3), g=1800, h=0, g/(g +h)=1. Recorded as PSL-24.

Example 41

PSL-17 and aziridine (XAMA-7 of Bayer, Germany) prepared in Example 33 were dissolved in water to prepare an aqueous solution having a PSL-17 concentration of 11% by weight and an aziridine concentration of 2% by weight;

Example 42

The PSL-18 and KL-1202 aqueous nonionic blocking cross-linking agent prepared by the method of Example 34 (Jiangsu Kangle New Material Technology Co., Ltd., blocked isocyanate) was dissolved in water to prepare a PSL-18 concentration of 10% by weight, isocyanate. An aqueous solution having a concentration of 3% by weight;

Example 43

PSL-19 prepared in Example 35 and epoxy resin GE-95 (Shanghai Run Carbon New Material Technology Co., Ltd.) were dissolved in water to prepare a PSL-19 concentration of 12% by weight and an epoxy resin GE-95 concentration of 1 % by weight aqueous solution;

Example 44

PSL-20 and epoxy resin GE-51 prepared in Example 36 (Shanghai Run Carbon New Material Technology Co., Ltd.) Dissolved in water, formulated into an aqueous solution having a PSL-20 concentration of 9% by weight and an aziridine concentration of 4% by weight;

Example 45

The PSL-21 and HD-115 trifunctional aziridine crosslinker (Jiangsu Kangle New Material Technology Co., Ltd.) prepared in Example 37 were dissolved in water to prepare a PSL-21 concentration of 12% by weight, and the aziridine concentration was 1% by weight aqueous solution;

Example 46

The PSL-22 and HD-110 trifunctional aziridine crosslinker prepared by the method of Example 38 (Jiangsu Kangle New Material Technology Co., Ltd.) were dissolved in water to prepare a PSL-22 concentration of 8% by weight, and the aziridine concentration was 5% by weight aqueous solution;

Example 47

The PSL-23 and HD-110 trifunctional aziridine crosslinker (Jiangsu Kangle New Material Technology Co., Ltd.) prepared in Example 39 were dissolved in water to prepare a PSL-23 concentration of 13% by weight, and the aziridine concentration was 0.5% by weight aqueous solution;

Example 48

The PSL-24 prepared in Example 40 was formulated into an aqueous solution having a PSL-24 concentration of 13% by weight and coated on the surface of a PET film (thickness 0.25 mm, Shenzhen Hongda Technology Applied Materials Co., Ltd.), and then baked at 140 ° C. Bake for 10 min, after cooling, a hydrophilic plate with a hydrophilic layer is formed, and the hydrophilic layer has a thickness of 3 μm;

Comparative example 1

Polyvinyl alcohol (Ningxia Dadi Chemical Co., Ltd. 1799) and HD-110 trifunctional aziridine crosslinker (Jiangsu Kangle New Material Technology Co., Ltd.) are soluble in water and formulated into polyvinyl alcohol 1799 at a concentration of 8% by weight. An aqueous solution having a pyridine concentration of 3% by weight;

The above solution was coated on the surface of PET (thickness 0.25 mm, Hai'an Jintong Adhesive Technology Co., Ltd.), and then baked at 140 ° C for 10 min, and cooled to obtain a hydrophilic plate formed with a hydrophilic layer; hydrophilic layer thickness 3 μm;

Comparative example 2

Polyvinyl alcohol (Ningxia Dadi Chemical Co., Ltd. 1799) and HD-110 trifunctional aziridine crosslinker (Jiangsu Kangle New Material Technology Co., Ltd.) are soluble in water and added titanium dioxide with a particle size of 30 nm to prepare polyvinyl alcohol 1799. a solution having a concentration of 6% by weight, an aziridine concentration of 1% by weight, and a titanium dioxide concentration of 8% by weight;

Comparative example 3

A printing plate was prepared in accordance with the method of Example 1 disclosed in CN102407653A.

Use a metal aluminum plate with a thickness of 0.05-0.5mm as the base, and first clean it to remove dirt and oil. The adhesive layer is coated on the aluminum plate, and the adhesive layer coating formula is 35 parts of an aqueous epoxy resin solution (50%), 15 parts of an aqueous phenol resin solution (30%), and 50 parts of water, and the above components are stirred and dispersed to make A uniform coating solution is applied to the aluminum plate by dip coating Then, it was baked in an oven at 200 ° C for 5 min, and the coating liquid was solidified into a bonding layer having a thickness of 2 to 15 μm, and then a hydrophilic layer was applied. The coating solution of the hydrophilic layer is 100 parts of polyvinyl alcohol (10% aqueous solution), 40 parts of nano or micro-sized zinc oxide, 5 parts of hexamethylol melamine resin (50% aqueous solution), and polysorbate of sorbitan ester. 5 parts of vinyl ether (4% aqueous solution) and 50 parts of water.

The hydrophilic layer coating liquid is stirred and dispersed to form a uniform coating liquid, and then applied to the bonding layer by dip coating, and then heated in an oven at 100 ° C for 5-10 minutes to dry and solidify the coating liquid. The aqueous layer and the hydrophilic layer have a thickness of 5-20 μm to form a lithographic printing plate base.

Table 1

编号Numbering	亲水层Hydrophilic layer	n/(m+n)n/(m+n)	接触角Contact angle	耐水性Water resistance	耐印率(份)Printing resistance (parts)	印品表面Printed surface
实施例9Example 9	PSL-1PSL-1	0.50.5	<10°<10°	>3h>3h	1400014000	干净clean
实施例10Example 10	PSL-2PSL-2	0.60.6	<10°<10°	>3h>3h	1500015000	干净clean
实施例11Example 11	PSL-3PSL-3	0.40.4	<10°<10°	>3h>3h	1300013000	干净clean
实施例12Example 12	PSL-4PSL-4	0.80.8	<10°<10°	>3h>3h	1150011500	干净clean
实施例13Example 13	PSL-5PSL-5	0.20.2	<10°<10°	>3h>3h	1200012000	干净clean
实施例14Example 14	PSL-6PSL-6	0.950.95	<10°<10°	>3h>3h	80008000	干净clean
实施例15Example 15	PSL-7PSL-7	0.050.05	<10°<10°	>3h>3h	65006500	干净clean
实施例16Example 16	PSL-8PSL-8	11	<10°<10°	>3h>3h	55005500	干净clean
编号Numbering	亲水层Hydrophilic layer	p/(p+q)p/(p+q)	接触角Contact angle	耐水性Water resistance	耐印率(份)Printing resistance (parts)	印品表面Printed surface
实施例25Example 25	PSL-9PSL-9	0.50.5	<10°<10°	>3h>3h	2000020000	干净clean
实施例26Example 26	PSL-10PSL-10	0.60.6	<10°<10°	>3h>3h	1500015000	干净clean
实施例27Example 27	PSL-11PSL-11	0.40.4	<10°<10°	>3h>3h	2000020000	干净clean
实施例28Example 28	PSL-12PSL-12	0.80.8	<10°<10°	>3h>3h	1000010000	干净clean
实施例29Example 29	PSL-13PSL-13	0.20.2	<10°<10°	>3h>3h	80008000	干净clean
实施例30Example 30	PSL-14PSL-14	0.950.95	<10°<10°	>3h>3h	70007000	干净clean
实施例31Example 31	PSL-15PSL-15	0.050.05	<10°<10°	>3h>3h	60006000	干净clean
实施例32Example 32	PSL-16PSL-16	11	<10°<10°	>3h>3h	50005000	干净clean
编号Numbering	亲水层Hydrophilic layer	g/(g+h)g/(g+h)	接触角Contact angle	耐水性Water resistance	耐印率(份)Printing resistance (parts)	印品表面Printed surface
实施例41Example 41	PSL-17PSL-17	0.50.5	<10°<10°	>3h>3h	1500015000	干净clean
实施例42Example 42	PSL-18PSL-18	0.60.6	<10°<10°	>3h>3h	1600016000	干净clean
实施例43Example 43	PSL-19PSL-19	0.40.4	<10°<10°	>3h>3h	1400014000	干净clean

实施例44Example 44	PSL-20PSL-20	0.80.8	<10°<10°	>3h>3h	1250012500	干净clean
实施例45Example 45	PSL-21PSL-21	0.20.2	<10°<10°	>3h>3h	1300013000	干净clean
实施例46Example 46	PSL-22PSL-22	0.950.95	<10°<10°	>3h>3h	90009000	干净clean
实施例47Example 47	PSL-23PSL-23	0.050.05	<10°<10°	>3h>3h	75007500	干净clean
实施例48Example 48	PSL-24PSL-24	11	<10°<10°	>3h>3h	65006500	干净clean
对比例1Comparative example 1	--	--	15°15°	>3h>3h	10001000	局部脏Partially dirty
对比例2Comparative example 2	--	--	15°15°	>3h>3h	15001500	局部脏Partially dirty
对比例3Comparative example 3	--	--	45°45°	>3h>3h	--	脏dirty

In the above examples and comparative examples, Examples 1-8 are polyvinyl alcohol sulfonate (PSL1-PAL8) prepared according to the present invention, and Examples 9-16 are printing plates of the present invention prepared using PSL1-PAL8, respectively. Examples 17-24 are polyvinyl alcohol sulfonates (PSL9-PAL16) prepared in accordance with the present invention, and Examples 25-32 are printing plates of the present invention prepared using PSL9-PAL16, respectively. Examples 33-40 are polyvinyl alcohol benzene sulfonates (PSL17-PAL24) prepared according to the present invention, and Examples 41-48 are printing plates of the present invention prepared using PSL17-PAL24, respectively. Comparative Example 1 is an ink jet printing plate prepared using polyvinyl alcohol, Comparative Example 2 is an ink jet printing plate prepared using polyvinyl alcohol and titanium oxide (water absorbing particles), and Comparative Example 3 is an ink jet prepared by using the related art (CN102407653A). printed version.

It can be seen from the above examples, comparative examples and the result data of Table 1 that the polyvinyl alcohol sulfonate provided by the present invention can be made into a hydrophilic layer in a printed hydrophilic plate to provide a hydrophilic plate for better hydrophilicity. Sex, water resistant and sufficient print durability. The hydrophilic version can be further applied to the preparation of various printing plates, such as ink jet printing plates, photosensitive photographic printing plates and thermal printing plates, and provides printing plates with better printing performance, resulting in clear and clean printed products.

Comparative Examples 1-3 It is not easy to obtain a clear and clean printed article using the prior art. Among them, the ink jet printing plate obtained in Comparative Example 3 could not obtain a clean printed product, and could not perform acceptable printing. Comparative Examples 1 and 2 were only partially dirty, but the printing yield of the printed product was low, and the printing plate was further printed as the hydrophilic plate obtained by using the polyvinyl alcohol sulfonate as the hydrophilic layer provided in the present application. performance.

Claims

a modified polyvinyl alcohol sulfonate, which is a polyvinyl alcohol sulfonate, a polyvinyl alcohol benzene sulfonate or a polyvinyl alcohol sulfonate;

The polyvinyl alcohol sulfonate contains a chemical structure represented by the formula (1),

Wherein m + n = a positive integer of 400 to 5000, n / (m + n) = 0.05 to 1, x is a positive integer of 1 to 3; and A 1 to A 4 are each independently hydrogen or C 1 - C 6 Alkyl

The polyvinyl alcohol sulfonate contains a chemical structure represented by the formula (2).

Wherein, p + q = a positive integer of 400 to 5000, p / (p + q) = 0.05 to 1, y is a positive integer of 1 to 3; A 5 to A 8 are each independently hydrogen, C 1 - C 6 Alkyl or C 1 -C 6 alkenyl;

The polyvinyl alcohol benzene sulfonate contains a chemical structure represented by the formula (3),

Wherein g + h = a positive integer of 400 to 5000, g / (g + h) = 0.05 ~ 1; A 9 - A 12 are each independently hydrogen, C 1 - C 6 alkoxy or a halogen element;

Wherein M is Li, Na, K or NH 4 .
The modified polyvinyl alcohol according to claim 1, wherein n/(m+n) is from 0.2 to 0.95, preferably from 0.2 to 0.8, more preferably from 0.4 to 0.6; and p/(p+q) is from 0.2 to 0.95 is preferably 0.2 to 0.8, more preferably 0.4 to 0.6; g/(g+h) is 0.2 to 0.95, preferably 0.2 to 0.8, and more preferably 0.4 to 0.6.
The modified polyvinyl alcohol according to claim 1 or 2, wherein an infrared spectrum of the polyvinyl alcohol sulfonate has an absorption peak of a polyvinyl alcohol hydroxyl group at a wave number of 3340 cm -1 , and the wave number is 1740 cm -1 is the absorption peak of the ester carbonyl group, and the wave number is 1240 cm -1 and 1120 cm -1 is the absorption peak of the sulfonic acid group;

Polyvinyl sulfonate of the absorption peak of the IR spectra, at the wavenumber 3340cm -1 for the hydroxyl group of polyvinyl alcohol, at the wavenumber 1120cm -1 ether bond absorption peak wave number of 1240cm -1 and 1090cm -1 is the absorption peak of the sulfonic acid group;

IR spectrum of the polyvinyl ester in benzenesulfonate, 3340 cm -1 wavenumber polyvinyl alcohol hydroxyl absorption peak, the absorption wave number of 1720cm -1 is a peak of the ester carbonyl, the wave number of 1500cm -1 absorption peak at 1450cm -1 and a benzene ring, the wavenumber 1220cm -1 and an absorption peak at 1110cm -1 is a sulfonic acid group.
The modified polyvinyl alcohol according to any one of claims 1 to 3, wherein

The polyvinyl alcohol sulfonate is an esterification product of polyvinyl alcohol and sulfopropionic anhydride; wherein the sulfopropanhydride is selected from the group consisting of 3-sulfopropionic anhydride, 4-methyl-3-sulfopropyl Anhydride, 5-methyl-3-sulfopropionic anhydride, 4,4-dimethyl-3-sulfopropionic anhydride, 5,5-dimethyl-3-sulfopropionic anhydride, 4,5-dimethyl At least one of 3-sulfopropionic anhydride, 4-propyl-3-sulfopropionic anhydride, and 5-isopropyl-3-sulfopropionic anhydride;

The polyvinyl alcohol sulfonate is an etherification product of polyvinyl alcohol and sultone; wherein the sultone is selected from the group consisting of 1,3-propane sultone, 1-methyl-1,3 - propane sultone, 1,1-dimethyl-1,3-propane sultone, 1-ethyl-1,3-propane sultone, 1,2-dimethyl-1, 3-propane sultone, 1,3-dimethyl-1,3-propane sultone, 1-propenyl-1,3-propane sultone, 1-methyl-2-ethyl -1,3-propane sultone, 1-methyl-1,4-butane sultone, 1-methyl-1,4-butane sultone, 1-propenyl-1,4- At least one of butane sultone and 1,5-pentane sultone;

The polyvinyl alcohol benzene sulfonate is an esterification product of polyvinyl alcohol and sulfobenzoic anhydride; wherein the sulfobenzoic anhydride is selected from the group consisting of 2-sulfobenzoic anhydride and 5-fluoro-2- Sulfobenzoic anhydride, 5-iodo-2-sulfobenzoic anhydride, 5-methoxy-2-sulfobenzoic anhydride, 5-ethoxy-2-sulfobenzoic anhydride, tetrabromo-2 At least one of sulfobenzoic acid cyclic anhydride and tetraiodo-2-sulfonic acid benzoic anhydride.
A method of synthesizing a modified polyvinyl alcohol according to any one of claims 1 to 4, the method comprising:

In the presence of solvent and activator,

Esterification of polyvinyl alcohol and sulfopropionic anhydride represented by formula (4),

Wherein x is a positive integer of 1 to 3, and each of A 1 to A 4 is independently hydrogen or a C 1 -C 6 alkyl group; or

The polyvinyl alcohol and the sultone lactone represented by the formula (5) are subjected to etherification reaction,

Wherein y is a positive integer of 1 to 3; and A 5 to A 8 are each independently hydrogen, a C 1 -C 6 alkyl group or a C 1 -C 6 alkenyl group; or

Esterification of polyvinyl alcohol and sulfobenzoic anhydride represented by formula (6),

Here, each of A 9 to A 12 is independently hydrogen, a C 1 -C 6 alkoxy group or a halogen element.
The method according to claim 5, wherein the sulfopropanhydride is selected from the group consisting of 3-sulfopropionic anhydride, 4-methyl-3-sulfopropionic anhydride, 5-methyl-3-sulfopropionic anhydride, 4,4-Dimethyl-3-sulfopropionic anhydride, 5,5-dimethyl-3-sulfopropionic anhydride, 4,5-dimethyl-3-sulfopropionic anhydride, 4-propyl- At least one of 3-sulfopropionic anhydride and 5-isopropyl-3-sulfopropionic anhydride;

The sultone is selected from the group consisting of 1,3-propane sultone, 1-methyl-1,3-propane sultone, and 1,1-dimethyl-1,3-propane sultone , 1-ethyl-1,3-propane sultone, 1,2-dimethyl-1,3-propane sultone, 1,3-dimethyl-1,3-propane sulfonic acid Ester, 1-propenyl-1,3-propane sultone, 1-methyl-2-ethyl-1,3-propane sultone, 1-methyl-1,4-butanesulfonic acid At least one of ester, 1-methyl-1,4-butane sultone, 1-propenyl-1,4-butane sultone, and 1,5-pentane sultone;

The sulfobenzoic anhydride is selected from the group consisting of sulfobenzoic anhydride selected from the group consisting of 2-sulfobenzoic anhydride, 5-fluoro-2-sulfobenzoic anhydride, 5-iodo-2-sulfobenzoic anhydride, 5- Of methoxy-2-sulfobenzoic anhydride, 5-ethoxy-2-sulfobenzoic anhydride, tetrabromo-2-sulfobenzoic acid cyclic anhydride and tetraiodo-2-sulfonic acid benzoic anhydride At least one

Preferably, the polyvinyl alcohol has a degree of polymerization of 400 to 5000;

Preferably, the solvent is water or an organic solvent capable of dissolving polyvinyl alcohol; the organic solvent is selected from the group consisting of dimethylformamide, r-butyrolactone, N-methylpyrrolidone, N-ethylpyrrolidone, tetrahydrofuran, At least one of ethanol and dioxane;

Preferably, the activator is a basic compound; preferably the activator is selected from the group consisting of tetramethylammonium hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydride, potassium hydride, sodium hydride and lithium metal, At least one of sodium and potassium.
The method according to claim 5 or 6, wherein

The weight ratio of the polyvinyl alcohol to the sultone is (0.1-4):1, preferably (0.1-1):1; the molar ratio of the sultone to the activator is 1 (1~1.2); preferably, the etherification reaction temperature is 40 ° C ~ 120 ° C, preferably 60 ° C ~ 100 ° C; etherification reaction time is 1 ~ 10h, preferably 3 ~ 5h;

The weight ratio of the polyvinyl alcohol to the sulfopropionic anhydride is (0.1-20):1, preferably (0.1-10):1; the molar ratio of the sulfopropionic anhydride to the activator is 1 :(1~1.1);

The weight ratio of the polyvinyl alcohol to the sulfobenzoic anhydride is (0.05-10):1, preferably (0.1-5):1; the molar ratio of the sulfobenzoic anhydride to the activator Is 1: (1 ~ 1.1);

Preferably, the esterification reaction temperature is from 40 ° C to 120 ° C, preferably from 60 ° C to 100 ° C; and the esterification reaction time is from 1 to 10 h, preferably from 3 to 5 h.
A hydrophilic plate for printing, comprising: a substrate, and a hydrophilic layer formed on the substrate; wherein, in the infrared absorption spectrum of the hydrophilic layer, the wave number is 3340 cm -1 at a polyvinyl alcohol hydroxyl group The absorption peak, the wave number is 1740 cm -1 is the absorption peak of the ester carbonyl group, and the wave number is 1240 cm -1 and 1120 cm -1 is the absorption peak of the sulfonic acid group;

Alternatively, the infrared absorption spectrum of the hydrophilic layer, at the wavenumber 3340cm -1 absorption peak of hydroxyl groups of polyvinyl alcohol, at the wavenumber 1120cm -1 ether bond absorption peak wavenumber of 1240cm -1 and 1090cm - 1 is the absorption peak of the sulfonic acid group;

Alternatively, in the infrared absorption spectrum of the hydrophilic layer, the wave number is 3340 cm -1 , which is the absorption peak of the polyvinyl alcohol hydroxyl group, and the wave number is 1720 cm -1 , which is the absorption peak of the ester carbonyl group, and the wave number is 1500 cm -1 and 1450 cm - an absorption peak at a benzene ring, at the wavenumber 1110cm -1 to 1220cm -1 and an absorption peak of a sulfonic acid group.
The hydrophilic plate according to claim 8, wherein the hydrophilic layer has a contact angle of less than 10°; the water resistance of the hydrophilic plate is immersed in water for 3 hours without falling off, and the printing durability of the hydrophilic plate Not less than 5,000 copies.
The hydrophilic plate according to claim 8 or 9, wherein the hydrophilic layer is obtained by coating the modified polyvinyl alcohol according to any one of claims 1 to 4 on the substrate.
The hydrophilic plate according to claim 10, wherein the coating process comprises: dissolving the modified polyvinyl alcohol in water to obtain a water-soluble coating liquid; and applying the coating liquid to the substrate Coating on the surface, baking at 100 ° C ~ 200 ° C for 1 ~ 10min, and then cooling to obtain the hydrophilic layer;

Preferably, in the water-soluble coating liquid, the content of the modified polyvinyl alcohol is 5 to 30% by weight.
The hydrophilic plate according to claim 11, wherein the water-soluble coating liquid further contains a curing agent, and the curing agent is contained in an amount of 1 to 10% by weight;

Preferably, the curing agent is selected from the group consisting of isocyanates, aziridines or compounds containing a plurality of epoxy groups.
Use of a hydrophilic plate according to any one of claims 8-12 in a printing plate.
A printing plate comprising: the hydrophilic plate according to any one of claims 8 to 12, and a graphic information layer formed on the hydrophilic layer in the hydrophilic plate.
An inkjet printing plate comprising: the hydrophilic plate according to any one of claims 8 to 12, and a graphic information layer formed on the hydrophilic layer in the hydrophilic plate, wherein the graphic information The layer is formed by spraying ink on the hydrophilic layer and drying.
A photosensitive photosensitive printing plate comprising: the hydrophilic plate according to any one of claims 8 to 12, and a photosensitive photosensitive adhesive on a hydrophilic layer in a hydrophilic plate, the photosensitive photosensitive adhesive forming graphic information Floor.
A heat-sensitive printing plate comprising: the hydrophilic plate according to any one of claims 8 to 12, and a thermographic layer on a hydrophilic layer in a hydrophilic plate, the thermographic layer forming pattern Text information layer.