WO2018133214A1 - Modified phenol-aldehyde resin and synthesis method therefor, hydrophilic plate for printing and use thereof, and printing plate - Google Patents

Abstract

The present invention relates to the field of printing plates, and disclosed are a modified phenol-aldehyde resin and a synthesis method therefor, a hydrophilic plate for printing and the use thereof, and a printing plate. The modified phenol-aldehyde resin is a phenol-aldehyde resin esterified benzene sulphonate or a phenol-aldehyde resin esterified sulphonate. By using same, the hydrophilicity of a coating can be greatly enhanced, and the printability of the hydrophilic plate can be improved.

Description

Modified phenolic resin and its synthesis method, hydrophilic plate and application for printing and printing plate Technical field

The invention relates to the field of printing plates, in particular to a modified phenolic resin and a synthetic method thereof, a hydrophilic plate for printing containing a hydrophilic layer formed by the modified phenolic resin, the hydrophilic plate is applied in a printing plate, and The hydrophilic version forms an ink jet printing plate, a photosensitive photosensitive printing plate, and a thermal printing 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

SUMMARY OF THE INVENTION The object of the present invention is to solve the problem of how to improve the performance of a hydrophilic plate for printing, and to provide a modified phenolic resin and a synthetic method thereof, a hydrophilic plate and application for printing, and a printing plate.

In order to achieve the above object, the present invention provides a modified phenolic resin, which is a phenolic resin esterified besylate or a phenolic resin esterified sulfonate;

The phenolic resin esterified sulfonate contains a chemical structure represented by the formula (1),

Wherein, p + q = a positive integer of 4 to 50, p / (p + q) = 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; B is present or absent, and when B is present, is selected from C ₁ -C ₁₂ alkyl;

The phenolic resin esterified besylate contains a chemical structure represented by the formula (2),

Wherein m + n = a positive integer of 4 to 50, n / (m + n) = 0.05 to 1, and A ₅ to A ₈ are each independently hydrogen, a halogen element or a C ₁ - C ₆ alkoxy group; D is present or absent, is selected from C ₁ -C ₁₂ alkyl when D is present; M is Li, Na, K or NH ₄ .

The present invention also provides a method for synthesizing the modified phenolic resin according to the present invention, which comprises: in the presence of a solvent and an activator,

The phenolic resin and the sulfopropionic anhydride represented by the formula (3) are subjected to an esterification reaction,

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;

The phenolic resin and the sulfobenzoic anhydride represented by the formula (4) are subjected to an esterification reaction,

Among them, A ₅ to A ₈ are each independently hydrogen, a halogen element or a C ₁ -C ₆ alkoxy group.

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 3400 cm ^-1 phenolic resin 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 an absorption peak at 1450cm ^-1 benzene ring, the wave number of 1220cm ^-1 and 1090cm ^-1 of the sulfonic acid absorption peak group; or the infrared absorption spectrum of the hydrophilic layer, at the wavenumber 3400cm ^-1 for the phenolic resin hydroxyl absorption peak, at a wave number of 1750cm ^-1 to the absorption peak of the ester carbonyl, the wave number of 1240cm The absorption peak of the sulfonic acid group at ^-1 and 1090 cm ^-1 .

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.

Through the above technical solution, a modified phenolic resin is provided, and the hydrophilic plate for printing prepared by using the modified phenolic resin can obtain very good hydrophilic effect, water resistance and printing resistance without additional addition of nanometer scale or Micron-sized 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 is to provide a modified phenolic resin which is a phenolic resin esterified benzenesulfonate An acid salt or a phenolic resin esterified sulfonate;

The phenolic resin esterified sulfonate contains a chemical structure represented by the formula (1),

Wherein, p + q = a positive integer of 4 to 50, p / (p + q) = 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; B is present or absent, and when B is present, is selected from C ₁ -C ₁₂ alkyl;

The phenolic resin esterified besylate contains a chemical structure represented by the formula (2),

Wherein m + n = a positive integer of 4 to 50, n / (m + n) = 0.05 to 1, and A ₅ to A ₈ are each independently hydrogen, a halogen element or a C ₁ - C ₆ alkoxy group; D is present or absent, is selected from C ₁ -C ₁₂ alkyl when D is present; M is Li, Na, K or NH ₄ .

In one embodiment of the invention, the specific B groups and their positions corresponding to each benzene ring may be different in the same phenolic resin esterified sulfonate molecule. Preferably, the B is absent or the B is a methyl group; when B is a methyl group, the position of the methyl group is not particularly limited and may be a meta or para position of a hydroxyl group.

In the present invention, in the chemical structure of the phenolic resin esterified sulfonate, the hydroxy group of the phenolic resin may be substituted with a sulfonate salt, such as a structural unit of the formula (1) with a lower corner labeled p (denoted as a structural unit). Further, it may be partially a phenol resin such as a structural unit (hereinafter referred to as structural unit-2) having a lower mark in the formula (1). Formula (1) is used to illustrate the chemical structure of the phenolic resin esterified sulfonate, wherein the connection mode of the structural unit-1 and the structural unit-2 in the phenolic resin esterified sulfonate is not limited, and It is random or block. Further, the structural unit-2 of the phenolic resin esterified sulfonate may or may not be present in the chemical structure. The content of the structural unit-1 in the phenolic resin esterified 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 between the structural unit-1 and the structural unit-2 satisfies the above range in the chemical structure of the phenolic resin esterified sulfonate, the hydrophilic version for printing prepared by the phenolic resin esterified sulfonate may be further prepared. Has better printing properties, such as hydrophilicity, water resistance, print durability and the like.

In another embodiment of the present invention, in the same phenolic resin esterified besylate molecule, the specific D group corresponding to each benzene ring and its position may be different. Preferably, the D is absent or the D is a methyl group; when D is a methyl group, the position of the methyl group is not particularly limited and may be a meta or para position of a hydroxyl group.

In the present invention, in the chemical structure of the phenolic resin esterified besylate, the hydroxy group of the phenolic resin may be substituted with a sulfonate salt, such as a structural unit of the formula (2) with a lower corner labeled n (denoted as a structure). The unit-3) may also be partially a phenol resin such as a structural unit (hereinafter referred to as structural unit-4) having a lower corner in the formula (2). Formula (2) is used to illustrate the chemical structure of the phenolic resin esterified besylate, wherein the connection mode of the structural unit-3 and the structural unit-4 in the phenolic resin esterified besylate is not limited Can be random or block. Further, the structural unit-3 in the chemical structure of the phenolic resin esterified besylate may or may not be. The content of the structural unit-3 in the phenolic resin esterified benzenesulfonate 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 between the structural unit-3 and the structural unit-4 satisfies the above range in the chemical structure of the phenolic resin esterified benzenesulfonate, the printing pro is further prepared by the phenolic resin esterified besylate The water version has better printing properties such as hydrophilicity, water resistance, print durability and the like.

The chemical structure of the phenolic resin esterified besylate and the phenolic resin esterified sulfonate in the present invention can be determined by an infrared spectrum method. The content of the hydroxyl group-substituted portion of the phenol resin can be determined by potentiometric titration.

According to the invention, Preferably, the esterified phenol resin salt of the IR spectra, at the wavenumber 3400cm ^-1 phenolic resin hydroxyl absorption peak at a wave number of 1720cm ^-1 to the ester carbonyl absorption peak at a wave number of 1450cm ^-1 to 1500cm ^-1 and an absorption peak of the benzene ring, at the wavenumber 1090cm ^-1 to 1220cm ^-1 and an absorption peak of a sulfonic acid group.

According to the present invention, preferably, the esterified phenol resin salt of IR spectra, wave number of 3400 cm ^-1 to the absorption peak of hydroxyl group of phenolic resin, the absorption wave number of 1750cm ^-1 is a peak of the ester carbonyl wavenumber 1090cm ^-1 to 1240cm ^-1 and an absorption peak at a sulfonic acid group.

According to a preferred embodiment of the present invention, the phenolic resin esterified besylate can be synthesized by the following method: the phenolic resin esterified besylate is an esterification product of a phenolic resin and a sulfobenzoic anhydride. .

According to the present invention, 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-2-sulfobenzoic anhydride, 5-ethoxy-2-sulfobenzoic anhydride, tetrabromo-2-sulfobenzoic acid cyclic anhydride and tetraiodo-2-sulfonic acid benzoic anhydride At least one of them. More preferably, it is 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, the phenol resin and the sulfobenzoic anhydride are subjected to an esterification reaction in the presence of a solvent and a basic compound. 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 phenolic resin esterified benzenesulfonate to obtain a phenolic resin esterified sodium benzenesulfonate, a phenolic resin esterified potassium benzenesulfonate, a phenolic resin ester. Lithium benzene sulfonate or phenolic resin esterified benzene sulfonate.

According to another preferred embodiment of the present invention, the phenolic resin esterified sulfonate can be synthesized by the following method: the phenolic resin esterified sulfonate is an esterified product of a phenolic resin and sulfopropionic anhydride.

According to the present invention, 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-sulfonate At least one of a group of propionic anhydride and 5-isopropyl-3-sulfopropionic anhydride.

In the present invention, the phenol resin and sulfopropanhydride are subjected to an esterification reaction in the presence of a solvent and an activator. 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 phenolic resin esterified sulfonate to obtain sodium phenolic resin esterified sulfonate, potassium phenolic resin esterified sulfonate, lithium phenolic resin esterified lithium sulfonate or phenolic resin ester. Sulfonic acid amine.

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

The phenolic resin and the sulfopropionic anhydride represented by the formula (3) are subjected to an esterification reaction,

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;

The phenolic resin and the sulfobenzoic anhydride represented by the formula (4) are subjected to an esterification reaction,

Among them, A ₅ to A ₈ are each independently hydrogen, a halogen element or a C ₁ -C ₆ alkoxy group.

According to the present invention, the phenol resin may provide a base material for a hydrophilic layer of a printing plate, and may contain a structural unit as shown in the formula (5)

Or contain a structural unit as shown in formula (6)

Wherein B or D is present or absent, and when B or D is present, is selected from C ₁ -C ₁₂ alkyl. The phenolic resin may be selected to satisfy a phenolic resin esterified sulfonate having a chemical structure represented by the formula (1) or a phenolic resin esterified benzenesulfonate having a chemical structure represented by the formula (2). Preferably, the phenolic resin has a degree of polymerization of from 4 to 50. The value of p+q in the chemical structure represented by the formula (1) or the value of m+n in the chemical structure represented by the formula (2) may be used. The degree of polymerization is preferably from 10 to 40, more preferably from 20 to 30. The phenolic resin is a known material and can be selected according to the final desired phenolic resin esterified besylate. For example, the BTB series phenolic resin (such as BTB-17, BTB-19, BTB-25, BTB-26G, BTB-27, BTB-29, BTB-225, BTB-225L) can be purchased from Weicheng Economic and Technological Development Zone Tiancheng Chemical Co., Ltd. , BTB-30, BTB-413P, BTB-M), or commercially available BX series phenolic resin (such as BX-10, BX-15, BX-20, BX-25, BX-) of Benxi Ruishida Chemical Co., Ltd. 30, BX-40, BX-265).

According to the present invention, the specific B or D groups and their positions corresponding to each phenol structure of the phenolic resin may be different. Preferably, the B or D is absent, or the B or D is a methyl group; when B or D is a methyl group, the position of the methyl group is not particularly limited and may be a meta or para position of a hydroxyl group. . That is, in a preferred case, the phenol structural unit in the phenol resin may be selected from a mixture of one or more of a phenol structural unit, a p-methylphenol structural unit, and an m-methylphenol structural unit.

According to the present invention, the solvent can be used in the esterification reaction process so that the reactant phenol resin and sulfobenzoic anhydride are better subjected to esterification reaction. Preferably, the solvent is an organic solvent that can dissolve the phenolic resin. Preferably, the organic solvent is at least one selected from the group consisting of dimethylformamide, dimethyl sulfoxide, r-butyrolactone, N-methylpyrrolidone, N-ethylpyrrolidone, tetrahydrofuran, ethanol and dioxane. Kind.

According to the invention, the activator is capable of effecting the esterification reaction. Preferably, the activator is a basic compound; 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.

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.

According to the present invention, in the synthesis method of obtaining a modified phenol resin by esterification reaction of a phenol resin with sulfopropionic anhydride, the selected sulfopropionic acid anhydride can promote the performance of improving the hydrophilic layer of the phenolic resin used as a printing plate, and improve Further, the printing property of the hydrophilic plate, such as hydrophilicity, water resistance, and printing durability, may satisfy the phenolic resin esterified sulfonate having a chemical structure represented by the formula (1). 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-sulfopropanic anhydride (CAS number is 1234622-75-3), 4-propyl-3-sulfopropionic anhydride (CAS No. 42228-01-3) and 5-isopropyl-3-sulfopropionic anhydride (CAS No. 4374-76-9) At least one of them.

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 (3). 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 (3).

According to the present invention, preferably, the weight ratio of the phenol resin to the sulfopropionic anhydride is (0.1 to 20): 1, preferably (0.5 to 13): 1. The amount of the phenol resin and the sulfopropionic acid anhydride can be such that the obtained phenol resin esterified sulfonate has p, q 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 1.2).

In the present invention, the phenolic resin and the sulfopropionic anhydride may be separately dissolved in the solvent to prepare a solution, and then separately contacted to carry out an esterification reaction.

In the present invention, in particular, a phenolic resin 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; 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 phenolic resin esterified sulfonate containing the chemical structure represented by the formula (1). Infrared absorption spectrum, at the wavenumber 3400cm ^-1 phenolic resin hydroxyl absorption peak at a wave number of 1750cm ^-1 to the absorption peak of the ester carbonyl group, wavenumber 1240cm ^-1 and 1090cm ^-1 of absorption at the sulfonic acid group peak.

According to the present invention, in the synthesis method of obtaining a modified phenol resin by esterification reaction of a phenol resin with sulfobenzoic anhydride, the selected sulfobenzoic anhydride can promote the improvement of the performance of the phenolic resin as a hydrophilic layer of a printing plate. , mention The printing property of the hydrophilic plate obtained further, such as hydrophilicity, water resistance, and printing durability, may satisfy the phenolic resin esterified besylate salt having a chemical structure represented by the formula (2). 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, preferably, the weight ratio of the phenol resin to the sulfobenzoic anhydride is (0.1 to 20): 1, preferably (0.5 to 11): 1. The amount of the phenol resin and the sulfobenzoic anhydride to be supplied can satisfy the obtained phenolic resin esterified benzenesulfonate having n, m in the structure represented by the formula (2).

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

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

In the present invention, in particular, a phenolic resin may be dissolved in the solvent, and then the activator may be added; and the solution in which the sulfobenzoic 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 phenolic resin esterified benzenesulfonate containing the chemical structure represented by the formula (2). Infrared absorption spectrum wavenumber of the absorption peak at 3400cm ^-1 for the hydroxyl group of the phenol resin, at the wavenumber 1720cm ^-1 for the ester carbonyl absorption peak wavenumber 1450cm ^-1 to 1500cm ^-1 and an absorption peak of the benzene ring, The wave number is an absorption peak of a sulfonic acid group at 1220 cm ^-1 and 1090 cm ^-1 .

A third object of the present invention 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 3400 cm ^{- 1} at the absorption peak of hydroxyl group of phenolic resin, at a wave number of 1720cm ^-1 to the absorption peak of the ester carbonyl group, wavenumber 1500cm ^-1 and an absorption peak at 1450cm ^-1 benzene ring, at the wavenumber 1220cm ^-1 and 1090cm ^-1 An absorption peak of a sulfonic acid group;

Alternatively, the infrared absorption spectrum of the hydrophilic layer, at the wavenumber 3400cm ^-1 to the absorption peak of hydroxyl group of phenolic resin, at the wavenumber 1750cm ^-1 for the ester carbonyl absorption peak wavenumber of 1240cm ^-1 and 1090cm ^-1 It 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 phenol resin of the present invention on the substrate. The modified phenol resin can be obtained by the modified phenolic resin synthesis method provided by the present invention.

According to a preferred embodiment of the present invention, the coating process comprises: dissolving the modified phenolic resin in water to obtain a water-soluble coating liquid; and coating the coating liquid on the surface of the substrate. The cloth is further baked at 100 ° C to 200 ° C for 1 to 10 minutes, and then cooled to obtain the hydrophilic layer.

Preferably, in the water-soluble paint, the content of the modified phenol resin 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 The layer 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, the photosensitive photosensitive adhesive forming graphic information Floor.

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 parts by mass of the background dye, 10 to 25 parts by mass of the film-forming resin, and 60 to 80 parts by mass of the 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-containing polymer, such as an alcohol-containing hydroxyl group 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 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 purchased.

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 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 may be selected from the group consisting of novolacs, poly-p-hydroxystyrene, and the like. Products, poly-o-hydroxystyrene and its modified products, 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 m-cresol-tert-butyl One or more of the phenol-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 phenolic resin esterified sulfonate of the present invention.

24g of pure p-methyl phenolic resin (Weihai Economic and Technological Development Zone Tiancheng Chemical Co., Ltd. BTB-25) was dissolved in 200mL of tetrahydrofuran (THF), 2.5g of sodium metal was chopped, added, and mixed at room temperature for 0.5h;

Then, 3-sulfopropanic anhydride (formula (3), wherein A ₁ , A ₂ , A ₃ and A ₄ are H, x = 1; purchased from Shanghai Sanmu Chemical Technology Co., Ltd.) in tetrahydrofuran solution ( 3- sulfopropanhydride 14.85g, tetrahydrofuran solution 200mL), phenolic resin: 3-sulfopropionic anhydride weight ratio of 1.62:1, about 1h, 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, wavenumber absorption peak at 3400cm ^-1 phenolic resin hydroxyl group at the wavenumber 1750cm ^-1 for the ester carbonyl absorption peak wavenumber of 1240cm ^-1 and 1090cm ^-1 of the sulfonic acid group The absorption peak. Using sodium as an activator, a phenolic resin esterified sodium sulfonate is obtained.

According to the ratio of the phenol resin and 3-sulfopropionic anhydride, the phenolic resin esterified sodium sulfonate corresponds to the structure represented by the formula (1), p = 20, q = 20, and p / (p + q) = 0.5. Recorded as PSL-1.

Example 2

This example illustrates the preparation of the phenolic resin esterified sulfonate of the present invention.

4.8 g of pure m-methyl phenolic resin (Benxi Ruishida Chemical Co., Ltd. BX-30) was dissolved in 40 mL of dioxane, and a total of 0.63 g of sodium hydride (dispersed in mineral oil) was slowly added in three batches. Wherein the concentration of sodium hydride is 60% by weight), and reacted at room temperature for 1 hour;

Then 4-methyl-3-sulfopropionic anhydride was added dropwise (the structural formula is as shown in formula (3), wherein A ₁ is methyl, A ₂ , A ₃ and A ₄ are both H, x = 1; purchased from BEHRINGER) a dioxane solution (3.93 g of 4-methyl-3-sulfopropionic anhydride, 20 mL of dioxane), and a weight ratio of phenolic resin: 4-methyl-3-sulfopropionic anhydride of 1.22:1. After about 1 h, the reaction mixture was obtained;

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

The solid powder IR spectroscopy, wavenumber absorption peak at 3400cm ^-1 phenolic resin hydroxyl group at the wavenumber 1750cm ^-1 for the ester carbonyl absorption peak wavenumber of 1240cm ^-1 and 1090cm ^-1 of the sulfonic acid group The absorption peak. Using sodium hydride as an activator, a phenolic resin esterified sodium sulfonate is obtained.

According to the ratio of the phenolic resin and 4-methyl-3-sulfopropionic anhydride, the phenolic resin esterified sodium sulfonate corresponds to the structure represented by the formula (1), p=24, q=16, p/(q+ p) = 0.6. Recorded as PSL-2.

Example 3

This example illustrates the preparation of the phenolic resin esterified sulfonate of the present invention.

5.6 g of a mixed phenolic phenolic resin (p-cresol: m-cresol = 5:5 (molar ratio); Benxi Ruishida Chemical Co., Ltd. BX-20) was dissolved in 20 mL of dimethylformamide (DMF). , 0.79 g of metal potassium was chopped and added, and mixed at room temperature for 0.5 h;

Then, 4,4-dimethyl-3-sulfopropionic anhydride was added dropwise (the structural formula is as shown in formula (3), wherein A ₁ and A ₂ are methyl groups, A ₃ and A ₄ are H, x=1; purchased from sigma Aldrich) dimethylformamide solution (3.44 g of 4,4-dimethyl-3-sulfopropanhydride, 40 mL of dimethylformamide), phenolic resin: 4,4-dimethyl-3-sulfonate The weight ratio of the base propionic anhydride is 1.67:1, and the reaction mixture is obtained after about 1 hour;

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

The solid powder IR spectroscopy, wavenumber absorption peak at 3400cm ^-1 phenolic resin hydroxyl group at the wavenumber 1750cm ^-1 for the ester carbonyl absorption peak wavenumber of 1240cm ^-1 and 1090cm ^-1 of the sulfonic acid group The absorption peak. Using potassium as an activator, a phenolic resin esterified potassium sulfonate is obtained.

According to the ratio of the phenolic resin and the 4,4-dimethyl-3-sulfopropionic anhydride, the phenolic resin esterified potassium sulfonate corresponds to the structure represented by the formula (1), p=16, q=24, p/ (q+p)=0.4. Recorded as PSL-3.

Example 4

36g of mixed phenolic phenolic resin (p-cresol: m-cresol = 7:3 (molar ratio); Weihai Economic and Technological Development Zone Tiancheng Chemical Co., Ltd. BTB-225) was dissolved in 200mL of tetrahydrofuran (THF), 2.09g Lithium hydride was added and mixed at room temperature for 0.5 h;

Then 5-methyl-3-sulfopropionic anhydride was added dropwise (the structural formula is as shown in formula (3), 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 39.31 g, tetrahydrofuran 200 mL), phenolic resin: 5-methyl-3-sulfopropionic anhydride in a weight ratio of 0.92:1, about 1 hour, obtained 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 product obtained after completion of the esterification reaction was spray-dried to obtain a solid powder.

The solid powder IR spectroscopy, wavenumber absorption peak at 3400cm ^-1 phenolic resin hydroxyl group at the wavenumber 1750cm ^-1 for the ester carbonyl absorption peak wavenumber of 1240cm ^-1 and 1090cm ^-1 of the sulfonic acid group The absorption peak. Using lithium hydride as an activator, a phenolic resin esterified lithium sulfonate is obtained.

According to the ratio of the phenolic resin and 5-methyl-3-sulfopropionic anhydride, the phenolic resin esterified lithium sulfonate corresponds to the structure represented by the formula (1), p=24, q=6, p/(q+ p) = 0.8. Recorded as PSL-4.

Example 5

24g of the mixed phenolic phenolic resin (p-cresol: m-cresol = 3:7 (molar ratio); Benxi Ruishida Chemical Co., Ltd. BX-15) was dissolved in 100mL of tetrahydrofuran, and slowly added to the total of 1.05 in three batches. g sodium hydride (dispersed in mineral oil, wherein the concentration of sodium hydride is 60% by weight), mixed at room temperature for 1h;

Then, 5,5-dimethyl-3-sulfopropionic anhydride was added dropwise (the structural formula is as shown in formula (3), wherein A ₃ and A ₄ are methyl groups, A ₁ and A ₂ are H, x=1; purchased from Shanghai Tetrahydrofuran solution (7.15 g of 5,5-dimethyl-3-sulfopropionic anhydride, 40 mL of tetrahydrofuran), phenolic resin: 5,5-dimethyl-3-sulfopropionic anhydride The weight ratio is 3.35:1, 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 75 ° 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, wavenumber absorption peak at 3400cm ^-1 phenolic resin hydroxyl group at the wavenumber 1750cm ^-1 for the ester carbonyl absorption peak wavenumber of 1240cm ^-1 and 1090cm ^-1 of the sulfonic acid group The absorption peak. Using sodium hydride as an activator, a phenolic resin esterified sodium sulfonate is obtained.

According to the ratio of the phenolic resin and the 5,5-dimethyl-3-sulfopropionic anhydride, the phenolic resin esterified sodium sulfonate corresponds to the structure represented by the formula (1), p=4, q=16, p/ (q+p)=0.2. Recorded as PSL-5.

Example 6

2.4 g of the mixed phenolic phenolic resin (p-cresol: phenol = 5:5 (molar ratio); Benxi Ruishida Chemical Co., Ltd. BX-10) was dissolved in 10 mL of dioxane, and 0.17 g of hydrogenated was slowly added. Lithium, mixed at room temperature for 1 h;

Then, 4-propyl-3-sulfopropionic anhydride was added dropwise (the structural formula is as shown in formula (3), wherein A ₁ is a propyl group, A ₂ , A ₃ and A ₄ are H, x=1; purchased from Sigma Co., Ltd.) a dioxane solution (3.69 g of 4-propyl-3-sulfopropionic anhydride, 40 mL of dioxane), and a weight ratio of phenolic resin: 4-propyl-3-sulfopropionic anhydride of 0.65:1. After about 1 h, the reaction mixture was obtained;

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

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

The solid powder IR spectroscopy, wavenumber absorption peak at 3400cm ^-1 phenolic resin hydroxyl group at the wavenumber 1750cm ^-1 for the ester carbonyl absorption peak wavenumber of 1240cm ^-1 and 1090cm ^-1 of the sulfonic acid group The absorption peak. Using lithium hydride as an activator, a phenolic resin esterified lithium sulfonate is obtained.

According to the ratio of the phenolic resin and 4-propyl-3-sulfopropionic anhydride, the phenolic resin esterified lithium sulfonate corresponds to the structure represented by the formula (1), p=19, q=1, p/(q+ p) = 0.95. Recorded as PSL-6.

Example 7

34g of mixed phenolic phenolic resin (p-cresol: phenol = 7:3 (molar ratio); Weihai Economic and Technological Development Zone Tiancheng Chemical Co., Ltd. BTB-19) was dissolved in 200mL of dimethyl sulfoxide, 0.6g of metal Potassium cut into pieces and slowly add, mix at room temperature for 0.5h;

Then 5-isopropyl-3-sulfopropionic anhydride was added dropwise (the structural formula is as shown in formula (3), wherein A ₃ is isopropyl, A ₁ , A ₂ and A ₄ are H, x=1; purchased from sigma aldrich a solution of dimethyl sulfoxide (2.75 g of 5-isopropyl-3-sulfopropanhydride, 20 mL of dimethyl sulfoxide), phenolic resin: weight of 5-isopropyl-3-sulfopropionic anhydride The ratio is 12.35:1, about 1 hour, and the reaction mixture is obtained;

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

The solid powder IR spectroscopy, wavenumber absorption peak at 3400cm ^-1 phenolic resin hydroxyl group at the wavenumber 1750cm ^-1 for the ester carbonyl absorption peak wavenumber of 1240cm ^-1 and 1090cm ^-1 of the sulfonic acid group The absorption peak. Using potassium as an activator, a phenolic resin esterified potassium sulfonate is obtained.

According to the ratio of the phenolic resin and 5-isopropyl-3-sulfopropionic anhydride, the phenolic resin esterified potassium sulfonate corresponds to the structure represented by the formula (1), p=1, q=19, p/(q +p) = 0.05. Recorded as PSL-7.

Example 8

5.5g of mixed phenolic phenolic resin (p-cresol: phenol = 3:7 (molar ratio); Weihai Economic and Technological Development Zone Tiancheng Chemical Co., Ltd. BTB-M) is dissolved in 20mL of N-methylpyrrolidone, 1.15g of sodium metal is 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 (3), wherein A ₁ and A ₃ are methyl groups, A ₂ and A ₄ are H, x=1; purchased from sigma Nd-methylpyrrolidone solution of aldrich) (8.21 g of 4,5-dimethyl-3-sulfopropanhydride, 100 mL of N-methylpyrrolidone), phenolic resin: 4,5-dimethyl-3-sulfonate The weight ratio of the base propionic anhydride is 0.67:1, 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 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, wavenumber absorption peak at 3400cm ^-1 phenolic resin hydroxyl group at the wavenumber 1750cm ^-1 for the ester carbonyl absorption peak wavenumber of 1240cm ^-1 and 1090cm ^-1 of the sulfonic acid group The absorption peak. Using lithium as an activator, a phenolic resin esterified lithium sulfonate is obtained.

According to the ratio of the phenolic resin and the 4,5-dimethyl-3-sulfopropionic anhydride, the phenolic resin esterified lithium sulfonate corresponds to the structure represented by the formula (1), p=20, q=0, p/ (q+p)=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 photosensitive photosensitive 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;

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;

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.

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 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.

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 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;

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

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., 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.

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 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;

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.

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 17

This example illustrates the preparation of the phenolic resin esterified besylate salt of the present invention.

24 g of pure p-methyl phenolic resin (Weihai Economic and Technological Development Zone Tiancheng Chemical Co., Ltd. BTB-25) was dissolved in 200 mL of tetrahydrofuran (THF), 2.51 g of sodium metal was chopped and added, and mixed at room temperature for 0.5 h;

Then, a solution of 2-sulfobenzoic anhydride (Belling Technology Co., Ltd.) in tetrahydrofuran (20.09 g of 2-sulfobenzoic anhydride, 200 mL of tetrahydrofuran) was added dropwise, and the weight ratio of phenol resin: 2-sulfobenzoic anhydride was 1.19: 1, about 1h, 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 absorption infrared spectroscopy, the spectrum wave number of the absorption peak at 3400cm ^-1 for the hydroxyl group of the phenol resin, at the wavenumber 1720cm ^-1 for the ester carbonyl, the wavenumber 1500cm ^-1 and 1450cm ^-1 of benzene at The absorption peak of the ring, the wave number of 1220 cm ^-1 and 1090 cm ^-1 is the absorption peak of the sulfonic acid group. Sodium is used as an activator to obtain a phenolic resin esterified sodium benzene sulfonate.

According to the ratio of the phenolic resin and the 2-sulfobenzoic anhydride, the phenolic resin esterified sodium benzenesulfonate corresponds to the structure represented by the formula (2), n=20, m=20, n/(m+n)= 0.5. Recorded as PSL-9.

Example 18

This example illustrates the preparation of the phenolic resin esterified besylate salt of the present invention.

4.8 g of pure m-methyl phenolic resin (Benxi Ruishida Chemical Co., Ltd. BX-30) was dissolved in 40 mL of dioxane, and a total of 0.63 g of sodium hydride (dispersed in mineral oil) was slowly added in three batches. The sodium hydride concentration is 60% by weight), and reacted at room temperature for 1 hour;

Then, a solution of 5-fluoro-2-sulfobenzoic anhydride (Sigma-Aldrich) in dioxane (5.29 g of 5-fluoro-2-sulfobenzoic anhydride, 20 mL of dioxane) was added dropwise, and the phenol resin: The weight ratio of 5-fluoro-2-sulfobenzoic anhydride is 0.91:1, and the reaction mixture is obtained after about 1 hour;

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

The solid powder absorption infrared spectroscopy, the spectrum wave number of the absorption peak at 3400cm ^-1 for the hydroxyl group of the phenol resin, at the wavenumber 1720cm ^-1 for the ester carbonyl, the wavenumber 1500cm ^-1 and 1450cm ^-1 of benzene at The absorption peak of the ring, the wave number of 1220 cm ^-1 and 1090 cm ^-1 is the absorption peak of the sulfonic acid group. Using sodium hydride as an activator, a phenolic resin esterified sodium benzene sulfonate is obtained.

According to the ratio of the phenolic resin and 5-fluoro-2-sulfobenzoic anhydride, the phenolic resin esterified sodium benzene sulfonate corresponds to the structure represented by the formula (2), n=24, m=16, n/(m +n) = 0.6. Recorded as PSL-10.

Example 19

This example illustrates the preparation of the phenolic resin esterified besylate salt of the present invention.

5.6 g of a mixed phenolic phenolic resin (p-cresol: m-cresol = 5:5 (molar ratio); Benxi Ruishida Chemical Co., Ltd. BX-20) was dissolved in 20 mL of dimethylformamide (DMF). , 0.79 g of metal potassium was chopped and added, and mixed at room temperature for 0.5 h;

Then, a solution of tetraiodo-2-sulfonic acid benzoic anhydride in dimethylformamide (14.01 g of tetraiodo-2-sulfonic acid benzoic anhydride, 40 mL of dimethylformamide) was added dropwise, and phenolic resin: tetraiodo-2- The weight ratio of sulfonic acid benzoic anhydride is 0.4:1, 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 product obtained after completion of the esterification reaction was spray-dried to obtain a solid powder.

The solid powder absorption infrared spectroscopy, the spectrum wave number of the absorption peak at 3400cm ^-1 for the hydroxyl group of the phenol resin, at the wavenumber 1720cm ^-1 for the ester carbonyl, the wavenumber 1500cm ^-1 and 1450cm ^-1 of benzene at The absorption peak of the ring, the wave number of 1220 cm ^-1 and 1090 cm ^-1 is the absorption peak of the sulfonic acid group. Using potassium as an activator to obtain a phenolic resin esterified potassium benzenesulfonate;

According to the ratio of the phenolic resin and the tetraiodo-2-sulfonic acid benzoic anhydride, the phenolic resin esterified potassium benzenesulfonate corresponds to the structure represented by the formula (2), n=16, m=24, n/(m+ n) = 0.4. Recorded as PSL-11.

Example 20

36g of mixed phenolic phenolic resin (p-cresol: m-cresol = 7:3 (molar ratio); Weihai Economic and Technological Development Zone Tiancheng Chemical Co., Ltd. BTB-225) was dissolved in 200mL of tetrahydrofuran (THF), 2.09g Lithium hydride was added and mixed at room temperature for 0.5 h;

Then, a solution of 2-sulfobenzoic anhydride (Belling Technology Co., Ltd.) in tetrahydrofuran (48.22 g of 2-sulfobenzoic anhydride, 200 mL of tetrahydrofuran) was added dropwise, and the weight ratio of phenol resin: 2-sulfobenzoic anhydride was 0.75: 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 esterification reaction for 4 h;

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

The solid powder absorption infrared spectroscopy, the spectrum wave number of the absorption peak at 3400cm ^-1 for the hydroxyl group of the phenol resin, at the wavenumber 1720cm ^-1 for the ester carbonyl, the wavenumber 1500cm ^-1 and 1450cm ^-1 of benzene at The absorption peak of the ring, the wave number of 1220 cm ^-1 and 1090 cm ^-1 is the absorption peak of the sulfonic acid group. Using lithium hydride as an activator to obtain a phenolic resin esterified lithium benzene sulfonate;

According to the ratio of the phenolic resin and the 2-sulfobenzoic anhydride, the phenolic resin esterified lithium benzenesulfonate corresponds to the structure represented by the formula (2), n=24, m=6, n/(m+n)= 0.8. Recorded as PSL-12.

Example 21

24g of the mixed phenolic phenolic resin (p-cresol: m-cresol = 3:7 (molar ratio); Benxi Ruishida Chemical Co., Ltd. BX-15) was dissolved in 100mL of tetrahydrofuran, and slowly added to the total of 1.05 in three batches. g sodium hydride (dispersed in mineral oil, sodium hydride concentration of 60% by weight), mixed at room temperature for 1h;

Then, a solution of 2-sulfobenzoic anhydride (Belling Technology Co., Ltd.) in tetrahydrofuran (8.04 g of 2-sulfobenzoic anhydride, 40 mL of tetrahydrofuran) was added dropwise, and the weight ratio of phenolic resin: 2-sulfobenzoic anhydride was 2.99: 1, about 1h, 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 product obtained after completion of the esterification reaction was spray-dried to obtain a solid powder.

The solid powder absorption infrared spectroscopy, the spectrum wave number of the absorption peak at 3400cm ^-1 for the hydroxyl group of the phenol resin, at the wavenumber 1720cm ^-1 for the ester carbonyl, the wavenumber 1500cm ^-1 and 1450cm ^-1 of benzene at The absorption peak of the ring, the wave number of 1220 cm ^-1 and 1090 cm ^-1 is the absorption peak of the sulfonic acid group. Using sodium hydride as an activator to obtain a phenolic resin esterified sodium benzene sulfonate;

According to the ratio of the phenolic resin and the 2-sulfobenzoic anhydride, the phenolic resin esterified sodium benzenesulfonate corresponds to the structure represented by the formula (2), n=4, m=16, n/(m+n)= 0.2. Recorded as PSL-13.

Example 22

2.4 g of the mixed phenolic phenolic resin (p-cresol: phenol = 5:5 (molar ratio); Benxi Ruishida Chemical Co., Ltd. BX-10) was dissolved in 10 mL of dioxane, and 0.17 g of hydrogenated was slowly added. Lithium, mixed at room temperature for 1 h;

Then, a solution of 2-sulfobenzoic anhydride (Belling Technology Co., Ltd.) in dioxane (3.82 g of 2-sulfobenzoic anhydride, 40 mL of dioxane), phenolic resin: 2-sulfobenzoic anhydride was added dropwise. The weight ratio is 0.63:1, 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 75 ° C for esterification reaction for 2 h;

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

The solid powder absorption infrared spectroscopy, the spectrum wave number of the absorption peak at 3400cm ^-1 for the hydroxyl group of the phenol resin, at the wavenumber 1720cm ^-1 for the ester carbonyl, the wavenumber 1500cm ^-1 and 1450cm ^-1 of benzene at The absorption peak of the ring, the wave number of 1220 cm ^-1 and 1090 cm ^-1 is the absorption peak of the sulfonic acid group. Using lithium hydride as an activator to obtain a phenolic resin esterified lithium benzene sulfonate;

According to the ratio of the phenolic resin and the 2-sulfobenzoic anhydride, the phenolic resin esterified lithium benzenesulfonate corresponds to the structure represented by the formula (2), n=19, m=1, n/(m+n)= 0.95. Recorded as PSL-14.

Example 23

34g of mixed phenolic phenolic resin (p-cresol: phenol = 7:3 (molar ratio); Weihai Economic and Technological Development Zone Tiancheng Chemical Co., Ltd. BTB-19) was dissolved in 200mL of dimethyl sulfoxide, 0.6g of metal Potassium cut into pieces and slowly add, mix at room temperature for 0.5h;

Then, a solution of 5-fluoro-2-sulfobenzoic anhydride (Sigma-Aldrich) in dimethyl sulfoxide (3.12 g of 5-fluoro-2-sulfobenzoic anhydride, 20 mL of dimethyl sulfoxide), phenolic Resin: 5-fluoro-2-sulfobenzoic anhydride in a weight ratio of 10.88:1, about 1 hour, to obtain a reaction mixture;

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

The solid powder absorption infrared spectroscopy, the spectrum wave number of the absorption peak at 3400cm ^-1 for the hydroxyl group of the phenol resin, at the wavenumber 1720cm ^-1 for the ester carbonyl, the wavenumber 1500cm ^-1 and 1450cm ^-1 of benzene at The absorption peak of the ring, the wave number of 1220 cm ^-1 and 1090 cm ^-1 is the absorption peak of the sulfonic acid group. Using potassium as an activator to obtain a phenolic resin esterified potassium benzenesulfonate;

According to the ratio of the phenolic resin and the 5-fluoro-2-sulfobenzoic anhydride, the phenolic resin esterified potassium benzenesulfonate corresponds to the structure represented by the formula (2), n=1, m=19, n/(m +n) = 0.05. Recorded as PSL-15.

Example 24

5.5g of the mixed phenolic phenolic resin (p-cresol: phenol = 3:7 (molar ratio); Weihai Economic and Technological Development Zone Tiancheng Chemical Co., Ltd. BTB-M) was dissolved in 20mL of N-methylpyrrolidone, 1.15g The metal sodium is cut into pieces and slowly added, and mixed at room temperature for 0.5 h;

Then a solution of 5-fluoro-2-sulfobenzoic anhydride (Sigma-Aldrich) in N-methylpyrrolidone (5-fluoro-2-sulfobenzoic anhydride 10.11 g, N-methylpyrrolidone 100 mL), phenolic Resin: 5-fluoro-2-sulfobenzoic anhydride in a weight ratio of 0.54:1, about 1 hour, to obtain a reaction mixture;

The reaction mixture was pre-reacted at room temperature for 1 h, and then heated to 120 ° 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 absorption infrared spectroscopy, the spectrum wave number of the absorption peak at 3400cm ^-1 for the hydroxyl group of the phenol resin, at the wavenumber 1720cm ^-1 for the ester carbonyl, the wavenumber 1500cm ^-1 and 1450cm ^-1 of benzene at The absorption peak of the ring, the wave number of 1220 cm ^-1 and 1090 cm ^-1 is the absorption peak of the sulfonic acid group. Using lithium as an activator to obtain a phenolic resin esterified lithium benzenesulfonate;

According to the ratio of the phenolic resin and the 5-fluoro-2-sulfobenzoic anhydride, the phenolic resin esterified lithium benzenesulfonate corresponds to the structure represented by the formula (2), n = 20, m = 0, n / (m +n)=1. Recorded as PSL-16.

Example 25

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

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-17 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 26

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

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 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 having a thickness of 2 μm to obtain a photosensitive photosensitive printing plate;

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

Example 27

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

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 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;

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

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

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

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.

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 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;

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.

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 30

The PSL-14 and HD-110 trifunctional aziridine crosslinker (Jiangsu Kangle New Material Technology Co., Ltd.) prepared in Example 22 were dissolved in water to prepare a PSL-14 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 layer having a thickness of 1.8 μm to obtain a photosensitive photosensitive printing plate;

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

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-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., 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.

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 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;

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.

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

Comparative example 1

Phenolic resin (Benxi Ruishida Chemical Co., Ltd. BX-20) and HD-110 trifunctional aziridine crosslinker (Jiangsu Kangle New Material Technology Co., Ltd.) are dissolved in dioxane and formulated into BX-20 phenolic resin. a dioxane solution having a concentration of 10% by weight and an aziridine concentration of 3% by weight;

The dioxane 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; The hydrophilic layer has a thickness of 3 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.

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

Comparative example 2

BTB-25 phenolic resin and HD-110 trifunctional aziridine crosslinker (Jiangsu Kangle New Material Technology Co., Ltd.) were dissolved in DMF, and titanium dioxide with a particle size of 30 nm was added and dispersed by an emulsifier at 4000 rpm for 1 hour. a solution having a BTB-25 phenolic resin concentration of 6% by weight, an aziridine concentration of 1% by weight, and a titanium dioxide concentration of 8% 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;

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.

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

Comparative example 3

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

A metal aluminum plate with a thickness of 0.27 mm is selected as the base plate, and the dirt and oil are first removed for cleaning. 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 liquid was applied to the aluminum plate by dip coating, and then baked in an oven at 200 ° C for 5 minutes to cure the coating liquid into a bonding layer having a thickness of 5 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 8 minutes to dry and solidify the coating liquid into a hydrophilic layer. The hydrophilic layer had a thickness of 5 μm to form a lithographic printing plate base.

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.

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

Table 1

Numbering	Hydrophilic layer	p/(p+q)	Contact angle	Water resistance	Printing resistance (parts)	Printed surface
Example 9	PSL-1	0.5	<10°	>3h	16000	clean
Example 10	PSL-2	0.6	<10°	>3h	17000	clean
Example 11	PSL-3	0.4	<10°	>3h	14000	clean
Example 12	PSL-4	0.8	<10°	>3h	13000	clean
Example 13	PSL-5	0.2	<10°	>3h	12000	clean
Example 14	PSL-6	0.95	<10°	>3h	7000	clean
Example 15	PSL-7	0.05	<10°	>3h	5500	clean
Example 16	PSL-8	1	<10°	>3h	6000	clean
Numbering	Hydrophilic layer	n/(m+n)	Contact angle	Water resistance	Printing resistance (parts)	Printed surface
Example 25	PSL-9	0.5	<10°	>3h	18000	clean
Example 26	PSL-10	0.6	<10°	>3h	19000	clean
Example 27	PSL-11	0.4	<10°	>3h	16000	clean
Example 28	PSL-12	0.8	<10°	>3h	15000	clean
Example 29	PSL-13	0.2	<10°	>3h	14000	clean
Example 30	PSL-14	0.95	<10°	>3h	10000	clean
Example 31	PSL-15	0.05	<10°	>3h	8000	clean
Example 32	PSL-16	1	<10°	>3h	6000	clean
Comparative example 1	-	-	95°	>3h		dirty
Comparative example 2	-	-	30°	>3h		dirty
Comparative example 3	-	-	45°	>3h		dirty

In the above examples and comparative examples, Examples 1-8 are phenolic resin esterified sulfonates (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 phenolic resin esterified besylate (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. Comparative Example 1 is an ink jet printing plate prepared using a phenol resin, Comparative Example 2 is an ink jet printing plate prepared using a phenol resin and titanium oxide (water absorbing particles), and Comparative Example 3 is an inkjet printing prepared by using the prior art (CN102407653A). Version.

It can be seen from the above examples, comparative examples and the result data of Table 1 that the phenolic resin esterified sulfonate provided by the present invention can be made into a hydrophilic layer in a printed hydrophilic plate to provide a hydrophilic version for better pro- Water-based, with water resistance 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. On the other hand, in Comparative Example 1-3, the ink jet printing plate obtained by the prior art could not obtain a clean printed product, and it was impossible to perform acceptable printing.

Claims (17)

1. a modified phenolic resin, which is a phenolic resin esterified besylate or a phenolic resin esterified sulfonate;

   The phenolic resin esterified sulfonate contains a chemical structure represented by the formula (1),

   

   Wherein, p + q = a positive integer of 4 to 50, p / (p + q) = 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; B is present or absent, and when B is present, is selected from C ₁ -C ₁₂ alkyl;

   The phenolic resin esterified besylate contains a chemical structure represented by the formula (2),

   

   Wherein m + n = a positive integer of 4 to 50, n / (m + n) = 0.05 to 1, and A ₅ to A ₈ are each independently hydrogen, a halogen element or a C ₁ - C ₆ alkoxy group; D is present or absent, and is selected from C ₁ to C ₁₂ alkyl groups when D is present;

   M is Li, Na, K or NH ₄ .
2. The modified phenol resin 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. It is preferably 0.2 to 0.8, and more preferably 0.4 to 0.6.
3. The modified phenol resin according to claim 1 or 2, wherein an infrared spectrum of the phenolic resin esterified besylate is an absorption peak of a phenolic resin hydroxyl group at a wave number of 3400 cm ^-1 , and the wave number is 1720 cm. ^-1 absorption peak of the ester carbonyl, the wave number of 1500cm ^-1 and an absorption peak at 1450 cm ^-1 benzene ring, the wave number 1220 cm ^-1 and 1090 ^{cm -1} as an absorption peak of a sulfonic acid group;

   The esterified phenol resin salt of IR spectrum, a wavenumber of the absorption peak at 3400cm ^-1 phenolic resin hydroxyl groups, the wave number of the absorption peak at 1750cm ^-1 for the ester carbonyl, the wave number of 1240cm ^-1 and 1090cm ^-1 is the absorption peak of the sulfonic acid group.
4. The modified phenol resin according to any one of claims 1 to 3, wherein the phenolic resin esterified besylate is an esterification product of a phenol resin and a sulfobenzoic anhydride; wherein the sulfo group The benzoic anhydride is selected from the group consisting of 2-sulfobenzoic anhydride, 5-fluoro-2-sulfobenzoic anhydride, 5-iodo-2-sulfobenzoic anhydride, 5-methoxy-2-sulfobenzoic anhydride And at least one of 5-ethoxy-2-sulfobenzoic anhydride, tetrabromo-2-sulfobenzoic acid cyclic anhydride, and tetraiodo-2-sulfonic acid benzoic anhydride;

   The phenolic resin esterified sulfonate is an esterification product of a phenolic resin and sulfopropionic anhydride; wherein the sulfopropanhydride is selected from the group consisting of 3-sulfopropionic anhydride and 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 At least one of -3-sulfopropionic anhydride, 4-propyl-3-sulfopropionic anhydride, and 5-isopropyl-3-sulfopropionic anhydride.
5. A method for synthesizing a modified phenolic resin according to any one of claims 1 to 4, which comprises: in the presence of a solvent and an activator,

   The phenolic resin and the sulfopropionic anhydride represented by the formula (3) are subjected to an esterification reaction,

   

   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;

   The phenolic resin and the sulfobenzoic anhydride represented by the formula (4) are subjected to an esterification reaction,

   

   Among them, A ₅ to A ₈ are each independently hydrogen, a halogen element or a C ₁ -C ₆ alkoxy group.
6. The method according to claim 5, wherein the sulfobenzoic anhydride is 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 formic anhydride;

   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-sulfonate Propionic anhydride, 5,5-dimethyl-3-sulfopropionic anhydride, 4,5-dimethyl-3-sulfopropionic anhydride, 4-propyl-3-sulfopropionic anhydride and 5-isopropyl At least one of -3-sulfopropionic anhydride;

   Preferably, the phenolic resin has a degree of polymerization of 4 to 50;

   Preferably, the solvent is an organic solvent capable of dissolving a phenolic resin; the organic solvent is selected from the group consisting of dimethylformamide, At least one of dimethyl sulfoxide, r-butyrolactone, N-methylpyrrolidone, N-ethylpyrrolidone, tetrahydrofuran, 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.
7. The method according to claim 5 or 6, wherein the weight ratio of the phenol resin to the sulfobenzoic anhydride is (0.1 to 20): 1, preferably (0.5 to 11): 1; The molar ratio of the benzoic anhydride to the activator is 1: (1 to 1.2); or

   The weight ratio of the phenolic resin to the sulfopropionic anhydride is (0.1-20):1, preferably (0.5-13):1; the molar ratio of the sulfopropionic anhydride to the activator is 1: (1~1.2);

   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.
8. 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 3400 cm ^-1 and the absorption of the phenolic resin hydroxyl group absorption peak at a wave number of 1720cm ^-1 to the ester carbonyl, the wave number of 1500cm ^-1 and an absorption peak at 1450cm ^-1 benzene ring, the wave number of 1220cm ^-1 and an absorption peak at 1090cm ^-1 sulfonic acid group ;

   Alternatively, the infrared absorption spectrum of the hydrophilic layer, at the wavenumber 3400cm ^-1 to the absorption peak of hydroxyl group of phenolic resin, at the wavenumber 1750cm ^-1 for the ester carbonyl absorption peak wavenumber of 1240cm ^-1 and 1090cm ^-1 It is the absorption peak of the sulfonic acid group.
9. 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.
10. The hydrophilic plate according to claim 8 or 9, wherein the hydrophilic layer is obtained by coating the modified phenol resin according to any one of claims 1 to 4 on the substrate.
11. The hydrophilic plate according to claim 10, wherein the coating process comprises: dissolving the modified phenol resin in water to obtain a water-soluble coating liquid; and applying the coating liquid to a surface of the substrate Coating on top, 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 phenol resin is 5 to 30% by weight.
12. 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.
13. Use of a hydrophilic plate according to any one of claims 8-12 in a printing plate.
14. 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.
15. 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 Layer by spraying ink on the hydrophilic layer And dried to form.
16. 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.
17. 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.