CN108329413B - A kind of polyvinyl alcohol sulfonate and its synthetic method, printing hydrophilic version and application and galley - Google Patents
A kind of polyvinyl alcohol sulfonate and its synthetic method, printing hydrophilic version and application and galley Download PDFInfo
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- CN108329413B CN108329413B CN201710045750.4A CN201710045750A CN108329413B CN 108329413 B CN108329413 B CN 108329413B CN 201710045750 A CN201710045750 A CN 201710045750A CN 108329413 B CN108329413 B CN 108329413B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41N1/00—Printing plates or foils; Materials therefor
- B41N1/12—Printing plates or foils; Materials therefor non-metallic other than stone, e.g. printing plates or foils comprising inorganic materials in an organic matrix
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41N1/00—Printing plates or foils; Materials therefor
- B41N1/16—Curved printing plates, especially cylinders
- B41N1/22—Curved printing plates, especially cylinders made of other substances
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Printing Plates And Materials Therefor (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to galley field, a kind of polyvinyl alcohol sulfonate and its synthetic method, printing hydrophilic version and application and galley are disclosed.The polyvinyl alcohol sulfonate contains chemical structure shown in formula (1),Formula (1), wherein the positive integer of m+n=400~5000, the positive integer that n/ (m+n)=0.05~1, x is 1~3；A1~A4It is each independently hydrogen, C1~C6Alkyl or C1~C6Alkenyl；M is Li, Na, K or NH4.The hydrophily of coating can be substantially improved in such hydrophilic high mol compound, improve the printability of hydrophilic version.
Description
Technical field
The present invention relates to galley fields, and in particular, to a kind of polyvinyl alcohol sulfonate and its synthetic method, containing should
The hydrophilic version of printing for the hydrophilic layer that polyvinyl alcohol sulfonate is formed, the hydrophilic version are applied in galley, and hydrophilic by this
Ink jet printing version, photosensitive photosensitive printed board and the thermosensitive printing plates that version is formed.
Background technique
Printing industry is one of the industry having a major impact to Chinese national economy.Preparing galley is wherein important skill
Art step.Hydrophilic version is first usually prepared in modern galley preparation, then can further prepare spray on the basis of hydrophilic version
Ink print version, photosensitive photosensitive printed board or thermosensitive printing plates etc..Therefore, the hydrophilic version for obtaining high quality becomes the most important thing.
CN103587273A discloses a kind of photosensitive grain-free printing plate, is made of version base, hydrophilic layer and photosensitive layer, hydrophilic
Layer, photosensitive layer are sequentially coated on version base.Wherein hydrophilic layer contains nanoscale and/or micron particles, resin.The parent of coating
Water layer have with similar hydrophilicity and water retention property after electrolytic graining and anodized, can replace through electrolytic graining
Version base after change and anodized, thus the purpose for spent acid and salkali waste the pollution environment for avoiding anodic oxidation to generate significantly.
CN103937303A discloses a kind of cationic polymerization hydrophilic coating materials, calculates in parts by mass, by 15~
45% vinyl ether monomers or its prepolymer, 1~5% cationic initiator, 50~80% nanoscale or micron order parent
Water particle composition.Solidify to obtain through ultraviolet light after the hydrophilic coating materials are coated on version base and exempts from sand screen mesh galley
Material.Hydrocolloid particle is added in the coating for forming hydrophilic layer and can be saved with providing finally obtained printing plate to version for this method
Base carries out sand screen mesh processing, simplifies technique and improves the viscosity and surface tension of plate.
CN102407653A discloses feature of environmental protection offset printing version base, including metal or nonmetallic version base, wherein the version
Adhesive layer and hydrophilic layer are successively stained on base, adhesive layer is solidified by adhesive layer coating fluid, and the hydrophilic layer is by hydrophilic layer
Coating fluid solidifies, and hydrophilic layer coating fluid is the hydrophilic polymer resin by 5%-10%, 10%-30% nanoscale or micro-
The metal or nonmetal oxide of meter level, the curing agent and 0.05%-3% surfactant of 0.5%-5% and 60%-80%'s
Water composition；The version base is metal material, adhesive layer coating fluid by 10%-40% heat reactive resin, 3%-20% curing agent and
The aqueous solvent of 50%-80% forms；The version base be nonmetallic materials, adhesive layer coating fluid by 5%-50% solvent borne tree
Rouge, the corrosive agent of 0-25% and the aqueous solvent composition of 30%-95%.But this method need nanoscale or micron-sized metal or
Nonmetal oxide helps to improve the hydrophilicity of hydrophilic layer, and additional adhesive layer is needed to provide cohesive force.
Prior art mostly uses nanoscale or micron order hydrocolloid particle that hydrophilic layer is made, and be easy to cause printed matter dirty, has
Flaw.
Summary of the invention
The purpose of the present invention is to solve how to improve the printing performance problem for printing hydrophilic version, provide a kind of poly-
Vinyl alcohol sulfonate and its synthetic method, printing hydrophilic version and application and galley.Clean printed matter can be obtained
And galley has high press resistance rate.
To achieve the goals above, the present invention provides a kind of polyvinyl alcohol sulfonate, which contains formula
(1) chemical structure shown in,
Wherein, the positive integer of m+n=400~5000, the positive integer that n/ (m+n)=0.05~1, x is 1~3；A1~A4Respectively
From independently being hydrogen, C1~C6Alkyl or C1~C6Alkenyl；M is Li, Na, K or NH4。
The present invention also provides a kind of synthetic methods of polyvinyl alcohol sulfonate of the invention, this method comprises: in solvent
In the presence of activator, sultones shown in polyvinyl alcohol and formula (2) is subjected to etherification reaction,
Wherein, the positive integer that x is 1~3, A1~A4It is each independently hydrogen, C1~C6Alkyl or C1~C6Alkenyl.
The present invention also provides a kind of hydrophilic versions of printing, comprising: substrate, and the hydrophilic layer being formed on the substrate；
Wherein, in the infrared absorption spectra of the hydrophilic layer, wave number 3340cm-1Place is the absorption peak of polyvinyl alcohol hydroxyl, and wave number is
1120cm-1Place is the absorption peak of ehter bond, wave number 1240cm-1And 1090cm-1Place is the absorption peak of sulfonic acid group.
The present invention also provides a kind of application of hydrophilic version of the invention in printing plate.
The present invention also provides a kind of galleys, comprising: hydrophilic version of the invention, and the shape on the hydrophilic layer in hydrophilic version
At graph text information layer.
The present invention also provides a kind of ink jet printing versions, comprising: hydrophilic version of the invention, and the hydrophilic layer in hydrophilic version
The graph text information layer of upper formation, wherein the graph text information layer to be formed by spraying ink on the hydrophilic layer and drying.
The present invention also provides a kind of photosensitive photosensitive printed boards, comprising: hydrophilic version of the invention, and the parent in hydrophilic version
Photosensitive photoresists on water layer, the photosensitive photoresists form graph text information layer.
The present invention also provides a kind of thermosensitive printing plates, comprising: hydrophilic version of the invention, and the hydrophilic layer in hydrophilic version
On thermographic layer, the thermographic layer forms graph text information layer.
Through the above technical solutions, providing a kind of polyvinyl alcohol sulfonate, printed using made from the polyvinyl alcohol sulfonate
Hydrophilic version is brushed, extraordinary hydrophilic effect, water resistance and printability resistance can be obtained, nanoscale or micron is added without additional
Grade hydrocolloid particle.Qualified printed matter can be obtained, surface cleaning is indefectible, and galley press resistance rate is high.
Other feature of the invention and technical effect are by the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The first object of the present invention provides a kind of polyvinyl alcohol sulfonate, which contains shown in formula (1)
Chemical structure,
Wherein, the positive integer of m+n=400~5000, the positive integer that n/ (m+n)=0.05~1, x is 1~3；A1~A4Respectively
From independently being hydrogen, C1~C6Alkyl or C1~C6Alkenyl；M is Li, Na, K or NH4。
According to the present invention, it in the chemical structure of the polyvinyl alcohol sulfonate, can be taken with the part of hydroxyl of polyvinyl alcohol
On behalf of sulfonate, as inferior horn is designated as the structural unit (being denoted as structural unit -1) of n in formula (1)；It can also partially be polyvinyl alcohol,
As inferior horn is designated as the structural unit (being denoted as structural unit -2) of m in formula (1).Formula (1) is for illustrating the polyvinyl alcohol sulfonate
Chemical structure, wherein connection type in the polyvinyl alcohol sulfonate of structural unit -1 and structural unit -2 is simultaneously unlimited
It is fixed, it can be random or block.Further, can there is structural unit -2 in the chemical structure of the polyvinyl alcohol sulfonate,
Can also not have.The content of structural unit -1 in the polyvinyl alcohol sulfonate can be represented by n/ (m+n).Preferable case
Under, n/ (m+n) is 0.2~0.95, preferably 0.2~0.8, more preferably 0.4~0.6.When the polyvinyl alcohol sulfonate
It, can the polyvinyl alcohol sulphur when relation with contents of structural unit -1 and structural unit -2 is met the above range in chemical structure
Hydrochlorate provides better printing performance, such as hydrophily, water resistance, resistance to print property with hydrophilic version for the printing further prepared.
The chemical structure of heretofore described polyvinyl alcohol sulfonate can be measured by the method for infrared spectroscopy.It can lead to
The hydroxyl of polyvinyl alcohol described in overpotential titration measuring is substituted the content of part.
In the case of, according to the invention it is preferred to, in the infrared spectrum spectrogram of the polyvinyl alcohol sulfonate, wave number is
3340cm-1Place is the absorption peak of polyvinyl alcohol hydroxyl, wave number 1120cm-1Place is the absorption peak of ehter bond, wave number 1240cm-1
And 1090cm-1Place is the absorption peak of sulfonic acid group.
According to the present invention, a kind of preferred embodiment, the polyvinyl alcohol sulfonate can synthesize by the following method:
The polyvinyl alcohol sulfonate is the etherification product of polyvinyl alcohol and sultones.
Preferably, the sultones is selected from 1,3-propane sultone, Isosorbide-5-Nitrae-propane sultone, 1- methyl-1, the third sulphur of 3-
Acid lactone, 1,1- dimethyl -1,3- propane sultone, 1- ethyl -1,3- propane sultone, 1,2- dimethyl -1,3- propane sulfonic acid
Lactone, 1,3- dimethyl -1,3- propane sultone, 1- acrylic -1,3- propane sultone, 1- methyl -2- ethyl the third sulphur of -1,3-
Acid lactone, 1- methyl-1,4- butyl sultone, 1- methyl-1,4- butyl sultone, 1- acrylic -1,4- butyl sultone and
At least one of penta sultones of 1,5-.It is further preferred that the sultones is selected from 1,3-propane sultone, 1- methyl-1,3-
Propane sultone, 1,1- dimethyl -1,3- propane sultone, 1- ethyl -1,3- propane sultone, 1,2- dimethyl -1,3- third
At least one of sultones and 1,4- propane sultone.
In the present invention, polyvinyl alcohol and sultones carry out etherification reaction in the presence of alkali compounds and solvent.Alkalinity
Compound can be selected from tetramethylammonium hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydride, hydrofining, sodium hydride
With at least one of lithium metal, sodium, potassium.Metallic element in alkali compounds can stay in the polyvinyl alcohol sulfonate
In, obtain polyvinyl alcohol sodium sulfonate, polyvinyl alcohol potassium sulfonate, polyvinyl alcohol Sulfonic Lithium or polyvinyl alcohol sulfanilic acid.
The second object of the present invention provides a kind of synthetic method of polyvinyl alcohol sulfonate of the invention, this method comprises:
In the presence of solvent and activator, sultones shown in polyvinyl alcohol and formula (2) is subjected to etherification reaction,
Wherein, the positive integer that x is 1~3, A1~A4It is each independently hydrogen, C1~C6Alkyl or C1~C6Alkenyl.
According to the present invention, the sultones of selection can promote to improve the property for the hydrophilic layer that polyvinyl alcohol is used as galley
Can, the printing performance of the hydrophilic version further obtained, such as hydrophily, water resistance, resistance to print property are improved, satisfaction obtains formula (1) institute
The polyvinyl alcohol sulfonate for the chemical structure shown.Under preferable case, the sultones is selected from 1,3-propane sultone, 1-
Methyl-1,3-N-morpholinopropanesulfonic acid lactone, 1,1- dimethyl -1,3- propane sultone, 1- ethyl -1,3- propane sultone, 1,2- diformazan
Base -1,3- propane sultone, 1,3- dimethyl -1,3- propane sultone, 1- acrylic -1,3- propane sultone, 1- methyl -2-
Ethyl -1,3- propane sultone, 1- methyl-1,4- butyl sultone, 1- methyl-1,4- butyl sultone, 1- acrylic -1,4-
At least one of penta sultones of butyl sultone and 1,5-.
According to the present invention, the polyvinyl alcohol can provide the basis material of the hydrophilic layer as galley, can have
The structural unit as shown in formula (3)The selection of the polyvinyl alcohol meets to obtain formula
(1) the polyvinyl alcohol sulfonate of chemical structure shown in.Under preferable case, the degree of polymerization of the polyvinyl alcohol is 400~
5000.It can be with the numerical value of m+n in chemical structure shown in corresponding (1).Preferred degree of polymerization is 1500~3000, more preferably
1700~2600.The alcoholysis degree of the polyvinyl alcohol can be 99% simultaneously.The polyvinyl alcohol can be known substance, can be with
The PVA1799 (degree of polymerization 1700, alcoholysis degree 99%) of commercially available Shanghai Petrochemial Co Ltd, China Petrochemical Corp, Ningxia
(degree of polymerization is by PVA1799, PVA1899 (degree of polymerization 1800, alcoholysis degree 99%) of the earth Chemical Co., Ltd., PVA2099
2000, alcoholysis degree 99%), PVA2499 (degree of polymerization 2400, alcoholysis degree 99%), PVA2699 (degree of polymerization 2600, alcohol
Xie Du is 99%) to obtain.
According to the present invention, the solvent can be used for the etherification reaction process, so as to reactant polyvinyl alcohol and sulfonic acid
Lactone preferably carries out etherification reaction.Under preferable case, the solvent can be the water or organic solvent of dissolvable polyvinyl alcohol.
It is preferred that the organic solvent is selected from dimethylformamide, r- butyrolactone, N-Methyl pyrrolidone, N- ethyl pyrrolidone, tetrahydro
At least one of furans, ethyl alcohol and dioxane.
According to the present invention, the activator can be used to implement the etherification reaction.Under preferable case, the activation
Agent is alkali compounds；It is preferred that the activator is selected from tetramethylammonium hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, hydrogen
Change at least one of lithium, hydrofining, sodium hydride and lithium metal, sodium, potassium.
According to the present invention, the available polyvinyl alcohol sulfonate above-mentioned of the condition of the etherification reaction.Preferred formula (1) institute
The polyvinyl alcohol sulfonate shown.Under preferable case, the weight ratio of the polyvinyl alcohol and the sultones is (0.1~4): 1,
Preferably (0.1~1): 1.The inventory of the polyvinyl alcohol and the sultones, the polyvinyl alcohol sulphur that can satisfy
Hydrochlorate has the n, m in structure shown in corresponding (1).
In the case of, according to the invention it is preferred to, the molar ratio of the sultones and the activator is 1:(1~1.2).
In the case of, according to the invention it is preferred to, etherification reaction temperature is 40 DEG C~120 DEG C, preferably 60 DEG C~100 DEG C；Ether
The change reaction time is 1~10h, preferably 3~5h.
In the present invention, the polyvinyl alcohol and the sultones first can be dissolved in the solvent respectively, are configured to molten
It is contacted again after liquid and carries out the etherification reaction.
In the present invention, specifically, polyvinyl alcohol can be dissolved in the solvent, the activator is then added；Again
It is stirred at room temperature and the solution that the sultones is dissolved in the solvent is added dropwise；After being added dropwise, by the reaction solution of formation
1~2h of pre-reaction is first carried out at room temperature, is then warming up to 60 DEG C~80 DEG C 2~4h of progress etherification reaction again.What reaction obtained
Product obtains solid powder by spray drying.Obtained solid powder is subjected to examination of infrared spectrum, is determined as shown in formula (1)
Chemical structure polyvinyl alcohol sulfonate.In infrared spectrum spectrogram, wave number 3340cm-1Place is the absorption of polyvinyl alcohol hydroxyl
Peak, wave number 1120cm-1Place is the absorption peak of ehter bond, wave number 1240cm-1And 1090cm-1Place is the absorption peak of sulfonic acid group.
And specific structural parameters are determined further combined with feeding intake.
The third object of the present invention provides a kind of hydrophilic version of printing, comprising: substrate, and the parent being formed on the substrate
Water layer；Wherein, in the infrared absorption spectra of the hydrophilic layer, wave number 3340cm-1Place is the absorption peak of polyvinyl alcohol hydroxyl, wave
Number is 1120cm-1Place is the absorption peak of ehter bond, wave number 1240cm-1And 1090cm-1Place is the absorption peak of sulfonic acid group.
According to the present invention, there is the hydrophilic layer of the hydrophilic version of printing provided above-mentioned chemical structure can provide better printing
Performance.Under preferable case, the contact angle of the hydrophilic version is less than 10 °；The water resistance of the hydrophilic version is to impregnate 3h not in water
It falls off, the press resistance rate of the hydrophilic version is not less than 5000 parts.Wherein, the contact angle for measuring the hydrophilic layer can illustrate the parent
The hydrophily of water layer, the numerical value of contact angle is smaller to illustrate that hydrophily is better.The water resistance of the hydrophilic version is related to press resistance rate, resistance to
The press resistance rate of the aqueous stronger explanation hydrophilic version is higher.
Preferably, the hydrophilic layer with a thickness of 0.5~10 μm.
In the case of, according to the invention it is preferred to, the hydrophilic layer by by polyvinyl alcohol sulfonate of the invention in the base
It is coated to obtain on plate.The polyvinyl alcohol sulfonate synthetic method that the polyvinyl alcohol sulfonate can provide through the invention
It obtains.
According to the present invention, a kind of preferred embodiment, the process of the coating include: that the polyvinyl alcohol sulfonate is molten
Water-soluble coating fluid is obtained in water；The coating fluid is coated on the surface of the substrate, then at 100 DEG C~200 DEG C
Then 1~10min of lower baking obtains the hydrophilic layer through cooling.
Preferably, in the water soluble paint, the content of the polyvinyl alcohol sulfonate is 5~30 weight %.
Preferably, the mode of the coating is extruding, spraying or roller coating.
In the case of, according to the invention it is preferred to, the water soluble paint also contains curing agent.
Preferably, in the water soluble paint, the content of the curing agent is 1~10 weight %.
Preferably, the curing agent is selected from isocyanates, aziridine or the compound containing multiple epoxy groups.Isocyanates
It can be closure isocyanates, can be obtained by Reagent Companies such as commercially available lark prestige, Chinese medicines group etc..It is described to contain multiple rings
The compound of oxygen groups can be in the structure of compound containing at least two epoxy groups, such as diepoxides, tricyclic
Oxygen compound etc..Specifically such as 3,4- expoxycyclohexyl formic acid -3 ', 4 '-expoxycyclohexyl methyl esters, three (glycidyl)
Chlorinated isocyanurates, glycidol ether, novolac epoxy resin etc., the compound containing multiple epoxy groups are known substance, can
With the acquisition such as Reagent Companies such as commercially available lark prestige, Chinese medicines group.
In the present invention, it is preferable that the substrate is selected from plastic base, aluminum substrate or aluminium alloy base plate；The substrate
With a thickness of 0.1mm~0.4mm.
In the present invention, it is preferable that the plastic base can be polypropylene foil base, PET sheet base or nylon base, can be with quotient
Purchase obtains.
In the present invention, it is preferable that the aluminium alloy can be the alloy of aluminium and magnesium, copper, carbon, iron, zinc or silicon etc., wherein aluminium
Content is not less than 90%, can be commercially available.
The fourth object of the present invention provides a kind of application of hydrophilic version of the invention in printing plate.
The fifth object of the present invention provides a kind of galley, comprising: hydrophilic version of the invention, and the parent in hydrophilic version
The graph text information layer formed on water layer.
The sixth object of the present invention provides a kind of ink jet printing version, comprising: hydrophilic version of the invention, and in hydrophilic version
Hydrophilic layer on the graph text information layer that is formed, wherein the graph text information layer on the hydrophilic layer by spraying ink and drying
Form at.
In ink jet printing version provided by the invention, forming ink used in the graph text information layer and can be this field makes
Ink-jetting forme-producing ink or ink, can be commercially available, such as the K series of Beijing Nano Think Technology Co., Ltd.
Plate-making ink.
In the present invention, the thickness of the graph text information layer can be 0.5 μm~10 μm.
In the present invention, the method and condition for spraying ink can be this field conventional technique, and details are not described herein.
The seventh object of the present invention provides a kind of photosensitive photosensitive printed board, comprising: hydrophilic version of the invention, and hydrophilic
The photosensitive photoresists on hydrophilic layer in version, the photosensitive photoresists form graph text information layer.
In the present invention, the graph text information layer can be formed by coating the photosensitive photoresists.
In the present invention, photosensitive photoresists described in a kind of embodiment contain the Photoactive compounds of 2~12 mass parts, and 0.1
The background dye of~0.5 mass parts, the solvent of the film-forming resin of 10~25 mass parts and 60~80 mass parts.
In the present invention, it is preferable that the Photoactive compounds are selected from 2- diazonium -1- naphthols -4- sulfonic acid chloride or 2- diazonium -1-
The product that naphthols -5- sulfonic acid chloride is reacted with hydroxy-containing compounds；The hydroxy-containing compounds are selected from alcohol, phenol or hydroxyl
Polymer, the polymer of the hydroxyl polymer-containing such as alcoholic hydroxy and/or phenolic hydroxy group.
In the present invention, it is preferable that the 2- diazonium -1- naphthols -4- sulfonic acid chloride or 2- diazonium -1- naphthols -5- sulfonic acid chloride with
The molar ratio of hydroxyl is 1:(1~20 in the hydroxy-containing compounds).
In the present invention, it is preferable that the background dye is selected from alkaline bright blue, crystal violet, Victoria pure blue, indigo, first
At least one of base purple, malachite green and solvent blue.
In the present invention, it is preferable that the film-forming resin be selected from polymer not soluble in water, be specifically as follows epoxy resin,
One or more of phenolic resin, polyvinyl acetal resin and polyurethane resin.The epoxy resin, gathers phenolic resin
Vinyl acetal resin and polyurethane resin are known substance, can be commercially available, such as the ring of Tao Shi DOW solid DER671
The limited public affairs of jade-like stone Ma chemical industry are liked in oxygen resin, Weihai Economic and Technological Development Zone Tiancheng Chemical Co., Ltd. BTB series phenolic resin, Xiamen
It is limited to take charge of Sekisui BL-1H, the polyvinyl acetal resin of the Sekisui S-LEC BL-1 trade mark or Guangzhou association space chemical industry
The polyurethane resin of company, the company PU408 trade mark.
In the present invention, it is preferable that the solvent be selected from for the only methyl ether of propylene glycol, glycol monoethyl ether, ethylene glycol monoethyl ether,
At least one in dihydroxypropane single-ether, methyl ethyl ketone, butyl acetate, dioxane, N-Methyl pyrrolidone, methanol and tetrahydrofuran
Kind.
In the present invention, the photosensitive photoresists are known substance, can the PS version of commercially available Taixing City Orient Industrial Company feel
Light liquid or CTcP photosensitive liquid.
In the present invention, the mode for coating the photosensitive photoresists can be extruding, spraying or roller coating.Implement the coating
Condition can be this field conventional technique, and details are not described herein.
The eighth object of the present invention provides a kind of thermosensitive printing plates, comprising: hydrophilic version of the invention, and in hydrophilic version
Hydrophilic layer on thermographic layer, the thermographic layer forms graph text information layer.
In the present invention, the graph text information layer can be formed by coating thermographic composition.
In the present invention, thermographic composition described in a kind of embodiment contains the photothermal conversion object of 0.1~2 mass parts,
The background dye of 0.1~0.5 mass parts, the solvent of the film-forming resin of 10~25 mass parts and 60~85 mass parts.
In the present invention, it is preferable that the photothermal conversion object is selected from benzindole system cyanine dyes, step cyanine dye and various
Maximum wavelength (λmax) be 780~840nm at least one of infrared absorbing dye.The photothermal conversion object is known substance,
Benzindole system cyanine dyes can commercially available Jingmen City Yukui Chemical Industry Co., Ltd. product, step cyanine dye can be with quotient
Purchase the product of Hubei Ju Sheng Science and Technology Ltd..Maximum wavelength (λmax) can be commercially available for the infrared absorbing dye of 780~840nm
Handan development zone is set up one's own business the IR dyes of Chemical Co., Ltd..
In the present invention, it is preferable that the background dye is selected from alkaline bright blue, crystal violet, Victoria pure blue, indigo, first
At least one of base purple, malachite green and solvent blue.
In the present invention, it is preferable that the film-forming resin can be selected from linear phenol-aldehyde resin, poly(4-hydroxystyrene) and its change
Property product, poly- o-hydroxystyrene and its modified product, phenol-formaldehyde resin, metacresol-formaldehyde resin, ortho-cresol-formaldehyde tree
Rouge, phenol-metacresol-formaldehyde resin, phenol-ortho-cresol-formaldehyde resin, phenol-paracresol-formaldehyde resin, phenol-tert-butyl
Resinox, phenol-metacresol-paracresol-formaldehyde resin, metacresol-paracresol-formaldehyde resin and metacresol-tert-butyl
One or more of resinox.
The solvent is selected from cyclohexanone, methyl ethyl ketone, glycol monoethyl ether, dihydroxypropane single-ether, gamma-butyrolacton, lactic acid second
One or more of ester, butyl acetate, dioxane, tetrahydrofuran, trichloro ethylene, chloroform, methylene chloride.
In the present invention, the mode for coating the thermographic composition can be extruding, spraying or roller coating.Implement the painting
The condition covered can be this field conventional technique, and details are not described herein.
In the present invention, the thermographic composition is known substance, can commercially available Taixing City Orient Industrial Company heat
Quick image forming composition.
The present invention will be described in detail by way of examples below.
In following embodiment, hydrophilic version hydrophily can (Ke Lvshi scientific instrument (Shanghai) be limited by contact angle instrument
Company, DSA100) measurement contact angle；
The measuring method of the water resistance of hydrophilic version can be with are as follows: sampling version is cut into 10cm × 10cm (being accurate to 1mm), uses balance
It weighs (being accurate to 0.1mg).It is then placed in the water that temperature is 25 ± 2 DEG C, impregnates 12h and take out, place into 100 DEG C of baking oven
Dry 15min, weighs after being cooled to room temperature.Hydrophilic layer is removed, then is rinsed well with clear water, it is dry in 100 DEG C of baking oven
15min is weighed after being cooled to room temperature.Water resistance is calculated as follows:
Water resistance %=[(m1-m2)/(m1-m3)] × 100%, wherein m1For the quality (g) before immersion, m2After impregnating
Quality (g), m3To remove the quality (g) after hydrophilic layer；
The resistance to print of hydrophilic version can be surveyed by press resistance rate simulator (Beijing Long Ruida Science and Technology Ltd. LR-1 model)
It is fixed, test method are as follows: the coating material made is fixed in press resistance rate simulator, phosphatase 11 5ml, isopropanol 75ml is added,
Water 225ml, quartz sand 75g, rubber stopper 15.Then dedicated aqueous solution (isopropanol 15%, phosphoric acid 3%), rubber stopper is added
The diamond dust (the 10% of dedicated aqueous solution) of (the 10% of dedicated aqueous solution), 100 mesh；It is rotated under 20 revs/min of speed resistance to
After print rate simulator 0.5h, 1h, 2h, 3h, the damaed cordition of hydrophilic layer is observed, it is desirable that hydrophilic layer is apparently unchanged.Rotation 0.5h,
The corresponding press resistance rate of 1h, 2h, 3h (part) is about 5000,10,000,30,000,50,000.
In following embodiment, according to the parameter for determining obtained product that feeds intake.
Embodiment 1
This example demonstrates that the preparation of polyvinyl alcohol sulfonate of the invention.
The polyvinyl alcohol (Ningxia the earth Chemical Co., Ltd. 1799) of 22g is dissolved in the dimethylformamide (DMF) of 200mL
In, it will be added after the chopping of 5.7g metallic sodium, mixed at room temperature 0.5h；
Then dimethyl formamide solution (third sulphur of 1,3- of 1,3- propane sultone (lark prestige Science and Technology Ltd.) is added dropwise
Acid lactone 30.5g, dimethylformamide 300mL), polyvinyl alcohol: the weight ratio of 1,3-propane sultone is 0.72:1, is about undergone
1h obtains reaction mixture；
By reaction mixture pre-reaction 1h at room temperature, then it is warming up to 70 DEG C of progress etherification reaction 3h；
The product obtained after the completion of etherification reaction is spray-dried, solid powder is obtained.
Solid powder is subjected to infrared spectrum analysis, wave number is 3340cm in spectrogram-1Place is the absorption of polyvinyl alcohol hydroxyl
Peak, wave number 1120cm-1Place is the absorption peak of ehter bond, wave number 1240cm-1And 1090cm-1Place is the absorption peak of sulfonic acid group.
The use of sodium is activator, obtains polyvinyl alcohol sodium sulfonate.
According to the ingredient proportion of polyvinyl alcohol and 1,3-propane sultone, shown in polyvinyl alcohol sodium sulfonate corresponding (1)
In structure, n=850, m=850, n/ (m+n)=0.5.It is denoted as PSL-1.
Embodiment 2
This example demonstrates that the preparation of polyvinyl alcohol sulfonate of the invention.
The polyvinyl alcohol (Ningxia the earth Chemical Co., Ltd. 1899) of 11g is dissolved in the dioxane of 100mL, in three batches
It is slowly added to total 6g sodium hydride (being scattered in mineral oil, wherein the concentration of sodium hydride is 60 weight %), mixed at room temperature 1h；
Then be added dropwise 1- methyl-1,3-N-morpholinopropanesulfonic acid lactone (Sigma-Aldrich) dioxane solution (1- methyl-1,
3-N-morpholinopropanesulfonic acid lactone 20.4g, dioxane 20mL), polyvinyl alcohol: the weight ratio of 1- methyl-1,3-N-morpholinopropanesulfonic acid lactone is 0.54:
1, about experience 1h, obtain reaction mixture；
By reaction mixture pre-reaction 1.2h at room temperature, then it is warming up to 75 DEG C of progress etherification reaction 2h；
The product obtained after the completion of etherification reaction is spray-dried, solid powder is obtained.
Solid powder is subjected to infrared spectrum analysis, wave number is 3340cm in spectrogram-1Place is the absorption of polyvinyl alcohol hydroxyl
Peak, wave number 1120cm-1Place is the absorption peak of ehter bond, wave number 1240cm-1And 1090cm-1Place is the absorption peak of sulfonic acid group；
The use of sodium hydride is activator, obtains polyvinyl alcohol sodium sulfonate.
According to polyvinyl alcohol and 1- methyl-1, the ingredient proportion of 3-N-morpholinopropanesulfonic acid lactone, polyvinyl alcohol sodium sulfonate corresponding (1)
Shown in structure, n=1080, m=720, n/ (m+n)=0.6.It is denoted as PSL-2.
Embodiment 3
This example demonstrates that the preparation of polyvinyl alcohol sulfonate of the invention.
The polyvinyl alcohol (Ningxia the earth Chemical Co., Ltd. 2099) of 22g is dissolved in the dimethylformamide (DMF) of 20mL
In, it will be added after the chopping of 7.8g metallic potassium, mixed at room temperature 0.5h；
Then dimethyl formamide solution (the 1,1- diformazan of 1,1- dimethyl -1,3- propane sultone (lark prestige) is added dropwise
Base -1,3-propane sultone 30g, dimethylformamide 40mL), polyvinyl alcohol: 1,1- methyl-1, the weight of 3-N-morpholinopropanesulfonic acid lactone
Than for 0.73:1, about experience 1h obtains reaction mixture；
By reaction mixture pre-reaction 0.8h at room temperature, then it is warming up to 65 DEG C of progress etherification reaction 3.5h；
The product obtained after the completion of etherification reaction is spray-dried, solid powder is obtained.
Solid powder is subjected to infrared spectrum analysis, wave number is 3340cm in spectrogram-1Place is the absorption of polyvinyl alcohol hydroxyl
Peak, wave number 1120cm-1Place is the absorption peak of ehter bond, wave number 1240cm-1And 1090cm-1Place is the absorption peak of sulfonic acid group；
The use of potassium is activator, obtains polyvinyl alcohol potassium sulfonate.
According to polyvinyl alcohol and 1,1- methyl-1, the ingredient proportion of 3-N-morpholinopropanesulfonic acid lactone, polyvinyl alcohol potassium sulfonate corresponding
(1) in structure shown in, n=800, m=1200, n/ (m+n)=0.4.It is denoted as PSL-3.
Embodiment 4
The polyvinyl alcohol (Ningxia the earth Chemical Co., Ltd. 2499) of 11g is dissolved in the tetrahydrofuran (THF) of 200mL,
1.6g lithium hydride is added, mixed at room temperature 0.5h；
Then tetrahydrofuran solution (the 1- second of 1- ethyl -1,3- propane sultone (lark prestige Science and Technology Ltd.) is added dropwise
Base -1,3-propane sultone 30g, tetrahydrofuran 200mL), polyvinyl alcohol: 1- ethyl -1,3-propane sultone weight ratio is
0.37:1, about experience 1h, obtain reaction mixture；
By reaction mixture pre-reaction 1h at room temperature, then it is warming up to 70 DEG C of progress etherification reaction 4h；
The product obtained after the completion of etherification reaction is spray-dried, solid powder is obtained.
Solid powder is subjected to infrared spectrum analysis, wave number is 3340cm in spectrogram-1Place is the absorption of polyvinyl alcohol hydroxyl
Peak, wave number 1120cm-1Place is the absorption peak of ehter bond, wave number 1240cm-1And 1090cm-1Place is the absorption peak of sulfonic acid group；
The use of lithium hydride is activator, obtains polyvinyl alcohol Sulfonic Lithium.
According to polyvinyl alcohol and 1- ethyl -1,3-propane sultone ingredient proportion, polyvinyl alcohol Sulfonic Lithium corresponding (1)
Shown in structure, n=1920, m=480, n/ (m+n)=0.8.It is denoted as PSL-4.
Embodiment 5
The polyvinyl alcohol (Ningxia the earth Chemical Co., Ltd. 1799) of 44g is dissolved in the tetrahydrofuran of 100mL, in three batches
It is slowly added to 8g sodium hydride (being scattered in mineral oil, wherein the concentration of sodium hydride is 60 weight %), mixed at room temperature 1h；
Then the tetrahydrofuran solution of 1,2- dimethyl -1,3- propane sultone (lark prestige Science and Technology Ltd.) is added dropwise
(1,2- dimethyl -1,3-propane sultone 30g, tetrahydrofuran 200mL), polyvinyl alcohol: 1,2- dimethyl -1, in 3-N-morpholinopropanesulfonic acid
The weight ratio of ester is 1.47:1, about experience 1h, obtains reaction mixture；
By reaction mixture pre-reaction 1h at room temperature, then it is warming up to 75 DEG C of progress etherification reaction 3h；
The product obtained after the completion of etherification reaction is spray-dried, solid powder is obtained.
Solid powder is subjected to infrared spectrum analysis, wave number is 3340cm in spectrogram-1Place is the absorption of polyvinyl alcohol hydroxyl
Peak, wave number 1120cm-1Place is the absorption peak of ehter bond, wave number 1240cm-1And 1090cm-1Place is the absorption peak of sulfonic acid group；
The use of sodium hydride is activator, obtains polyvinyl alcohol sodium sulfonate.
According to polyvinyl alcohol and 1,2- dimethyl -1,3-propane sultone ingredient proportion, polyvinyl alcohol sodium sulfonate is corresponding
In structure shown in formula (1), n=340, m=1360, n/ (m+n)=0.2.It is denoted as PSL-5.
Embodiment 6
The polyvinyl alcohol (Ningxia the earth Chemical Co., Ltd. 1799) of 11g is dissolved in the dioxane of 100mL, is slowly added
Enter 1.9g lithium hydride, mixed at room temperature 1h；
Then the dioxane solution of 1,3- propane sultone (lark prestige Science and Technology Ltd.) is added dropwise (in 1,3- propane sulfonic acid
Ester 29g, dioxane 200mL), polyvinyl alcohol: the weight ratio of 1,3-propane sultone is 0.38:1, about experience 1h, is obtained anti-
Answer mixed liquor；
By reaction mixture pre-reaction 1h at room temperature, then it is warming up to 75 DEG C of progress etherification reaction 2h；
The product obtained after the completion of etherification reaction is spray-dried, solid powder is obtained.
Solid powder is subjected to infrared spectrum analysis, wave number is 3340cm in spectrogram-1Place is the absorption of polyvinyl alcohol hydroxyl
Peak, wave number 1120cm-1Place is the absorption peak of ehter bond, wave number 1240cm-1And 1090cm-1Place is the absorption peak of sulfonic acid group；
The use of lithium hydride is activator, obtains polyvinyl alcohol Sulfonic Lithium.
According to the ingredient proportion of polyvinyl alcohol and 1,3-propane sultone, shown in polyvinyl alcohol Sulfonic Lithium corresponding (1)
In structure, n=1615, m=85, n/ (m+n)=0.95.It is denoted as PSL-6.
Embodiment 7
The polyvinyl alcohol (Shanghai Petrochemial Co Ltd, China Petrochemical Corp 1799) of 44g is dissolved in the diformazan of 300mL
In base sulfoxide, 3.9g metallic potassium is cut into fragment and is slowly added to, mixed at room temperature 0.5h；
Then dimethyl sulphoxide solution (the 1,4- propane sultone of 1,3- propane sultone (Sigma-Aldrich) is added dropwise
13.6g, dimethyl sulfoxide 40mL), polyvinyl alcohol: the weight ratio of 1,3-propane sultone is 3.25:1, about experience 1h, is obtained anti-
Answer mixed liquor；
By reaction mixture pre-reaction 0.5h at room temperature, then it is warming up to 80 DEG C of progress etherification reaction 2h；
The product obtained after the completion of etherification reaction is spray-dried, solid powder is obtained.
Solid powder is subjected to infrared spectrum analysis, wave number is 3340cm in spectrogram-1Place is the absorption of polyvinyl alcohol hydroxyl
Peak, wave number 1120cm-1Place is the absorption peak of ehter bond, wave number 1240cm-1And 1090cm-1Place is the absorption peak of sulfonic acid group；
The use of potassium is activator, obtains polyvinyl alcohol potassium sulfonate.
According to the ingredient proportion of polyvinyl alcohol and 1,3-propane sultone, shown in polyvinyl alcohol potassium sulfonate corresponding (1)
In structure, n=85, m=1615, n/ (m+n)=0.05.It is denoted as PSL-7.
Embodiment 8
The polyvinyl alcohol (Ningxia the earth Chemical Co., Ltd. 1899) of 11g is dissolved in the N-Methyl pyrrolidone of 200mL,
1.75g lithium metal is cut into fragment to be slowly added to, mixed at room temperature 0.5h；
Then the N-Methyl pyrrolidone solution of 1,3-propane sultone, (1,3-propane sultone 30g, N- methyl is added dropwise
Pyrrolidones 100mL), polyvinyl alcohol: the weight ratio of 1,3-propane sultone is 0.37:1, about experience 1h, obtains reaction mixing
Liquid；
By reaction mixture pre-reaction 1h at room temperature, then it is warming up to 120 DEG C of progress etherification reaction 3h；
The product obtained after the completion of etherification reaction is spray-dried, solid powder is obtained.
Solid powder is subjected to infrared spectrum analysis, wave number is 3340cm in spectrogram-1Place is the absorption of polyvinyl alcohol hydroxyl
Peak, wave number 1120cm-1Place is the absorption peak of ehter bond, wave number 1240cm-1And 1090cm-1Place is the absorption peak of sulfonic acid group；
The use of lithium is activator, obtains polyvinyl alcohol Sulfonic Lithium.
According to the ingredient proportion of polyvinyl alcohol and 1,3-propane sultone, shown in polyvinyl alcohol Sulfonic Lithium corresponding (1)
In structure, n=1800, m=0, n/ (m+n)=1.It is denoted as PSL-8.
Embodiment 9
This example demonstrates that preparing ink jet printing version of the invention.
PSL-1 and aziridine (XAMA-7 of Bayer Bitterfeld GmbH) prepared by embodiment 1 are dissolved in water, are configured to PSL-1 concentration
For 11 weight %, aziridine concentration is the aqueous solution of 2 weight %；
The aqueous solution is coated on to the table of aluminium base (thickness 0.27mm, Chengde day is at printing Science and Technology Co., Ltd.)
Then face toasts 5min at 160 DEG C, obtains the hydrophilic version for being formed with hydrophilic layer after cooling；Hydrophilic layer is with a thickness of 2 μm；
Graph text information as needed, with ink-jetting forme-producing machine ink-jetting forme-producing (Beijing Nano Think Technology Co., Ltd.,
Ink-jetting forme-producing machine 116C, K series ink-jetting forme-producing ink) and 3min formation is toasted at 180 DEG C with a thickness of 3 μm of graph text information
Layer, obtains ink jet printing version.
Ink jet printing version is subjected to contact angle, water resistance, the test of resistance to print property, the results are shown in Table 1.
Embodiment 10
This example demonstrates that preparing photosensitive photosensitive printed board of the invention.
The aqueous nonionic blocked crosslinkers of PSL-2 and KL-1202 prepared by embodiment 2 (Jiangsu health and happiness new material section
Skill Co., Ltd, closure isocyanates) it is dissolved in water, being configured to PSL-2 concentration is 10 weight %, and isocyanate concentration is 3 weights
Measure the aqueous solution of %；
The aqueous solution is coated on to the table of aluminium base (thickness 0.15mm, Chengde day is at printing Science and Technology Co., Ltd.)
Then face toasts 3min at 100 DEG C, obtains the hydrophilic version for being formed with hydrophilic layer after cooling；3 μm of hydrophilic layer thickness；
PS editions photosensitive photoresists (Taixing City Orient Industrial Company) are sprayed to hydrophilic version and the baking of 5min is carried out at 130 DEG C
It is dry, the photosensitive photosensitive layer with a thickness of 2 μm is formed, photosensitive photosensitive printed board is obtained after plate-making；
Photosensitive photosensitive printed board is subjected to contact angle, water resistance, the test of resistance to print property, the results are shown in Table 1.
Embodiment 11
This example demonstrates that preparing thermosensitive printing plates of the invention.
PSL-3 and epoxy resin GE-95 (Shanghai Run Tan new material Science and Technology Ltd.) prepared by embodiment 3 are dissolved in
Water, being configured to PSL-3 concentration is 12 weight %, and epoxy resin GE-95 concentration is the aqueous solution of 1 weight %；
The aqueous solution is coated on to the surface of 0.25mm aluminium base, 4min is then toasted at 180 DEG C, obtains shape after cooling
At the hydrophilic version for having hydrophilic layer；Hydrophilic layer is with a thickness of 2 μm；
Carry out 10min's to hydrophilic version spraying thermographic composition (Taixing City Orient Industrial Company) and at 130 DEG C
Drying forms the thermographic layer with a thickness of 1.8 μm, obtains thermosensitive printing plates after plate-making；
Thermosensitive printing plates are subjected to contact angle, water resistance, the test of resistance to print property, the results are shown in Table 1.
Embodiment 12
PSL-4 and epoxy resin GE-51 (Shanghai Run Tan new material Science and Technology Ltd.) prepared by embodiment 4 are dissolved in
Water, being configured to PSL-4 concentration is 9 weight %, and aziridine concentration is the aqueous solution of 4 weight %；
The aqueous solution is coated on to the surface of PET film (thickness 0.25mm, Hai'an Jin Tong gluing Science and Technology Ltd.), then
10min is toasted at 130 DEG C, obtains the hydrophilic version for being formed with hydrophilic layer after cooling；Hydrophilic layer is with a thickness of 2 μm；
Graph text information as needed, with ink-jetting forme-producing machine ink-jetting forme-producing, (BeiJing ZhongKe takes in the fresh the limited public affairs of printing technology
Department, ink-jetting forme-producing machine 116C, K series ink-jetting forme-producing ink) and 10min formation is toasted at 140 DEG C with a thickness of 3 μm of picture and text letter
Layer is ceased, ink jet printing version is obtained.
Ink jet printing version is subjected to contact angle, water resistance, the test of resistance to print property, the results are shown in Table 1.
Embodiment 13
By PSL-5 and HD-115 trifunctional aziridine crosslinker prepared by embodiment 5, (Jiangsu health and happiness new material science and technology has
Limit company) it is dissolved in water, being configured to PSL-5 concentration is 12 weight %, and aziridine concentration is the aqueous solution of 1 weight %；
The aqueous solution is coated on to the surface of PET film (thickness 0.25mm, Hai'an Jin Tong gluing Science and Technology Ltd.), then
10min is toasted at 140 DEG C, obtains the hydrophilic version for being formed with hydrophilic layer after cooling；Hydrophilic layer is with a thickness of 2 μm；
Graph text information as needed, with ink-jetting forme-producing machine ink-jetting forme-producing (Beijing Nano Think Technology Co., Ltd.,
Ink-jetting forme-producing machine 116C, K series ink-jetting forme-producing ink) and 10min formation is toasted at 140 DEG C with a thickness of 3 μm of graph text information
Layer, obtains ink jet printing version.
Ink jet printing version is subjected to contact angle, water resistance, the test of resistance to print property, the results are shown in Table 1.
Embodiment 14
By PSL-6 and HD-110 trifunctional aziridine crosslinker prepared by embodiment 6, (Jiangsu health and happiness new material science and technology has
Limit company) it is dissolved in water, being configured to PSL-6 concentration is 8 weight %, and aziridine concentration is the aqueous solution of 5 weight %；
The aqueous solution is coated on to the surface of PET film (thickness 0.25mm, Hai'an Jin Tong gluing Science and Technology Ltd.), then
10min is toasted at 140 DEG C, obtains the hydrophilic version for being formed with hydrophilic layer after cooling；Hydrophilic layer is with a thickness of 3 μm；
Carry out 10min's by the hydrophilic version spraying photosensitive photoresists of CTcP (Taixing City Orient Industrial Company) and at 130 DEG C
Drying forms the photosensitive photosensitive layer with a thickness of 1.8 μm, photosensitive photosensitive printed board is obtained after plate-making；
Photosensitive photosensitive printed board is subjected to contact angle, water resistance, the test of resistance to print property, the results are shown in Table 1.
Embodiment 15
By PSL-7 and HD-110 trifunctional aziridine crosslinker prepared by embodiment 7, (Jiangsu health and happiness new material science and technology has
Limit company) it is dissolved in water, being configured to PSL-7 concentration is 13 weight %, and aziridine concentration is the aqueous solution of 0.5 weight %；
The aqueous solution is coated on to the surface of PET film (thickness 0.15mm, Hai'an Jin Tong gluing Science and Technology Ltd.), then
10min is toasted at 140 DEG C, obtains the hydrophilic version for being formed with hydrophilic layer after cooling, hydrophilic layer is with a thickness of 2 μm；
Graph text information as needed, with ink-jetting forme-producing machine ink-jetting forme-producing, (BeiJing ZhongKe takes in the fresh the limited public affairs of printing technology
Department, ink-jetting forme-producing machine 116C, K series ink-jetting forme-producing ink) and 10min formation is toasted at 140 DEG C with a thickness of 3 μm of picture and text letter
Layer is ceased, ink jet printing version is obtained.
Ink jet printing version is subjected to contact angle, water resistance, the test of resistance to print property, the results are shown in Table 1.
Embodiment 16
PSL-8 prepared by embodiment 8 is configured to the aqueous solution that PSL-8 concentration is 13 weight % and is coated on PET film (thickness
0.25mm, hongda technological applications Materials Co., Ltd, Shenzhen) surface, then toast 10min at 140 DEG C, it is cooling after
To the hydrophilic version for being formed with hydrophilic layer, 3 μm of hydrophilic layer thickness；
Graph text information as needed, with ink-jetting forme-producing machine ink-jetting forme-producing (Beijing Nano Think Technology Co., Ltd.,
Ink-jetting forme-producing machine 116C, K series ink-jetting forme-producing ink) and 10min formation is toasted at 140 DEG C with a thickness of 3 μm of graph text information
Layer, obtains ink jet printing version.
Ink jet printing version is subjected to contact angle, water resistance, the test of resistance to print property, the results are shown in Table 1.
Comparative example 1
Polyvinyl alcohol (Ningxia the earth Chemical Co., Ltd. 1799) and HD-110 trifunctional aziridine crosslinker (Jiang Sukang
Happy new material Science and Technology Ltd.) it is dissolved in water, being configured to 1799 concentration of polyvinyl alcohol is 8 weight %, and aziridine concentration is 3 weights
Measure the aqueous solution of %；
By above-mentioned solution coating on the surface of PET (thickness 0.25mm, Hai'an Jin Tong gluing Science and Technology Ltd.), then exist
10min is toasted at 140 DEG C, obtains the hydrophilic version for being formed with hydrophilic layer after cooling；Hydrophilic layer is with a thickness of 3 μm；
Graph text information as needed, with ink-jetting forme-producing machine ink-jetting forme-producing (Beijing Nano Think Technology Co., Ltd.,
Ink-jetting forme-producing machine 116C, K series ink-jetting forme-producing ink) and 10min formation is toasted at 140 DEG C with a thickness of 3 μm of graph text information
Layer, obtains ink jet printing version.
Ink jet printing version is subjected to contact angle, water resistance, the test of resistance to print property, the results are shown in Table 1.
Comparative example 2
Polyvinyl alcohol (Ningxia the earth Chemical Co., Ltd. 1799) and HD-110 trifunctional aziridine crosslinker (Jiang Sukang
Happy new material Science and Technology Ltd.) it is dissolved in water, and the titanium dioxide of partial size 30nm is added, being configured to 1799 concentration of polyvinyl alcohol is
6 weight %, aziridine concentration are 1 weight %, and titanium dioxide concentration is the solution of 8 weight %；
By above-mentioned solution coating on the surface of PET (thickness 0.25mm, Hai'an Jin Tong gluing Science and Technology Ltd.), then exist
10min is toasted at 140 DEG C, obtains the hydrophilic version for being formed with hydrophilic layer after cooling；Hydrophilic layer is with a thickness of 3 μm；
Graph text information as needed, with ink-jetting forme-producing machine ink-jetting forme-producing (Beijing Nano Think Technology Co., Ltd.,
Ink-jetting forme-producing machine 116C, K series ink-jetting forme-producing ink) and 10min formation is toasted at 140 DEG C with a thickness of 3 μm of graph text information
Layer, obtains ink jet printing version.
Ink jet printing version is subjected to contact angle, water resistance, the test of resistance to print property, the results are shown in Table 1.
Comparative example 3
Galley is prepared according to the method for CN102407653A disclosed embodiment 1.
Selecting the metal aluminum sheet with a thickness of 0.05-0.5mm is version base, first carries out cleaning and removes foul and greasy dirt.In aluminium sheet
Upper coating adhesive layer, the formula of adhesive layer coating are (50%) 35 part of epoxy resin aqueous solution, phenolic resin aqueous solution (30%)
15 parts, 50 parts of water, the above component is dispersed with stirring, uniform coating fluid is made into, is coated on aluminium sheet with the mode of dip-coating, then
200 DEG C of baking 5min in an oven, make coating fluid be solidified into adhesive layer, with a thickness of 2-15 μm, are then coated with hydrophilic layer.Hydrophilic layer
Coating fluid formula be polyvinyl alcohol (10% aqueous solution) 100 part, nanometers or 40 parts of micron order zinc oxide, hexamethylol melamine
5 parts of polyimide resin (50% aqueous solution), 5 parts, 50 parts of water of anhydrous sorbitol ester APEO (4% aqueous solution).
Hydrophilic layer coating fluid is dispersed with stirring, uniform coating fluid is made into, is then coated on adhesive layer with the mode of dip-coating,
100 DEG C of heating 5-10min in an oven again, make coating fluid dry solidification at hydrophilic layer, and hydrophilic layer is formed flat with a thickness of 5-20 μm
Plate is printing plate-based.
Graph text information as needed, with ink-jetting forme-producing machine ink-jetting forme-producing (Beijing Nano Think Technology Co., Ltd.,
Ink-jetting forme-producing machine 116C, K series ink-jetting forme-producing ink) and 10min formation is toasted at 140 DEG C with a thickness of 3 μm of graph text information
Layer, obtains ink jet printing version.
Ink jet printing version is subjected to contact angle, water resistance, the test of resistance to print property, the results are shown in Table 1.
Table 1
The polyvinyl alcohol sulfonic acid provided by the present invention it can be seen from the result data of above embodiments, comparative example and table 1
The hydrophilic layer printed in hydrophilic version can be made in salt, provide hydrophilic version with better hydrophily, while having water resistance and satisfaction
Enough press resistance rates.The hydrophilic version, which can further apply, prepares various galleys, such as ink jet printing version, photosensitive photosensitive printing
Version and thermosensitive printing plates, and provide galley better printing performance, obtain clear and clean printed matter.
Comparative example 1-3 is difficult to obtain clear and clean printed matter using the prior art.Wherein, comparative example 3 obtains
Ink jet printing version cannot obtain clean printed matter, be unable to complete qualified printing.Only part is dirty for comparative example 1 and 2, but complete
It is low at the press resistance rate of printed matter, not as good as provided by the present application using polyvinyl alcohol sulfonate as hydrophilic version obtained by hydrophilic layer, into
The printing performance of galley made from one step.
Claims (30)
1. a kind of synthetic method of polyvinyl alcohol sulfonate, this method comprises: in the presence of solvent and activator, by polyvinyl alcohol
Etherification reaction is carried out with sultones shown in formula (2),
Wherein, the positive integer that x is 1~3；A1~A4Each independently
For hydrogen, C1~C6Alkyl or C1~C6Alkenyl；
The polyvinyl alcohol sulfonate contains chemical structure shown in formula (1),
Wherein, the positive integer of m+n=400~5000, the positive integer that n/ (m+n)=0.05~1, x is 1~3；A1~A4Respectively solely
It is on the spot hydrogen, C1~C6Alkyl or C1~C6Alkenyl；M is Li, Na, K or NH4。
2. according to the method described in claim 1, wherein, n/ (m+n) is 0.2~0.95.
3. according to the method described in claim 2, wherein, n/ (m+n) is 0.2~0.8.
4. according to the method described in claim 3, wherein, n/ (m+n) is 0.4~0.6.
5. method described in any one of -4 according to claim 1, wherein the infrared spectroscopy of the polyvinyl alcohol sulfonate is composed
In figure, wave number 3340cm-1Place is the absorption peak of polyvinyl alcohol hydroxyl, wave number 1120cm-1Place is the absorption peak of ehter bond, wave
Number is 1240cm-1And 1090cm-1Place is the absorption peak of sulfonic acid group.
6. according to the method described in claim 1, wherein, the sultones is selected from 1,3-propane sultone, 1- methyl-1,3-
Propane sultone, 1,1- dimethyl -1,3- propane sultone, 1- ethyl -1,3- propane sultone, 1,2- dimethyl -1,3- third
Sultones, 1,3- dimethyl -1,3- propane sultone, 1- acrylic -1,3- propane sultone, 1- methyl -2- ethyl -1,3-
Propane sultone, 1- methyl-1, in penta sultones of 4- butyl sultone, 1- acrylic -1,4- butyl sultone and 1,5-
It is at least one.
7. according to the method described in claim 6, wherein, the degree of polymerization of the polyvinyl alcohol is 400~5000.
8. according to the method described in claim 6, wherein, the solvent is the water or organic solvent of solvable Polyvinyl alcohol；Institute
It states organic solvent and is selected from dimethylformamide, r- butyrolactone, N-Methyl pyrrolidone, N- ethyl pyrrolidone, tetrahydrofuran, second
At least one of pure and mild dioxane.
9. according to the method described in claim 6, wherein, the activator is alkali compounds.
10. according to the method described in claim 9, wherein, the activator is selected from tetramethylammonium hydroxide, lithium hydroxide, hydrogen
At least one of sodium oxide molybdena, potassium hydroxide, lithium hydride, hydrofining, sodium hydride and lithium metal, sodium, potassium.
11. method described in any one of -4 according to claim 1, wherein the polyvinyl alcohol and the sultones
Weight ratio is (0.1~4): 1；The molar ratio of the sultones and the activator is 1:(1~1.2).
12. according to the method for claim 11, wherein the weight ratio of the polyvinyl alcohol and the sultones is (0.1
~1): 1.
13. according to the method for claim 11, wherein etherification reaction temperature is 40 DEG C~120 DEG C；The etherification reaction time is
1~10h.
14. according to the method for claim 13, wherein etherification reaction temperature is 60 DEG C~100 DEG C；The etherification reaction time is
3~5h.
15. a kind of hydrophilic version of printing, comprising: substrate, and the hydrophilic layer being formed on the substrate；Wherein, the hydrophilic layer
Infrared absorption spectra in, wave number 3340cm-1Place is the absorption peak of polyvinyl alcohol hydroxyl, wave number 1120cm-1Place is ehter bond
Absorption peak, wave number 1240cm-1And 1090cm-1Place is the absorption peak of sulfonic acid group；
The hydrophilic layer is by being coated to obtain on the substrate polyvinyl alcohol sulfonate；The polyvinyl alcohol sulfonate
Containing chemical structure shown in formula (1),
Wherein, the positive integer of m+n=400~5000, the positive integer that n/ (m+n)=0.05~1, x is 1~3；A1~A4Respectively solely
It is on the spot hydrogen, C1~C6Alkyl or C1~C6Alkenyl；M is Li, Na, K or NH4。
16. hydrophilic version according to claim 15, wherein n/ (m+n) is 0.2~0.95.
17. hydrophilic version according to claim 15, wherein n/ (m+n) is 0.2~0.8.
18. hydrophilic version according to claim 15, wherein n/ (m+n) is 0.4~0.6.
19. hydrophilic version according to claim 15, wherein the polyvinyl alcohol sulfonate is polyvinyl alcohol and sultones
Etherification product.
20. hydrophilic version according to claim 19, wherein the sultones is selected from 1,3-propane sultone, 1- methyl-
1,3- propane sultone, 1,1- dimethyl -1,3- propane sultone, 1- ethyl -1,3- propane sultone, dimethyl -1 1,2-,
3-N-morpholinopropanesulfonic acid lactone, 1,3- dimethyl -1,3- propane sultone, 1- acrylic -1,3- propane sultone, 1- methyl -2- ethyl -
1,3- propane sultone, 1- methyl-1, penta sultones of 4- butyl sultone, 1- acrylic -1,4- butyl sultone and 1,5-
At least one of.
21. hydrophilic version according to claim 15, wherein the contact angle of the hydrophilic layer is less than 10 °；The hydrophilic version
Water resistance is to impregnate 3h in water not falling off, and the press resistance rate of the hydrophilic version is not less than 5000 parts.
22. hydrophilic version according to claim 15, wherein the process of the coating includes: by the polyvinyl alcohol sulfonic acid
Salt is dissolved in water and obtains water-soluble coating fluid；The water-soluble coating fluid is coated on the surface of the substrate, then 100
DEG C~200 DEG C at toast 1~10min, then through cooling obtain the hydrophilic layer.
23. hydrophilic version according to claim 22, wherein in the water solubility coating fluid, the polyvinyl alcohol sulfonate
Content be 5~30 weight %.
24. the hydrophilic version according to claim 22 or 23, wherein the water solubility coating fluid also contains curing agent, described
The content of curing agent is 1~10 weight %.
25. hydrophilic version according to claim 24, wherein the curing agent is selected from isocyanates, aziridine or containing multiple
The compound of epoxy group.
26. application of the hydrophilic version in printing plate described in a kind of any one of claim 15-25.
27. a kind of galley, comprising: hydrophilic version described in any one of claim 15-25, and it is hydrophilic in hydrophilic version
The graph text information layer formed on layer.
28. a kind of ink jet printing version, comprising: hydrophilic version described in any one of claim 15-25, and in hydrophilic version
The graph text information layer formed on hydrophilic layer, wherein the graph text information layer on the hydrophilic layer by spraying ink and drying
It is formed.
29. a kind of photosensitive photosensitive printed board, comprising: hydrophilic version described in any one of claim 15-25, and in hydrophilic version
In hydrophilic layer on photosensitive photoresists, the photosensitive photoresists form graph text information layer.
30. a kind of thermosensitive printing plates, comprising: hydrophilic version described in any one of claim 15-25, and in hydrophilic version
Thermographic layer on hydrophilic layer, the thermographic layer form graph text information layer.
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| CN201710045750.4A CN108329413B (en) | 2017-01-20 | 2017-01-20 | A kind of polyvinyl alcohol sulfonate and its synthetic method, printing hydrophilic version and application and galley |
| PCT/CN2017/079564 WO2018133213A1 (en) | 2017-01-20 | 2017-04-06 | Modified polyvinyl alcohol and synthesis method therefor, hydrophilic plate for printing and application thereof, and printing plate |
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| CN114561137B (en) * | 2020-11-27 | 2022-09-02 | 中国科学院化学研究所 | Antifogging agent, preparation method and application thereof, and antifogging product |
| CN114561128B (en) * | 2020-11-27 | 2022-09-02 | 中国科学院化学研究所 | Antifogging agent, preparation method and application thereof, and antifogging product |
| CN114680106B (en) * | 2020-12-29 | 2022-09-20 | 中国科学院化学研究所 | Antibacterial liquid, preparation method and application thereof, and antibacterial product |
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