CN108329446B - Phenolic resin is esterified sulfonate and its synthetic method, printing hydrophilic version and application and galley - Google Patents
Phenolic resin is esterified sulfonate and its synthetic method, printing hydrophilic version and application and galley Download PDFInfo
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- CN108329446B CN108329446B CN201710044848.8A CN201710044848A CN108329446B CN 108329446 B CN108329446 B CN 108329446B CN 201710044848 A CN201710044848 A CN 201710044848A CN 108329446 B CN108329446 B CN 108329446B
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- phenolic resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
- C08G8/32—Chemically modified polycondensates by organic acids or derivatives thereof, e.g. fatty oils
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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
- B41N1/14—Lithographic printing foils
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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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Abstract
The present invention relates to ink-jet printing field, a kind of phenolic resin esterification sulfonate and its synthetic method, printing hydrophilic version and application and galley are disclosed.The phenolic resin, which is esterified sulfonate, has chemical structure shown in formula (1),Wherein, the positive integer of m+n=4~50, the positive integer that n/ (m+n)=0.05~1, x is 1~3；A1~A4It is each independently hydrogen or C1~C6Alkyl；M is Li, Na, K or NH4；B existence or non-existence is selected from C in the presence of B1~C12Alkyl.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 ink-jet printing fields, and in particular, to a kind of phenolic resin esterification sulfonate and synthetic method contain
The hydrophilic version of printing for the hydrophilic layer for having phenolic resin esterification sulfonate to be formed, the hydrophilic version are applied in galley, and
Ink jet printing version, photosensitive photosensitive printed board and the thermosensitive printing plates formed by the hydrophilic version.
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 hydrophily and water-retaining property after electrolytic graining and anodized, can replace through electrolytic graining and
Version base after 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 performance issue for printing hydrophilic version, a kind of phenolic aldehyde tree is provided
Rouge is esterified 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 phenolic resin esterification sulfonate, which is esterified sulfonic acid
Salt has chemical structure shown in formula (1),
Wherein, the positive integer of m+n=4~50, the positive integer that n/ (m+n)=0.05~1, x is 1~3；A1~A4Respectively solely
It is on the spot hydrogen or C1~C6Alkyl；M is Li, Na, K or NH4；B existence or non-existence is selected from C in the presence of B1~C12Alkane
Base.
The present invention also provides a kind of synthetic method of phenolic resin esterification sulfonate of the present invention, this method packets
It includes:
In the presence of solvent and activator, Sulfo propionic acid acid anhydride shown in phenolic resin and formula (2) is subjected to esterification,
Wherein, the positive integer that x is 1~3, A1~A4It is each independently hydrogen or C1~C6Alkyl.
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 3400cm-1Place is the absorption peak of phenolic resin hydroxyl, and wave number is
1750cm-1Place is the absorption peak of ester carbonyl group, 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 phenolic resin esterification sulfonate, sulfonate is esterified using the phenolic resin
The hydrophilic version of printing obtained, can obtain extraordinary hydrophilic effect, water resistance and printability resistance, and nanometer is added without additional
Grade or micron order hydrocolloid particle.Qualified printed matter can be obtained, surface cleaning is indefectible, and galley press resistance rate is high.
Other features and advantages of the present invention will 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 phenolic resin esterification sulfonate, and phenolic resin esterification sulfonate has
Chemical structure shown in formula (1),
Wherein, the positive integer of m+n=4~50, the positive integer that n/ (m+n)=0.05~1, x is 1~3；A1~A4Respectively solely
It is on the spot hydrogen or C1~C6Alkyl；M is Li, Na, K or NH4；B existence or non-existence is selected from C in the presence of B1~C12Alkane
Base.
In the present invention, in same phenolic resin esterification sulfonate molecules, specific B group corresponding to each phenyl ring
And its position can be different.Preferably, the B is not present or the B is methyl；When B is methyl, the methyl
There is no particular limitation for position, can be the meta or para position of hydroxyl.
In the present invention, in the chemical structure of the phenolic resin esterification sulfonate, the hydroxyl of phenolic resin can takes
It can also partially be phenolic aldehyde tree if inferior horn is designated as the structural unit (being denoted as structural unit -1) of n in formula (1) on behalf of sulphonic acid ester salt
Rouge, 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 phenolic resin to be esterified
The chemical structure of sulfonate, wherein the connection of structural unit -1 and structural unit -2 in phenolic resin esterification sulfonate
Mode does not limit, and can be random or block.Further, middle knot in the chemical structure of the phenolic resin esterification sulfonate
Structure unit -2 may or may not be present.Structure list in the phenolic resin esterification sulfonate can be represented by n/ (m+n)
The content of member -1.Under preferable case, n/ (m+n) is 0.2~0.95, preferably 0.2~0.8, more preferably 0.4~0.6.Work as institute
In the chemical structure for stating phenolic resin esterification sulfonate, the relation with contents of structural unit -1 and structural unit -2 is met the above range
When, can the printing that further prepares of phenolic resin esterification sulfonate there is better printing performance with hydrophilic version, it is such as close
Aqueous, water resistance, resistance to print property etc..
The chemical structure of heretofore described phenolic resin esterification sulfonate can be measured by the method for infrared spectroscopy.It can
To be substituted the content of part by the hydroxyl of phenolic resin described in potentiometric determination.
In the case of, according to the invention it is preferred to, in the infrared spectrum spectrogram of the phenolic resin esterification sulfonate, wave number is
3400cm-1Place is the absorption peak of phenolic resin hydroxyl, wave number 1750cm-1Place is the absorption peak of ester carbonyl group, wave number 1240cm-1And 1090cm-1Place is the absorption peak of sulfonic acid group.
According to the present invention, a kind of preferred embodiment, the phenolic resin esterification sulfonate can be by the following method
Synthesis: the phenolic resin esterification sulfonate is the esterification products of phenolic resin and Sulfo propionic acid acid anhydride.
In the case of, according to the invention it is preferred to, the Sulfo propionic acid acid anhydride is selected from 3- Sulfo propionic acid acid anhydride, 4- methyl -3- sulfo group third
Acid anhydrides, 5- methyl -3- Sulfo propionic acid acid anhydride, 4,4- dimethyl -3- Sulfo propionic acid acid anhydride, 5,5- dimethyl -3- Sulfo propionic acid acid anhydride, 4,5-
At least one of dimethyl -3- Sulfo propionic acid acid anhydride, 4- propyl -3- Sulfo propionic acid acid anhydride and 5- isopropyl -3- Sulfo propionic acid acid anhydride.
In the present invention, phenolic resin and Sulfo propionic acid acid anhydride carry out esterification in the presence of solvent and activator.The work
Agent is preferably alkali compounds, for example, the activator can selected from tetramethylammonium hydroxide, lithium hydroxide, sodium hydroxide,
At least one of potassium hydroxide, lithium hydride, hydrofining, sodium hydride and lithium metal, sodium, potassium.Metal member in the activator
Element can stay in phenolic resin esterification sulfonate, obtain phenolic resin esterification sodium sulfonate, phenolic resin esterification potassium sulfonate,
Phenolic resin is esterified Sulfonic Lithium or phenolic resin is esterified sulfanilic acid.
The second object of the present invention provides a kind of synthetic method of phenolic resin esterification sulfonate of the invention, this method
It include: that Sulfo propionic acid acid anhydride shown in phenolic resin and formula (2) is subjected to esterification in the presence of solvent and activator,
Wherein, the positive integer that x is 1~3, A1~A4It is each independently hydrogen or C1~C6Alkyl.
According to the present invention, the Sulfo propionic acid acid anhydride of selection can promote to improve the property for the hydrophilic layer that phenolic resin 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 phenolic resin for the chemical structure shown is esterified sulfonate.Under preferable case, the Sulfo propionic acid acid anhydride is selected from 3- Sulfo propionic acid
Acid anhydride (No. CAS is 5961-88-6), 4- methyl -3- Sulfo propionic acid acid anhydride (No. CAS is 1058711-91-3), 5- methyl -3- sulfo group third
Acid anhydrides (No. CAS is 21010-17-3), 4,4- dimethyl -3- Sulfo propionic acid acid anhydride (No. CAS is 35638-12-1), 5,5- diformazan
Base -3- Sulfo propionic acid acid anhydride (No. CAS is 5927-70-8), (No. CAS is 1234622-75- to 4,5- dimethyl -3- Sulfo propionic acid acid anhydride
3), (No. CAS is 4374- for 4- propyl -3- Sulfo propionic acid acid anhydride (No. CAS is 42028-01-3) and 5- isopropyl -3- Sulfo propionic acid acid anhydride
At least one of 76-9).
According to the present invention, the Sulfo propionic acid acid anhydride is commercially available, and can also be prepared.When being prepared, system
Standby method for example may include: to be by structural formulaBromo carboxylic acid in acetone, be warming up to 50
After DEG C, 10% sodium sulfite aqueous solution is added dropwise, dripping quantity makes the molar ratio at least 1:1 of sodium sulfite Yu bromo carboxylic acid, drop
It is warming up to after the completion of adding 75-80 DEG C of reaction 5 hours or more, obtaining structural formula isIntermediate product, so
Afterwards in SOCl2In the presence of carry out esterification, obtain compound shown in formula (2).The reaction equation of the preparation process is as follows
Shown in formula:
A in the above preparation method1~A4It is each independently hydrogen or C1~C6Alkyl, x be 1~3 positive integer.?
To product can be measured by infrared analysis its structure be formula (2) indicate compound.
According to the present invention, the phenolic resin can provide the basis material of the hydrophilic layer as galley, can contain
The structural unit as shown in formula (3)Wherein, B is worked as in B existence or non-existence
In the presence of be selected from C1~C12Alkyl.The selection of the phenolic resin meets to obtain the phenolic resin of chemical structure shown in formula (1)
It is esterified sulfonate.Under preferable case, the degree of polymerization of the phenolic resin is 4~50.It can be with chemistry shown in corresponding (1)
The numerical value of m+n in structure.Preferred degree of polymerization is 10~40, more preferably 20~30.The phenolic resin is known substance, can be with
According to the phenolic resin esterification sulfonate selection finally needed, for example, can commercially available Weihai economic and technological development zone day have at chemical industry
Limit company BTB series phenolic resin (such as BTB-17, BTB-19, BTB-25, BTB-26G, BTB-27, BTB-29, BTB-225,
BTB-225L, BTB-30, BTB-413P, BTB-M), or can commercially available RuiShiDa Chemical Engineering Co., Ltd., Benxi City BX series phenol
Urea formaldehyde (such as BX-10, BX-15, BX-20, BX-25, BX-30, BX-40, BX-265).
According to the present invention, specific B group corresponding on each phenol structure of the phenolic resin and its position can be with
It is different.Preferably, the B is not present or the B is methyl；When B is methyl, the position of the methyl is not special
Restriction, can be hydroxyl meta or para position.That is, in situations where it is preferred, phenol structure in the phenolic resin
Unit can selected from phenol structure unit, to one of sylvan structural unit and sylvan structural unit or a variety of mixed
It closes.
According to the present invention, the solvent can be used for the esterification reaction process, so as to reactant phenolic resin and sulfo group
Propionic andydride preferably carries out esterification.Under preferable case, the solvent can be the organic solvent of dissolvable phenolic resin.It is excellent
Selection of land, the organic solvent are selected from such as dimethylformamide, dimethyl sulfoxide, r- butyrolactone, N-Methyl pyrrolidone, N- ethyl
At least one of pyrrolidones, tetrahydrofuran, ethyl alcohol and dioxane.
According to the present invention, the activator can be realized the esterification.Under preferable case, the activator is
Alkali compounds；The activator is preferably selected from tetramethylammonium hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, hydrogenation
At least one of lithium, hydrofining, sodium hydride and lithium metal, sodium, potassium.
According to the present invention, the condition of the esterification makes finally obtained phenolic resin esterification sulfonate meet aforementioned phenol
The requirement of urea formaldehyde esterification sulfonate.Under preferable case, the weight ratio of the phenolic resin and the Sulfo propionic acid acid anhydride is (0.1
~20): 1, preferably (0.5~13): 1.The inventory of the phenolic resin and the Sulfo propionic acid acid anhydride, can satisfy
Phenolic resin is esterified sulfonate with 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 Sulfo propionic acid acid anhydride and the activator is 1:(1~1.2).
In the case of, according to the invention it is preferred to, esterification reaction temperature is 40 DEG C~120 DEG C, preferably 60 DEG C~100 DEG C；Ester
The change reaction time is 1~10h, preferably 3~5h.
In the present invention, the phenolic resin and the Sulfo propionic acid acid anhydride first can be dissolved in the solvent respectively, are configured to
It is contacted again after solution and carries out the esterification.
In the present invention, specifically, phenolic resin can be dissolved in the solvent, the activator is then added；Again
It is stirred at room temperature and the solution that the Sulfo propionic acid acid anhydride is dissolved in the solvent is added dropwise；It is after being added dropwise, the reaction of formation is molten
Liquid first carries out 1~2h of pre-reaction at room temperature, is then warming up to 60 DEG C~80 DEG C 2~4h of progress esterification again.Reaction obtains
Product by spray drying obtain solid powder.Obtained solid powder is subjected to examination of infrared spectrum, is determined as containing formula
(1) phenolic resin of chemical structure shown in is esterified sulfonate.In infrared absorption spectra, wave number 3400cm-1Place is phenol
The absorption peak of urea formaldehyde hydroxyl, wave number 1750cm-1Place is the absorption peak of ester carbonyl group, wave number 1240cm-1And 1090cm-1Place
For the absorption peak of sulfonic acid group.
The third object of the present invention provides a kind of printing hydrophilic version, comprising: substrate, and be formed on the substrate
Hydrophilic layer；Wherein, in the infrared absorption spectra of the hydrophilic layer, wave number 3400cm-1Place is the absorption peak of phenolic resin hydroxyl,
Wave number is 1750cm-1Place is the absorption peak of ester carbonyl group, 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 is by being esterified sulfonate in institute for phenolic resin of the invention
It states and is coated to obtain on substrate.The phenolic resin esterification sulphur that the phenolic resin esterification sulfonate can provide through the invention
Hydrochlorate synthetic method obtains.
According to the present invention, a kind of preferred embodiment, the process of the coating include: that the phenolic resin is esterified sulfonic acid
Salt is dissolved in water and obtains water-soluble coating fluid；The coating fluid is coated on the surface of the substrate, then 100 DEG C~
1~10min is toasted at 200 DEG C, then obtains the hydrophilic layer through cooling.
Preferably, in the water soluble paint, the content of the phenolic resin esterification 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
In hydrophilic layer on the graph text information layer that is formed, wherein the graph text information layer is by spraying ink simultaneously on the hydrophilic layer
Drying is formed.
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, He Qin
Photosensitive photoresists on hydrophilic layer in water 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 SekisuiBL-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, be added phosphatase 11 5ml, isopropanol 75ml,
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 phenolic resin esterification sulfonate of the invention.
The pure Para-cresol-formaldehyde resin (Weihai Economic and Technological Development Zone Tiancheng Chemical Co., Ltd. BTB-25) of 24g is dissolved in
In the tetrahydrofuran (THF) of 200mL, it will be added after the chopping of 2.5g metallic sodium, mixed at room temperature 0.5h；
Then 3- Sulfo propionic acid acid anhydride (structural formula such as formula (2), wherein A is added dropwise1、A2、A3And A4It is H, x=1；Purchased from Shanghai
Three herd Chemical Engineering Technology Co., Ltd) tetrahydrofuran solution (3- Sulfo propionic acid acid anhydride 14.85g, tetrahydrofuran solution 200mL), phenol
Urea formaldehyde: the weight ratio of 3- Sulfo propionic acid acid anhydride is 1.62:1, about experience 1h, obtains reaction mixture；
Reaction mixture is reacted into 1h at room temperature, then is warming up to 70 DEG C of progress esterification 3h；
The product obtained after the completion of esterification is spray-dried, solid powder is obtained.
Solid powder is subjected to infrared spectrum analysis, wave number 3400cm-1Place is the absorption peak of phenolic resin hydroxyl, wave number
For 1750cm-1Place is the absorption peak of ester carbonyl group, wave number 1240cm-1And 1090cm-1Place is the absorption peak of sulfonic acid group.It uses
Sodium is activator, obtains phenolic resin esterification sodium sulfonate.
According to the ingredient proportion of phenolic resin and 3- Sulfo propionic acid acid anhydride, phenolic resin is esterified shown in sodium sulfonate corresponding (1)
Structure in, n=20, m=20, n/ (m+n)=0.5.It is denoted as PSL-1.
Embodiment 2
This example demonstrates that the preparation of phenolic resin esterification sulfonate of the invention.
The pure methyl phenolic resin (RuiShiDa Chemical Engineering Co., Ltd., Benxi City BX-30) of 4.8g is dissolved in the dioxy of 40mL
In six rings, it is slowly added to total 0.63g sodium hydride in three batches and (is scattered in mineral oil, wherein the concentration of sodium hydride is 60 weights
Measure %), react at room temperature 1h；
Then 4- methyl -3- Sulfo propionic acid acid anhydride (structural formula such as formula (2), wherein A is added dropwise1For methyl, A2、A3And A4It is H,
X=1；Purchased from Bellingwell company) dioxane solution (4- methyl -3- Sulfo propionic acid acid anhydride 3.93g, dioxane 20mL), phenol
Urea formaldehyde: the weight ratio of 4- methyl -3- Sulfo propionic acid acid anhydride is 1.22:1, about experience 1h, obtains reaction mixture；
By reaction mixture pre-reaction 1.2h at room temperature, then it is warming up to 75 DEG C of progress esterification 2h；
The product obtained after the completion of esterification is spray-dried, solid powder is obtained.
Solid powder is subjected to infrared spectrum analysis, wave number 3400cm-1Place is the absorption peak of phenolic resin hydroxyl, wave number
For 1750cm-1Place is the absorption peak of ester carbonyl group, wave number 1240cm-1And 1090cm-1Place is the absorption peak of sulfonic acid group.It uses
Sodium hydride is activator, obtains phenolic resin esterification sodium sulfonate.
According to the ingredient proportion of phenolic resin and 4- methyl -3- Sulfo propionic acid acid anhydride, phenolic resin is esterified sodium sulfonate corresponding
(1) in structure shown in, n=24, m=16, n/ (m+n)=0.6.It is denoted as PSL-2.
Embodiment 3
This example demonstrates that the preparation of phenolic resin esterification sulfonate of the invention.
By the mixed phenol phenolic resin (paracresol: metacresol=5:5 (molar ratio) of 5.6g；The auspicious thing in Benxi is limited up to chemical industry
Company BX-20) it is dissolved in the dimethylformamide (DMF) of 20mL, it will be added after the chopping of 0.79g metallic potassium, mixed at room temperature 0.5h；
Then 4,4- dimethyl -3- Sulfo propionic acid acid anhydride (structural formula such as formula (2), wherein A is added dropwise1And A2For methyl, A3And A4
For H, x=1；Purchased from sigma aldrich company) dimethyl formamide solution (4,4- dimethyl -3- Sulfo propionic acid acid anhydride
3.34g, dimethylformamide 40mL), phenolic resin: the weight ratio of 4,4- dimethyl -3- Sulfo propionic acid acid anhydrides is 1.67:1, is about passed through
1h is gone through, reaction mixture is obtained；
By reaction mixture pre-reaction 0.8h at room temperature, then it is warming up to 65 DEG C of progress esterification 3.5h；
The product obtained after the completion of esterification is spray-dried, solid powder is obtained.
Solid powder is subjected to infrared spectrum analysis, wave number 3400cm-1Place is the absorption peak of phenolic resin hydroxyl, wave number
For 1750cm-1Place is the absorption peak of ester carbonyl group, wave number 1240cm-1And 1090cm-1Place is the absorption peak of sulfonic acid group.It uses
Potassium is activator, obtains phenolic resin esterification potassium sulfonate.
According to phenolic resin and 4, the ingredient proportion of 4- dimethyl -3- Sulfo propionic acid acid anhydride, phenolic resin is esterified potassium sulfonate pair
It answers in structure shown in formula (1), n=16, m=24, n/ (m+n)=0.4.It is denoted as PSL-3.
Embodiment 4
By the mixed phenol phenolic resin (paracresol: metacresol=7:3 (molar ratio) of 36g；Weihai economic and technological development zone day at
Chemical Co., Ltd. BTB-225) it is dissolved in the tetrahydrofuran (THF) of 200mL, 2.09g lithium hydride is added, mixed at room temperature
0.5h；
Then 5- methyl -3- Sulfo propionic acid acid anhydride (structural formula such as formula (2), wherein A is added dropwise3For methyl, A1、A2And A4For H, x
=1；Purchased from sigma aldrich company) tetrahydrofuran solution (5- methyl -3- Sulfo propionic acid acid anhydride 39.31g, tetrahydrofuran
200mL), phenolic resin: the weight ratio of 5- methyl -3- Sulfo propionic acid acid anhydride is 0.92:1, about experience 1h, obtains reaction mixture；
By reaction mixture pre-reaction 1h at room temperature, then it is warming up to 70 DEG C of progress esterification 4h；
The product obtained after the completion of esterification is spray-dried, solid powder is obtained.
Solid powder is subjected to infrared spectrum analysis, wave number 3400cm-1Place is the absorption peak of phenolic resin hydroxyl, wave number
For 1750cm-1Place is the absorption peak of ester carbonyl group, wave number 1240cm-1And 1090cm-1Place is the absorption peak of sulfonic acid group.It uses
Lithium hydride is activator, obtains phenolic resin esterification Sulfonic Lithium.
According to the ingredient proportion of phenolic resin and 5- methyl -3- Sulfo propionic acid acid anhydride, phenolic resin is esterified Sulfonic Lithium corresponding
(1) in structure shown in, n=24, m=6, n/ (m+n)=0.8.It is denoted as PSL-4.
Embodiment 5
By the mixed phenol phenolic resin (paracresol: metacresol=3:7 (molar ratio) of 24g；The auspicious thing in Benxi reaches the limited public affairs of chemical industry
Department BX-15) be dissolved in the tetrahydrofuran of 100mL, be slowly added in three batches total 1.05g sodium hydride (be scattered in mineral oil, wherein
The concentration of sodium hydride is 60 weight %), mixed at room temperature 1h；
Then 5,5- dimethyl -3- Sulfo propionic acid acid anhydride (structural formula such as formula (2), wherein A is added dropwise3And A4For methyl, A1And A2
For H, x=1；Purchased from Shanghai an ancient unit of weight sharpen learn Science and Technology Ltd.) tetrahydrofuran solution (5,5- dimethyl -3- Sulfo propionic acid acid anhydride
7.16g, tetrahydrofuran 40mL), phenolic resin: the weight ratio of 5,5- dimethyl -3- Sulfo propionic acid acid anhydrides is 3.35:1, is about undergone
1h obtains reaction mixture；
By reaction mixture pre-reaction 1h at room temperature, then it is warming up to 75 DEG C of progress esterification 3h；
The product obtained after the completion of esterification is spray-dried, solid powder is obtained.
Solid powder is subjected to infrared spectrum analysis, wave number 3400cm-1Place is the absorption peak of phenolic resin hydroxyl, wave number
For 1750cm-1Place is the absorption peak of ester carbonyl group, wave number 1240cm-1And 1090cm-1Place is the absorption peak of sulfonic acid group.It uses
Sodium hydride is activator, obtains phenolic resin esterification sodium sulfonate.
According to phenolic resin and 5, the ingredient proportion of 5- dimethyl -3- Sulfo propionic acid acid anhydride, phenolic resin is esterified sodium sulfonate pair
It answers in structure shown in formula (1), n=4, m=16, n/ (m+n)=0.2.It is denoted as PSL-5.
Embodiment 6
By the mixed phenol phenolic resin (paracresol: phenol=5:5 (molar ratio) of 2.4g；The auspicious thing in Benxi reaches the limited public affairs of chemical industry
Department BX-10) it is dissolved in the dioxane of 10mL, it is slowly added to 0.17g lithium hydride, mixed at room temperature 1h；
Then 4- propyl -3- Sulfo propionic acid acid anhydride (structural formula such as formula (2), wherein A is added dropwise1For propyl, A2、A3And A4For H, x
=1；Purchased from sigma aldrich company) dioxane solution (4- propyl -3- Sulfo propionic acid acid anhydride 3.69g, dioxane
40mL), phenolic resin: the weight ratio of 4- propyl -3- Sulfo propionic acid acid anhydride is 0.65:1, 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 esterification 2h；
The product obtained after the completion of esterification is spray-dried, solid powder is obtained.
Solid powder is subjected to infrared spectrum analysis, wave number 3400cm-1Place is the absorption peak of phenolic resin hydroxyl, wave number
For 1750cm-1Place is the absorption peak of ester carbonyl group, wave number 1240cm-1And 1090cm-1Place is the absorption peak of sulfonic acid group.It uses
Lithium hydride is activator, obtains phenolic resin esterification Sulfonic Lithium.
According to the ingredient proportion of phenolic resin and 4- propyl -3- Sulfo propionic acid acid anhydride, phenolic resin is esterified Sulfonic Lithium corresponding
(1) in structure shown in, n=19, m=1, n/ (m+n)=0.95.It is denoted as PSL-6.
Embodiment 7
By the mixed phenol phenolic resin (paracresol: phenol=7:3 (molar ratio) of 34g；Weihai economic and technological development zone day is at change
Work Co., Ltd BTB-19) it is dissolved in the dimethyl sulfoxide of 200mL, 0.6g metallic potassium is cut into fragment and is slowly added to, room temperature is mixed
Close 0.5h；
Then 5- isopropyl -3- Sulfo propionic acid acid anhydride (structural formula such as formula (2), wherein A is added dropwise3For isopropyl, A1、A2And A4For
H, x=1；Purchased from sigma aldrich company) dimethyl sulphoxide solution (5- isopropyl -3- Sulfo propionic acid acid anhydride 2.75g, diformazan
Base sulfoxide 20mL), phenolic resin: the weight ratio of 5- isopropyl -3- Sulfo propionic acid acid anhydride is 12.35:1, about experience 1h, is reacted
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 3400cm-1Place is the absorption peak of phenolic resin hydroxyl, wave number
For 1750cm-1Place is the absorption peak of ester carbonyl group, wave number 1240cm-1And 1090cm-1Place is the absorption peak of sulfonic acid group.It uses
Potassium is activator, obtains phenolic resin esterification potassium sulfonate.
According to the ingredient proportion of phenolic resin and 5- isopropyl -3- Sulfo propionic acid acid anhydride, it is corresponding that phenolic resin is esterified potassium sulfonate
In structure shown in formula (1), n=1, m=19, n/ (m+n)=0.05.It is denoted as PSL-7.
Embodiment 8
By the mixed phenol phenolic resin (paracresol: phenol=3:7 (molar ratio) of 5.5g；Weihai economic and technological development zone day at
Chemical Co., Ltd. BTB-M) it is dissolved in the N-Methyl pyrrolidone of 20mL, 1.15g metallic sodium is cut into fragment and is slowly added to, room
Temperature mixing 0.5h；
Then 4,5- dimethyl -3- Sulfo propionic acid acid anhydride (structural formula such as formula (2), wherein A is added dropwise1And A3For methyl, A2And A4
For H, x=1；Purchased from sigma aldrich company) N-Methyl pyrrolidone solution (4,5- dimethyl -3- Sulfo propionic acid acid anhydride
8.21g, N-Methyl pyrrolidone 100mL), phenolic resin: the weight ratio of 4,5- dimethyl -3- Sulfo propionic acid acid anhydrides is 0.67:1,
1h is about undergone, reaction mixture is obtained；
By reaction mixture pre-reaction 1h at room temperature, then it is warming up to 120 DEG C of progress esterification 3h；
The product obtained after the completion of esterification is spray-dried, solid powder is obtained.
Solid powder is subjected to infrared spectrum analysis, wave number 3400cm-1Place is the absorption peak of phenolic resin hydroxyl, wave number
For 1750cm-1Place is the absorption peak of ester carbonyl group, wave number 1240cm-1And 1090cm-1Place is the absorption peak of sulfonic acid group.It uses
Lithium is activator, obtains phenolic resin esterification Sulfonic Lithium.
According to phenolic resin and 4, the ingredient proportion of 5- dimethyl -3- Sulfo propionic acid acid anhydride, phenolic resin is esterified Sulfonic Lithium pair
It answers in structure shown in formula (1), n=20, 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 photosensitive photosensitive printed board 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
Phenolic resin (RuiShiDa Chemical Engineering Co., Ltd., Benxi City BX-20) and HD-110 trifunctional aziridine crosslinker
(Jiangsu Kangle New Materials Technology Co., Ltd.) is dissolved in dioxane, and being configured to BX-20 phenolic resin concentration is 10 weight %, nitrogen
Third pyridine concentration is the dioxane solution of 3 weight %；
The dioxane solution is coated on to the surface of PET (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；
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
BTB-25 phenolic resin and HD-110 trifunctional aziridine crosslinker (the limited public affairs of Jiangsu health and happiness new material science and technology
Department) it is dissolved in DMF, and the titanium dioxide of partial size 30nm is added, dispersed 1 hour with 4000 revs/min of mulser, is configured to BTB-
25 phenolic resin concentration are 6 weight %, and aziridine concentration is 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
| Number | Hydrophilic layer | n/(m+n) | Contact angle | Water resistance | Press resistance rate (part) | Printing product surface |
| Embodiment 9 | PSL-1 | 0.5 | <10° | >3h | 16000 | Completely |
| Embodiment 10 | PSL-2 | 0.6 | <10° | >3h | 17000 | Completely |
| Embodiment 11 | PSL-3 | 0.4 | <10° | >3h | 14000 | Completely |
| Embodiment 12 | PSL-4 | 0.8 | <10° | >3h | 13000 | Completely |
| Embodiment 13 | PSL-5 | 0.2 | <10° | >3h | 12000 | Completely |
| Embodiment 14 | PSL-6 | 0.95 | <10° | >3h | 7000 | Completely |
| Embodiment 15 | PSL-7 | 0.05 | <10° | >3h | 5500 | Completely |
| Embodiment 16 | PSL-8 | 1 | <10° | >3h | 6000 | Completely |
| Comparative example 1 | - | - | 30° | >3h | - | It is dirty |
| Comparative example 2 | - | - | 20° | >3h | - | It is dirty |
| Comparative example 3 | - | - | 45° | >3h | - | It is dirty |
The phenolic resin esterification 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 sulfonate, provide hydrophilic version with better hydrophily, at the same have water resistance and
Meet enough press resistance rates.The hydrophilic version, which can further apply, prepares various galleys, such as ink jet printing version, photosensitive photosensitive
Galley and thermosensitive printing plates, and provide galley better printing performance, obtain clear and clean printed matter.And it compares
The ink jet printing version that example 1-3 is obtained using the prior art cannot obtain clean printed matter, be unable to complete qualified printing.
Claims (27)
1. a kind of phenolic resin is esterified sulfonate, which, which is esterified sulfonate, has chemical structure shown in formula (1),
Wherein, the positive integer of m+n=4~50, the positive integer that n/ (m+n)=0.05~1, x is 1~3；A1~A4Each independently
For hydrogen or C1~C6Alkyl；M is Li, Na, K or NH4；B existence or non-existence is selected from C in the presence of B1~C12Alkyl.
2. phenolic resin according to claim 1 is esterified sulfonate, wherein n/ (m+n) is 0.2~0.95.
3. phenolic resin according to claim 2 is esterified sulfonate, wherein n/ (m+n) is 0.2~0.8.
4. phenolic resin according to claim 3 is esterified sulfonate, wherein n/ (m+n) is 0.4~0.6.
5. phenolic resin described in any one of -4 is esterified sulfonate according to claim 1, wherein the phenolic resin esterification
In the infrared spectrum spectrogram of sulfonate, wave number 3400cm-1Place is the absorption peak of phenolic resin hydroxyl, wave number 1750cm-1Place
For the absorption peak of ester carbonyl group, wave number 1240cm-1And 1090cm-1Place is the absorption peak of sulfonic acid group.
6. phenolic resin described in any one of -4 is esterified sulfonate according to claim 1, wherein the phenolic resin esterification
Sulfonate is the esterification products of phenolic resin and Sulfo propionic acid acid anhydride；The Sulfo propionic acid acid anhydride is selected from 3- Sulfo propionic acid acid anhydride, 4- methyl-
3- Sulfo propionic acid acid anhydride, 5- methyl -3- Sulfo propionic acid acid anhydride, 4,4- dimethyl -3- Sulfo propionic acid acid anhydride, 5,5- dimethyl -3- sulfo group third
In acid anhydrides, 4,5- dimethyl -3- Sulfo propionic acid acid anhydride, 4- propyl -3- Sulfo propionic acid acid anhydride and 5- isopropyl -3- Sulfo propionic acid acid anhydride extremely
Few one kind.
7. phenolic resin described in a kind of any one of claim 1-5 is esterified the synthetic method of sulfonate, this method comprises:
In the presence of solvent and activator, phenolic resin and formula (2) compound represented are subjected to esterification,
Wherein, the positive integer that x is 1~3, A1~A4It is each independently hydrogen or C1~C6Alkyl.
8. according to the method described in claim 7, wherein, formula (2) compound represented is selected from 3- Sulfo propionic acid acid anhydride, 4- first
Base -3- Sulfo propionic acid acid anhydride, 5- methyl -3- Sulfo propionic acid acid anhydride, 4,4- dimethyl -3- Sulfo propionic acid acid anhydride, 5,5- dimethyl -3- sulfo group
In propionic andydride, 4,5- dimethyl -3- Sulfo propionic acid acid anhydride, 4- propyl -3- Sulfo propionic acid acid anhydride and 5- isopropyl -3- Sulfo propionic acid acid anhydride
It is at least one.
9. according to the method described in claim 7, wherein, the degree of polymerization of the phenolic resin is 4~50.
10. according to the method described in claim 7, wherein, the solvent is the organic solvent that can dissolve phenolic resin；It is described to have
Solvent is selected from dimethylformamide, dimethyl sulfoxide, gamma-butyrolacton, N-Methyl pyrrolidone, N- ethyl pyrrolidone, four
At least one of hydrogen furans, ethyl alcohol and dioxane.
11. according to the method described in claim 7, wherein, the activator is alkali compounds.
12. according to the method for claim 11, 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.
13. the method according to any one of claim 7-12, wherein shown in the phenolic resin and the formula (2)
Compound dosage weight ratio be (0.1~20): 1, the dosage mole of formula (2) compound represented and the activator
Than for 1:(1~1.2).
14. according to the method for claim 13, wherein the use of the phenolic resin and the formula (2) compound represented
Measuring weight ratio is (0.5~13): 1.
15. the method according to any one of claim 7-12, wherein esterification reaction temperature is 40 DEG C~120 DEG C, ester
The change reaction time is 1~10h.
16. according to the method for claim 15, wherein esterification reaction temperature is 60 DEG C~100 DEG C, and reaction time of esterification is
3~5h.
17. a kind of hydrophilic version of printing, comprising: substrate, and the hydrophilic layer being formed on the substrate；The hydrophilic layer pass through by
The esterification sulfonate of phenolic resin described in any one of claim 1-6 is applied to obtain on the substrate；Wherein, institute
It states in the infrared absorption spectra of hydrophilic layer, wave number 3400cm-1Place is the absorption peak of phenolic resin hydroxyl, wave number 1750cm-1
Place is the absorption peak of ester carbonyl group, wave number 1240cm-1And 1090cm-1Place is the absorption peak of sulfonic acid group.
18. hydrophilic version according to claim 17, 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.
19. hydrophilic version according to claim 17, wherein the process of the coating includes: to be esterified the phenolic resin
Sulfonate is dissolved in water and obtains water-soluble coating fluid；The water-soluble coating fluid is coated on the surface of the substrate, then
1~10min is toasted at 100 DEG C~200 DEG C, then obtains the hydrophilic layer through cooling.
20. hydrophilic version according to claim 19, wherein in the water solubility coating fluid, the phenolic resin is esterified sulphur
The content of hydrochlorate is 5~30 weight %.
21. hydrophilic version described in 9 or 20 according to claim 1, wherein also contain curing agent in the water solubility coating fluid, institute
The content for stating curing agent is 1~10 weight %.
22. hydrophilic version according to claim 21, wherein the curing agent is selected from isocyanates, aziridine or containing multiple
The compound of epoxy group.
23. application of the hydrophilic version in printing plate described in a kind of any one of claim 17-22.
24. a kind of galley, comprising: hydrophilic version described in any one of claim 17-22, and in the hydrophilic version
The graph text information layer formed on hydrophilic layer.
25. a kind of ink jet printing version, comprising: hydrophilic version described in any one of claim 17-22, and in the hydrophilic version
In hydrophilic layer on the graph text information layer that is formed, wherein the graph text information layer is by spraying ink simultaneously on the hydrophilic layer
Drying is formed.
26. a kind of photosensitive photosensitive printed board, comprising: hydrophilic version described in any one of claim 17-22, and in the parent
Photosensitive photoresists on hydrophilic layer in water version, the photosensitive photoresists form graph text information layer.
27. a kind of thermosensitive printing plates, comprising: hydrophilic version described in any one of claim 17-22, and in the hydrophilic version
In hydrophilic layer on thermographic layer, the thermographic layer forms graph text information layer.
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| CN201710044848.8A CN108329446B (en) | 2017-01-20 | 2017-01-20 | Phenolic resin is esterified sulfonate and its synthetic method, printing hydrophilic version and application and galley |
| PCT/CN2017/079566 WO2018133214A1 (en) | 2017-01-20 | 2017-04-06 | Modified phenol-aldehyde resin and synthesis method therefor, hydrophilic plate for printing and use thereof, and printing plate |
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| CN201710044848.8A CN108329446B (en) | 2017-01-20 | 2017-01-20 | Phenolic resin is esterified sulfonate and its synthetic method, printing hydrophilic version and application and galley |
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| CN110032041B (en) * | 2019-05-07 | 2020-11-10 | 深圳市华星光电半导体显示技术有限公司 | Photoresist composition, display panel and preparation method thereof |
| CN112239453A (en) * | 2019-07-16 | 2021-01-19 | 杉杉新材料（衢州）有限公司 | Preparation method of acyl sulfonate compound |
| 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 |
| CN114752273B (en) * | 2020-12-29 | 2022-09-06 | 中国科学院化学研究所 | Antibacterial liquid, preparation method and application thereof, and antibacterial product |
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