CN108227384A - Negative type heat-sensitive CTP plate precursor with double-layer structure - Google Patents
Negative type heat-sensitive CTP plate precursor with double-layer structure Download PDFInfo
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- CN108227384A CN108227384A CN201611153669.XA CN201611153669A CN108227384A CN 108227384 A CN108227384 A CN 108227384A CN 201611153669 A CN201611153669 A CN 201611153669A CN 108227384 A CN108227384 A CN 108227384A
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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
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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
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Abstract
The invention discloses a kind of negative type heat-sensitive CTP plate precursors with double-layer structure, are coated with alkali soluble resins layer and negative type photosensitive layer successively on the support of water-wetted surface, and alkali soluble resins layer contains alkali soluble resins, addition resin and illuminating colour；Negative type photosensitive layer includes film-forming resin, crosslinking agent, infrared absorbing agents, light production acid source and illuminating colour.The plate has many advantages, such as high film speed, high development latitude, solvent resistance and high press resistance rate, and possesses good storage stability, so as to be adaptive to the needs of current UV ink printing.
Description
Technical field
The present invention relates to a kind of negative type sensitive offset press versions for having double-layer structure formed on aluminum substrate, specifically relate to
And it is a kind of can be used for the negative type heat-sensitive CTP plate with double-layer structure of temperature-sensitive 800-830nm directly laser Graphic modes before
Body.
Background technology
CTP（Computer direct plate making）The advantages that technology is because of its digitlization, high-effect high-quality and simplicity, environmental protection,
Replace traditional simulation plate-making mode, become the approach of printing enterprise's technology upgrading.CTP plate-making mode is broadly divided into temperature-sensitive at present
CTP（800-830nm）, purple laser c TP（405nm）And UV-CTP three types, and thermosensitive CTP is with imaging precision height, skill
Art maturation becomes the mainstream in market.
Thermal CTP plate material is divided into positive-type and negative type according to imaging mechanism difference.Compared with positive-type plate, negative image
Version has many advantages, such as press resistance rate height, and plate-making is efficient and operation tolerance is big.It is red in negative image temperature-sensitive version when plate exposes
The luminous energy that outer absorbent absorbs 800-830nm is converted into heat, and active material thermal decomposition generates free radicals or generates Bronsted acid, causes
Polymerization or cross-linking reaction make curing of coatings；It is dissolved in alkaline-based developer in unexposed region.However because of reactive compound, can gather
Dark reaction caused by the stability deficiency of conjunction or crosslinkable component is also easy to produce the halfway phenomenon of development, to negative type plate
Storage period makes a significant impact.With transition of the printing market to packages printing business, the printing of environment-friendly type UV ink is gradually universal,
It is required that thermal CTP plate material has the good ink of resistance to UV printing performance.
Invention content
The purpose of the present invention is to provide one kind to have high film speed, high development latitude, high solvent resistance and height
The negative type thermal CTP plate material of the double-layer structure of press resistance rate solves the problems, such as to keep on file in negative engraving storing process.
The technical solution adopted by the present invention is：A kind of negative type heat-sensitive CTP plate precursor with double-layer structure, including negative image
Type thermosensitive printing plates ontology, negative type thermosensitive printing plates ontology include support, are alkali soluble resins layer on support,
With negative type photosensitive layer on alkali soluble resins layer, the alkali soluble resins layer contains alkali soluble resins, addition resin and coloring
Dyestuff, 0.5 ~ 1.5g/m of the alkali soluble resins layer coating weight2, it is 0.5 ~ 1.0 g/m compared with the figure of merit2。
Alkali soluble resins allows for being dissolved in alkaline developer, is had using soluble or swellability in buck or water
One or more of machine high molecular polymer, as such organic high molecular polymer, including：
（1）Side chain has the addition polymer of carboxylic acid group, i.e. methacrylic acid copolymer, acrylic copolymer, itaconic acid copolymerization
Object, crotonic acid-copolymers, maleic acid, partial esterification maleic acid etc.,
（2）There is the acid cellulose derivative of carboxylic acid group in side chain；
（3）Polymer of addition cyclic acid anhydride etc. on the addition polymer with hydroxyl；
（4）Side chain has the polyvinyl acetaldehyde polymer of carboxylic acid group；
（5）Linear phenolic resin and polyethylene phenol resin, linear phenolic resin can be prepared by polycondensation reaction, wherein one of monomer
Must be aromatic hydrocarbons, such as：Phenol, o-cresol, metacresol, paracresol, 2,5- xylenols, 3,5- xylenols, resorcinol, adjacent benzene three
Phenol, bisphenols, bis-phenol-A, triphenol face ethyl phenol, ethyl phenol, to ethyl phenol, propyl phenoxy, normal-butyl phenol, tert-butyl phenol, 1-
Naphthols, beta naphthal.Minimum of one aldehyde or ketone.Wherein aldehyde can be formaldehyde, acetaldehyde, valeral, benzaldehyde, furfural.Ketone can be
Acetone, methyl ethyl ketone, methyl n-butyl ketone, metaformaldehyde.Weight average molecular weight is determined by GPC.It is advisable with 1000 to 15000,
1500 to 10000 is best.Linear phenol-aldehyde resin is condensed by aldehyde and phenol.Metacresol/paracresol/2,5- diphenol/3,5- diphenol in phenol/
Phloroglucin/mixed proportion is 40 to 100/0 to 50/0 to 20/0 to 20/0 to 20/.Or phenol/o-cresol/paracresol/mixed
Composition and division in a proportion example is 1 to 100/0 to 70/0 to 60/.Polyethylene phenol resin can be polymerize by one or more hydroxy styrenes, than
Such as：Adjacent this ethylene of hydroxyl, hydroxy styrenes, 4-Vinyl phenol, 2-（O-hydroxy-phenyl）Propylene, 2-（Between hydroxy phenyl）Third
Alkene, 2-（P-hydroxybenzene）Propylene.It can be by substituent group on these hydroxy styrenes.Such as：The halogen atoms such as chlorine, bromine, iodine and fluorine,
Or the alkyl of C1-4, so as to carry these groups on corresponding resin.These polyethylene phenol resin are by one or more hydroxy benzenes
Vinyl polymerization.It can be associated with that C1-4 alkyl is preferable, and unsubstituted is more preferable on the aromatic ring of polyethylene phenol with substituted base thereon.
（6）Side chain has addition polymer of the addition polymer of phosphate such as containing vinyl phosphoric acid unit.
Alkali soluble resins in alkali soluble resins layer weight percent be 40-90%, most preferably 70-90%, alkali solubility
The weight average molecular weight 1000-1000000 of resin.
Resin is added in alkali soluble resins layer to play the whole alkali solubility of adjustment alkali soluble resins layer and increase alkali solubility
The effect of resin layer intensity, addition resin are polyurethane polymer, vinyl-addition polymer, esters of acrylic acid addition polymerization
Object, acetals polymer or cellulosic polymer, addition resin are 10-60% in the weight percent of alkali soluble resins layer,
Most preferably 10-30%.
In alkali soluble resins layer illuminating colour for Victoria pure blue, alkaline bright blue, solvent blue, crystal violet, crystal violet or
Methylene blue, weight percent of the illuminating colour in alkali soluble resins layer are 0.5-5%, most preferably 0.5-2%.
Negative type photosensitive layer includes film-forming resin, crosslinking agent, infrared absorbing agents, light production acid source and illuminating colour, negative type
Photosensitive layer coating weight is 0.5 ~ 1.5g/m2, preferably 0.5 ~ 1.0 g/m2。
In negative type photosensitive layer film-forming resin be linear phenolic resin, wherein comprising phenol-formaldehyde resin, metacresol-
Formaldehyde resin, ortho-cresol-formaldehyde resin, paracresol-formaldehyde resin, phenol-metacresol（Mole ratio 3：7-7：3）First
Urea formaldehyde, phenol-tertiary butyl phenol (mole ratio 3：1-1.5：1)-formaldehyde resin, metacresol-paracresol（Mole ratio 9：1-
5：5）A kind of phenols such as formaldehyde resin, metacresol-ortho-cresol-formaldehyde resin, two kinds of phenols even three kinds of phenols and formaldehyde
The linear phenolic resin formed by different proportion polycondensation；Film-forming resin dosage accounts for the 30-90% of photosensitive composition total weight, preferably
50-85%, film-forming resin weight average molecular weight are typically chosen 2000-10000, preferably 2500-7500, Mw/MnFor 1.5-20, preferably
1.5-10；When molecular weight is more than 10000, the linearity of phenolic resin declines, and the degree of branching increases, so as in alkaline developer
Solubility declines, and development is met difficulty；Molecular weight is too small, is easy to generate stripping phenomenon in developing process, and the pressrun of plate is weak,
Also the resolution ratio of plate and the reproducibility of site are influenced.Film-forming resin dosage accounts for photosensitive composition total weight as 30-90%.
In order to promote or increase the crosslinking of photosensitive layer, it is ensured that fully curing adds in melamine in the composition of photosensitive layer
Amine derivative is as crosslinking agent, preferably hexamethoxymethyl melamine；The dosage of crosslinking agent accounts for photosensitive composition total weight
8-20 %, preferably 8-12 %.
Middle infrared absorption agent of the present invention is not particularly limited, as long as can absorb infrared light and it is converted into the chemical combination of heat
Object can.It is a kind of absorption dyestuff for the light that can absorb 760-1200nm wavelength, however, it does not absorb or absorb substantially
But UV light is not felt, and is not changed by the Weak ultraviolet containing white light.This light absorbing dyestuff structural formula is：
Wherein each X can independently be S, O, NR or C (alkyl)2；
Each R1Alkyl, alkyl azochlorosulfonate or alkyl ammonium group can independently be；
R2Can be hydrogen, halogen, SR, S02R, OR or NR2；
Each R3Hydrogen, alkyl, COOR, OR, SR, S0 can independently be3 —、NR2, halogen and the fused benzo ring not necessarily replaced；
A—Represent anion；
--- represent nonessential five yuan or six-membered carbon ring；
Wherein each R can independently be hydrogen, alkyl and aryl；With
Wherein each n can independently be 0,1,2 or 3.
If R1It is alkyl azochlorosulfonate, then due to foring inner salt, so A—It can be not present and alkali metal cation conduct
Counter ion will be required.If R1It is alkyl ammonium group, then will needs second of anion as counter ion.Second of anion can
With with A—Identical or different anion.
Among these dyestuffs, preferred cyanine dye, polymethin dyes, rectangular salt dyestuff chrome dye, pyrans or sulphur
For pyrylium dye, what is be particularly suitable is cyanine dye, polymethin dyes, pyrylium dye or thiopyrylium dye.
The dosage of infrared absorbing agents accounts for the 0.5-3% of photosensitive composition total weight, preferably 1-2%.
Compound of the light production acid source for the reaction that can smoothly decompose under heat effect, preferably trichlorine in negative type photosensitive layer
Methyl compound in triazine class is such as：- 3,5 pairs of trichloromethyl triazines of 1- phenyl, -3,5 pairs of trichloromethyl triazines of 1- anisyls, 1- pairs
- 3,5 pairs of -3,5 pairs of trichloromethyl triazines of methoxy styryl, 1- methoxy-naphthyls trichloromethyl triazines etc..Light produces the dosage of acid source
Account for the 0.1-5% of photosensitive composition total weight, preferably 0.1-2%
Illuminating colour may be selected from Victoria pure blue, alkaline bright blue, solvent blue, crystal violet, crystal violet, Asia in negative type photosensitive layer
Methyl blue, due to consideration that can reduce plate sensitivity to the absorption of ultraviolet light, preferably Victoria pure blue, alkaline bright blue, oil are molten
It is blue.Its dosage accounts for the 0.5-5% of photosensitive composition total weight, preferably 0.5-2%.
Using the negative type Thermal sensitive plate of double-layer structure made from said components, there is high film speed, high development tolerance
The advantages that degree, high solvent resistance and high press resistance rate, and possess good storage stability.
Specific embodiment
To make the purpose of the present invention, technical solution and effect clearer, clear and definite, below to the present invention further specifically
It is bright.It should be appreciated that specific embodiment described herein is not intended to limit the present invention only to explain the present invention.
Just details are as follows for the specific manufacturing process of double-deck negative type temperature-sensitive version below.
[support]
The support used in the present invention can use dimensionally stable aluminium or its alloy (such as with silicon, copper, manganese, magnesium, chromium, zinc,
Lead, bismuth, nickel alloy).It can usually use in the previous public affairs described in aluminium handbook the 4th edition (1990, the distribution of light metal association)
The material known.Aluminium plate can be the aluminium sheet manufactured using common semi-continuous casting method (DC methods), may be the company of use in addition
The aluminium plate of continuous casting rolling process manufacture.As the method for continuously casting calendering, double roller therapy, tape casting method, block can be used
Casting method etc..The content of xenogenesis element is below 10 weight % in alloy.The thickness of aluminium plate is preferably about mono- 0.6 mm of a 0.1mm left sides
It is right.In addition it is also possible to use the plastic foil or paper that are laminated or have been deposited aluminium, aluminium alloy.
[surface treatment of support]
Using known technology, various processing are implemented to its surface generally according to purpose when support is aluminium plate.As general
Processing method is handled by carrying out degreasing or electrolytic polishing processing and crude removal to aluminium sheet, aluminium surface is cleaned first.So
Afterwards, implement mechanical surface roughening processing or/and electrochemically grained processing, give aluminium plate surface fine bumps.This
Outside, also increase chemical etching processing and crude removal processing sometimes.Then, in order to improve the abrasion performance of surface of aluminum plate, implement anode
Then oxidation processes implement hydrophilicity-imparting treatment or/and sealing pores to aluminium surface as needed.
Throughout manage between, in order to which the treatment fluid of previous processed is made not bring next processing into, preferably carry out using nip rolls into
Capable liquid removal and the washing using progress such as injections.Furthermore, it is possible to the electricity that will be used in electrochemically grained processing
The overflow waste liquid for solving liquid is used as crude removal treatment fluid, but can be omitted crude removal at this time treated washing process.
[formation of alkali soluble resins layer]
The coating fluid of alkali soluble resins layer is coated in the version base of processing and is dried, forms alkali soluble resins layer.
Alkali soluble resins layer composition is applied to support aluminium with solid component concentration dissolving, the dispersion of 2-50 weight %
In version base and it is dried.The generally preferably dried weight of alkali soluble resins layer coating weight being coated on support aluminum substrate
For 0.5-1.0g/m2.As coating weight is reduced, film-strength reduces；As coating weight increases, film strength enhancing.
In alkali soluble resins layer composition on support aluminium plate, it is dissolved in organic solvent for using.As making here
Solvent, including acetone, methyl ethyl ketone, hexamethylene, ethyl acetate, dichloroethylene, tetrahydrofuran, toluene, ethylene glycol list
Methyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, acetylacetone,2,4-pentanedione, cyclohexanone, double third
Keto-alcohol, ethylene glycol monomethyl ether acetate, ethyl cellosolve acetate, ethyleneglycol monopropylether, ethylene glycol monomethyl ether acetate, 3
One methoxypropanol, methoxymethoxy ethyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol (DEG) two
Ether, propylene glycol methyl ether acetate, one 3 one Methoxypropylacetate of propylene glycol monoethyl ether acetate, mono- dimethyl methyl of N, N
Amide, N, mono- dimethylacetylamides of N, dimethyl sulfoxide (DMSO), mono- butyrolactone of Y, methyl lactate, ethyl lactate etc..These solvents can be with
It is used alone or as a mixture
In order to improve the coating appearance, surface-active can be added in the alkali soluble resins layer of the negative type temperature-sensitive version of the present invention
Agent.
As the coating method of alkali soluble resins layer, silk stick (coating rod) method, extrusion type coating machine can be used
Method, the method for roll coater (slide blade coater) etc., but be not limited to these.
[formation of photosensitive layer]
It the coating of photosensitive coated layer and is dried on the version base of alkali soluble resins layer is coated with, ultimately forms the moon of the present invention
Pattern temperature-sensitive version.
Photosensitive layer composition is applied to solid component concentration dissolving, the dispersion of 2-50 weight % and is coated with alkali solubility tree
In the version base of lipid layer and it is dried.It is 0.5-1.0g/m in the generally preferably dried weight of photosensitive layer amount2.With
Coating weight is reduced, and is reduced for obtaining the light exposure of image, but film-strength reduces.As coating weight increases, increased with light exposure,
But film strength enhances
Photosensitive layer composition is dissolved in organic solvent for using.As solvent used herein, including acetone, Methylethyl
Ketone, hexamethylene, ethyl acetate, dichloroethylene, tetrahydrofuran, toluene, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol two
Methyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, acetylacetone,2,4-pentanedione, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, second
Glycol ether acetic acid esters, ethyleneglycol monopropylether, ethylene glycol monomethyl ether acetate, 3 one methoxypropanols, methoxymethoxy second
Alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethyl carbitol, propylene glycol methyl ether acetate, third
One 3 one Methoxypropylacetate of 2-ethoxyethanol acetic acid esters, N, N dimethyl formamides, dimethyl sulfoxide (DMSO), mono- butyrolactone of Y,
Methyl lactate, ethyl lactate etc..These solvents can be used alone or as a mixture
In order to improve the coating appearance, surfactant can be added in the photosensitive layer of the positive-working lithographic printing plate of the present invention.
As the coating method of photosensitive layer, the method for silk stick (coating rod), the side of extrusion type coating machine can be used
Method, method of roll coater (slide blade coater) etc., but it is not limited to these.
[exposed and developed processing]
The light of negative type temperature-sensitive version of the present invention 800-830nm wave-length coverages carries out image exposure to photosensitive layer, passes through development
Processing, can form image on aluminium sheet support surface.
After image exposure, the photosensitive layer of unexposed portion and alkali soluble resins layer are removed by development.It is cloudy in the present invention
The development of pattern temperature-sensitive version uses usual method：At a temperature of 0-60 DEG C, preferably 15-40 DEG C or so, by exposure-processed mistake
Negative type temperature-sensitive version be impregnated in developer solution, with brush wipe etc. carry out.
The negative type temperature-sensitive version of development treatment has been carried out in this way, by washing, has been derived with containing gum arabic or starch
The lipoprotein liquid of not feeling of object etc. is post-processed.These processing can be combined in the post processing of the negative type temperature-sensitive version of the present invention
It uses.The galley prepared by above-mentioned processing such as by using post-exposure can handle, roast at the heat treatment, put forward printing resistance
It is high.
The present invention will be described with reference to embodiments, but the present invention and is not limited to the examples restriction.
Embodiment 1
The making of negative type temperature-sensitive version
Aluminium volume of aluminium sheet (support) curling of thick 0.30mm for web-like (curly) is fixed on submitting machine.It is being surface-treated
10% sodium hydroxide of part impregnates the aluminium sheet continuously sent out from the submitting machine 60 seconds at 70 DEG C, after being etched, uses
After flowing water is washed, 20%HN0 is used3Carry out neutralization washing, washing.The alternating of sine wave is used under conditions of VA=12.7V
Waveform-shaped current, with 300 coulombs/dm in 1% aqueous solution of nitric acid2Anode when electricity electrolytic surface roughening place is carried out to it
Reason.Its surface roughness is measured, is 0.6u m (Ra expressions).
Then it is impregnated in 30% H2SO4In aqueous solution, after carrying out 2 minutes crude removals at 55 DEG C, 33 DEG C, 20%
H2SO4In aqueous solution, cathode is configured on the face of graining, in current density 5A/dm2Under, anodic oxidation in 50 seconds is carried out, it is thick
It spends for 2.7g/m2.In addition, the anode oxide film at the back side in the central portion of aluminium sheet is about 0.5g/m at this time2, it is about 1.0g/ in end
m2。
Following primary coats with coating composition is mixed, is stirred at 30 DEG C.About after five minutes, it finds fever, reacts 60 points
Content is transferred in other container by Zhong Hou, by adding 10000 parts by weight Methanol again, modulates primary coat coating.
(primary coat composition)
100 parts by weight of methanol
120 parts by weight of water
Phosphoric acid (85% aqueous solution) 10 parts by weight
3~methacryloxypropyl triethoxysilane, 25 parts by weight
The liquid coating is applied on above-mentioned processed aluminium sheet and reaches 0.1g/m2, it is dried until aluminium temperature reaches 70
DEG C, cooling is then carried out until aluminum substrate temperature reaches less than 50 DEG C.
(alkali soluble resins layer)
N,N-Dimethylformamide（DMF）6 parts by weight
2 parts by weight of water
25 parts by weight of ethyl cellosolve
Acrylic resin（1）1.5 parts by weight
Oily orchid 603（Beijing Chemical Plant）0.07 parts by weight
BYK-307 polyethoxylated dimethyl silicone copolymers
（BYK Chemie, Wallingford, CT, USA）0.0035 parts by weight
Acrylic resin（1）Structure it is as follows：
The liquid coating is applied on above-mentioned processed aluminium sheet and reaches 0.8g/m2, it is dried until aluminium temperature reaches 105
DEG C, cooling is then carried out until aluminium plate temperature reaches less than 50 DEG C.
On the alkali soluble resins coating obtained in this way, the negative type photosensitive composition of following compositions is coated with, makes dry painting
Cloth weight reaches 1.0g/m2, be dried until aluminium temperature reach 120 DEG C, then carry out cooling until aluminium plate temperature reach 50
Below DEG C.
（Photosensitive layer coating liquid composition）
Linear phenolic resin BTB-24 (Weihai day into chemical plant) 6.90 parts by weight
IR absorbs dyestuff HCD-21 (Japanese woods protochrome Co., Ltd.) 0.15 parts by weight
CYMEL 303 (CYTEC Specialty Chemicals) 0.80 parts by weight
0.52 parts by weight of triazine B (Lucky Huaguang Graphics Co., Ltd.)
Oily orchid 603（Beijing Chemical Plant）0.11 parts by weight
Surfactant FC-4432 (3M companies) 0.02 parts by weight
91.50 parts by weight of propylene glycol monomethyl ether
Embodiment 2
In embodiment l, other than alkali soluble resin layer coating fluid composition change, manufactured using method similarly to Example 1
Negative type temperature-sensitive version.
（Alkali soluble resins layer）
N,N-Dimethylformamide（DMF）6 parts by weight
2 parts by weight of water
25 parts by weight of ethyl cellosolve
PVB modified resins（Diversitec corporation,DT-5）1.5 parts by weight
Oily orchid 603（Beijing Chemical Plant）0.07 parts by weight
BYK-307 polyethoxylated dimethyl silicone copolymers
（BYK Chemie, Wallingford, CT, USA）0.0035 parts by weight
The structural formula of DT-5 is as follows：
Embodiment 3
In embodiment 3, it other than alkali soluble resin layer coating fluid composition change, is manufactured using method similarly to Example 1
Positive-working lithographic printing plate.
(alkali soluble resins layer)
N,N-Dimethylformamide（DMF）6 parts by weight
2 parts by weight of water
25 parts by weight of ethyl cellosolve
Linear phenolic resin BTB29 resins（Weihai day is into Chemical Co., Ltd.）1.3 parts by weight
Tertiary butyl phenol phenolic resin（SP-1077, Lucky Huaguang Graphics Co., Ltd.）0.3 parts by weight
Polyurethane resin 5715（Nuo Yu companies of the U.S.）0.5 parts by weight
Oily orchid 603（Beijing Chemical Plant）0.07 parts by weight
BYK-307 polyethoxylated dimethyl silicone copolymers
（BYK Chemie, Wallingford, CT, USA）0.0035 parts by weight
Comparative example 1
In comparative example 1, the processing before being coated using method similarly to Example 1 to aluminum substrate, and directly coating sense
Photosphere obtains negative type temperature-sensitive version.Photosensitive layer dry coating weight reaches 1.6g/m2, it is dried until aluminium plate temperature reaches
120 DEG C, cooling is then carried out until aluminium temperature reaches less than 50 DEG C.
(photosensitive layer coating liquid composition)
Linear phenolic resin BTB-24 (Weihai day into chemical plant) 6.90 parts by weight
IR absorbs dyestuff HCD-21 (Japanese woods protochrome Co., Ltd.) 0.15 parts by weight
CYMEL 303 (CYTEC Specialty Chemicals) 0.80 parts by weight
0.52 parts by weight of triazine B (Lucky Huaguang Graphics Co., Ltd.)
Oily orchid 603（Beijing Chemical Plant）0.11 parts by weight
Surfactant FC-4432 (3M companies) 0.02 parts by weight
91.50 parts by weight of propylene glycol monomethyl ether
Comparative example 2
In comparative example 2, the processing before being coated using method similarly to Example 1 to aluminum substrate, and directly coating sense
Photosphere obtains negative type temperature-sensitive version.Photosensitive layer dry coating weight reaches 1.6g/m2, it is dried until aluminium temperature reaches 120
DEG C, cooling is then carried out until aluminium temperature reaches less than 50 DEG C.
(photosensitive layer coating liquid composition)
Linear phenolic resin BTB-24 (Weihai day into chemical plant) 5.40 parts by weight
Tertiary butyl phenol phenolic resin（SP-1077, Lucky Huaguang Graphics Co., Ltd.）1.50 parts by weight
IR absorbs dyestuff HCD-21 (Japanese woods protochrome Co., Ltd.) 0.15 parts by weight
CYMEL 303 (CYTEC Specialty Chemicals) 0.80 parts by weight
0.52 parts by weight of triazine B (Lucky Huaguang Graphics Co., Ltd.)
Oily orchid 603（Beijing Chemical Plant）0.11 parts by weight
Surfactant FC-4432 (3M companies) 0.02 parts by weight
91.50 parts by weight of propylene glycol monomethyl ether
Test method
（1）Solvent resistance detection method
The plate obtained by the above method is made a plate using 800 type thermo-sensitive platemaking machines of kodak trendsetter, light source
830nm semiconductor lasers, external drum rotating speed 150rpm, make a plate energy 5W, exports image on the spot.By the image-region on the spot of plate,
The test-strips of 10cm*40cm are cut into, drop experiment, mixed solvent composition ethylene glycol monobutyl ether are carried out with mixed solvent：Isopropyl
Alcohol：Methyl isopropyl Ketone=20：60：20, it is dripped in test-strips within 5 seconds with dropper interval, it is close with 528 types of Ai Seli after washing and drying
It spends instrument and measures solid density.Density is smaller, and density loss is bigger, and solvent resistance is poorer.
（2）Sensitivity is tested
The plate obtained by the above method is made a plate using 800 type thermo-sensitive platemaking machines of kodak trendsetter, light source
830nm semiconductor lasers, external drum rotating speed 150rpm since laser energy 2.5W, are incremented by 0.5mw exposures, maximum laser energy
For 8W, 50% image of plain net is exported.After use（Prosperous prosperous 32CDN developing machines）Development, developer solution are " Hua Guang " TND types（Lekai Hua Guangyin
Brush Science and Technology Ltd.）, 23 DEG C are developed 30 seconds.When plain net reality output is 50 ± 0.5%, laser energy used is suitable
Exposure energy represents sensitivity with laser energy herein, and numerical value is bigger, and sensitivity is lower, and the smaller sensitivity of numerical value is higher.Comparison
Sample needs 135 DEG C of preheating 30s of progress, enhancing plate curing because sensitivity is low after plate exposure, no person makes a plate energy more than platemaking machine
Ceiling capacity.
（3）Development latitude detects：
On 800 type thermo-sensitive platemaking machines of kodak trendsetter, according to 1.2 times of the value of optimum exposure obtained above
Light exposure be exposed, after developed at 23 DEG C with different developing times（Here 10s, 20s, 30s, 40s are selected）, this
Under part, plank can be made to reach requirement（Blank space is not kept on file, density OD values<0.29；Coating does not subtract film on the spot, after development
Field density and plate density ratio before development>0.9；Site reductase 12-99%）The peak of developing time and the difference of minimum
The as development latitude of the plate.
（4）Press resistance rate measures
It exposes and develops under suitable energy, plate is exposed and is developed and is processed and using magnificent light PG-1 type Protection glues
（Lucky Huaguang Graphics Co., Ltd.）Sealing processing is carried out to the space of a whole page.Plate is placed in J4104D type sheet printing machines afterwards
（Print instrument in Jing Dezhen）, carry out printing test（Fountain solution Wei Gela, Hang Hua ink）.After 20000 print of printing, before comparison printing
The abrasion condition of 50% site of the space of a whole page afterwards（Dot density is tested using ICPLATE printing plates measuring instrument）, abrasion is smaller to represent Nai Yin
Rate is higher.
Test result is shown in Table 1.
* after plate exposure, 30s is preheated at 135 DEG C.
What has been described above is only a preferred embodiment of the present invention, it is noted that for those skilled in the art,
Under the premise of general idea of the present invention is not departed from, several changes and improvements can also be made, these should also be considered as the present invention's
Protection domain.
Claims (14)
1. a kind of negative type heat-sensitive CTP plate precursor with double-layer structure, including negative type thermosensitive printing plates ontology, negative type heat
Quick galley ontology includes support, is alkali soluble resins layer on support, has negative type on alkali soluble resins layer
Photosensitive layer, it is characterised in that：The alkali soluble resins layer contains alkali soluble resins, addition resin and illuminating colour.
2. the negative type temperature-sensitive plate precursor according to claim 1 with double-layer structure, it is characterised in that：Alkali soluble resins
Using one or more of organic high molecular polymer soluble or swellability in buck or water, alkali soluble resins is in alkali
Weight percent is 40-90% in soluble resin layer, and the weight average molecular weight of alkali soluble resins is 1000-1000000.
3. the negative type temperature-sensitive plate precursor according to claim 1 with double-layer structure, it is characterised in that：Alkali soluble resins
Addition resin is polyurethane polymer, vinyl-addition polymer, esters of acrylic acid addition polymer, acetal Type of Collective in layer
Object or cellulosic polymer, addition resin are 10-60% in the weight percent of alkali soluble resins layer.
4. the negative type temperature-sensitive plate precursor according to claim 1 with double-layer structure, it is characterised in that：Alkali soluble resins
Illuminating colour is Victoria pure blue, alkaline bright blue, solvent blue, crystal violet, crystal violet or methylene blue in layer, and illuminating colour exists
Weight percent in alkali soluble resins layer is 0.5-5%.
5. the negative type temperature-sensitive plate precursor according to claim 1 with double-layer structure, it is characterised in that：The alkali solubility
0.5 ~ 1.5g/m of resin layer coating weight2。
6. the negative type temperature-sensitive plate precursor according to claim 1 with double-layer structure, it is characterised in that：Negative type is photosensitive
Layer includes film-forming resin, crosslinking agent, infrared absorbing agents, light production acid source and illuminating colour.
7. the negative type temperature-sensitive plate precursor with double-layer structure according to claim 1 or 6, it is characterised in that：Negative type
Film-forming resin is linear phenolic resin in photosensitive layer, and film-forming resin dosage accounts for the 30-90% of photosensitive composition total weight, film forming tree
Fat weight average molecular weight is 2000-10000, Mw/MnFor 1.5-20.
8. the negative type temperature-sensitive plate precursor with double-layer structure according to claim 1 or 6, it is characterised in that：Crosslinking agent
Dosage account for the 8-20 % of photosensitive composition total weight.
9. the negative type temperature-sensitive plate precursor with double-layer structure according to claim 1 or 6, it is characterised in that：Negative type
Crosslinking agent is melamine derivative in photosensitive layer.
10. the negative type temperature-sensitive plate precursor with double-layer structure according to claim 1 or 6, it is characterised in that：Negative type
Photosensitive layer middle infrared absorption agent is a kind of absorption dyestuff for the light that can absorb 760-1200nm wavelength, and the dosage of infrared absorbing agents accounts for
Photosensitive composition is 0.5-3%.
11. the negative type temperature-sensitive plate precursor with double-layer structure according to claim 1 or 6, it is characterised in that：Negative type
The agent of photosensitive layer middle infrared absorption is cyanine dye, polymethin dyes, rectangular salt dyestuff chrome dye, pyrans or thio-pyrylium
Dyestuff.
12. the negative type temperature-sensitive plate precursor with double-layer structure according to claim 1 or 6, it is characterised in that：Negative type
Compound of the light production acid source for the reaction that can smoothly decompose under heat effect in photosensitive layer, the dosage of light production acid source account for photosensitive composition
The 0.1-5% of object total weight.
13. the negative type temperature-sensitive plate precursor according to claim 12 with double-layer structure, it is characterised in that：Negative type sense
Light production acid source is trichloromethyl compound in triazine class in photosphere.
14. the negative type temperature-sensitive plate precursor with double-layer structure according to claim 1 or 6, it is characterised in that：Negative type
Illuminating colour is Victoria pure blue, alkaline bright blue, solvent blue, crystal violet, crystal violet or methylene blue in photosensitive layer, and coloring contaminates
It is 0.5-5% to expect the weight percent in photosensitive layer.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113655690A (en) * | 2021-08-11 | 2021-11-16 | 彭朝珍 | On-press development type negative heat-sensitive CTP plate material |
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