CN106324991B - Elastomer composition for water-washable flexographic plate and water-washable flexographic plate containing same - Google Patents

Elastomer composition for water-washable flexographic plate and water-washable flexographic plate containing same Download PDF

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CN106324991B
CN106324991B CN201510344319.0A CN201510344319A CN106324991B CN 106324991 B CN106324991 B CN 106324991B CN 201510344319 A CN201510344319 A CN 201510344319A CN 106324991 B CN106324991 B CN 106324991B
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water
grafted
bond
urethanized
double
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CN106324991A (en
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宋小伟
张涛
高英新
张刚
邵国安
张攀
李喜乐
马天如
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Lucky Huaguang Graphics Co Ltd
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Lucky Huaguang Graphics Co Ltd
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Abstract

The present invention relates to an elastomer composition for a water-washable flexographic plate, comprising: (A) water-soluble copolymers with branched, grafted, reactive urethanized double bonds; (B) liquid polybutadiene with a urethane double bond grafted at the end; (C) unsaturated monomer containing at least more than 1 double bond; (D) a photopolymerization initiator; (E) dyes and (F) further additives. The product of the invention has excellent printing durability and ink affinity.

Description

Elastomer composition for water-washable flexographic plate and water-washable flexographic plate containing same
Technical Field
The invention belongs to the technical field of relief printing, and particularly relates to an elastomer composition for a water-washable flexible plate and the water-washable flexible plate containing the elastomer composition.
Background
In recent years, flexible photosensitive resin plates are widely used for printing of easily deformable or softer printing materials such as cartons, flexible packages, labels and the like. At present, the technology of the common flexible photosensitive resin plate is mature, foreign companies such as DuPont, Asahi, Maide and Fulinte produce plate materials, and Lekai Huaguang printing technology Limited company produces plate materials at home. The common flexible photosensitive resin plate needs to be developed by adopting a solvent, the waste solvent is generated to have adverse effects on production, use and physical and mental of operators, and meanwhile, the pollution is caused to the surrounding environment.
The prior art is as follows: the development of water-washed flexographic plates has been essentially achieved by water development through water-soluble polymers or low molecules in photosensitive elastomers. US 4540649-aqueous developable photopolymerizable compositions and printing plates made therefrom, the photopolymerizable compositions comprising at least one soluble high molecular polymer, such as polyvinyl alcohol or partially saponified polyvinyl acetate; US 5175076-aqueous developable photosensitive composition for producing relief printing plates, photopolymerizable composition comprising amino, amide based compounds such as compound N, N-dimethylaminoethyl (meth) acrylate, N-dimethylaminopropyl (meth) acrylamide, etc. used alone or in combination; WO2011013601 adds a latex such as polybutadiene latex, natural rubber latex, styrene-butadiene copolymer latex, and the like to the photosensitive elastomer in addition to polyvinyl alcohol.
The water-washing flexible plate material technology solves the problem of water development of the plate material, but brings a negative effect, namely the printing resistance and the ink affinity of the plate material are reduced. The water developability, the printing resistance and the ink affinity of the water-washed flexible plate are a group of contradictory problems, the water dominance of the plate is improved, and the printing resistance and the ink affinity of the plate are usually sacrificed. The problem of solving the contradiction between the two is a technical hotspot for developing the water-washing flexible printing plate.
The present invention is to solve the above problems. The invention is characterized in that: 1. the special aqueous polymer contains an externally suspended polyether group to realize hydrophilicity, the polymer introduces urethane double bonds through polyurethane reaction grafting, the urethane group has good toughness and strong printing resistance and ink affinity, and the printing resistance and the ink affinity of the exposed part of the plate are improved by curing the grafted double bonds; 2. meanwhile, double bonds are grafted at the tail end of the ammonia esterification to modify the liquid polybutadiene, the urethane double bonds increase the crosslinking density of the exposed part, and the printing resistance and the ink affinity of the exposed part of the printing plate are improved.
Disclosure of Invention
The invention provides an elastomer composition for a water-washable flexible plate and a water-washable flexible plate containing the same, wherein the product has excellent printing resistance and ink affinity.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
The present invention provides an elastomer composition for water-washed flexographic plates, comprising: (A) water-soluble copolymers with branched, grafted, reactive urethanized double bonds; (B) liquid polybutadiene with a urethane double bond grafted at the end; (C) unsaturated monomer containing at least more than 1 double bond; (D) a photopolymerization initiator; (E) dyes and (F) further additives.
the water-soluble copolymer (A) with branched chain grafted with active double-bond of amino esterification accounts for 45 ~ 77% of the total mass of the elastomer composition, the liquid polybutadiene (B) with tail end grafted with double-bond of amino esterification accounts for 10 ~ 30% of the total mass of the elastomer composition, the unsaturated monomer (C) with at least more than 1 double-bond accounts for 10 ~ 15% of the total mass of the elastomer composition, the photopolymerization initiator (D) accounts for 1 ~ 5% of the total mass of the elastomer composition, the dye (E) accounts for 1 ~ 5% of the total mass of the elastomer composition, and the other additives (F) are added.
The water-soluble copolymer (A) with branched grafted active aminoesterified double bonds has the following structure:
Wherein R 1 is H or CH 3, R 2 is H or CH 3, the copolymerization ratio (weight percentage) a is 20 ~ 80%, b is 10 ~ 40%, c is 10 ~ 40, and the polymerization degree n of polyether is 9 ~ 125.
the water-soluble copolymer of the present invention contains a thermoplastic styrene structural unit, it is known that the styrene structural unit has good rigidity, lipophilicity and thermoplasticity, the good rigidity contributes to the dimensional stability of the elastomer, the good lipophilicity contributes to the printing resistance and the ink affinity of the elastomer, and the good thermoplasticity contributes to the hot extrusion processing of the elastomer, and the copolymerization ratio a of the thermoplastic styrene structural unit of the water-soluble copolymer of the present invention is 20 ~ 80% by weight.
The water-soluble copolymer of the present invention contains an aminoesterification active double bond. The urethane reactive double bond is grafted through urethane reaction, and a polymer copolymerization unit is designed with a graft bridge: acrylic acid copolymerization units containing branched hydroxyl groups are grafted with urethane-forming active double bonds through the reaction of hydroxyl groups and isocyanate groups. Optional hydroxyl group-containing acrylic monomers as copolymerized units are 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate (HPA), 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl methacrylate (HPMA), etc., with 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate (HEMA) being preferred in the present invention.
The structural formula of the grafting active monoisocyanate is as follows:
R 1 is a hydrogen atom or a methyl group, R 2 is an ester group, phenylene group, valence bond or the like, and R is an integer of 1 to 3.
The detailed examples are shown in the following structural formulas, but the present invention is not limited to the following structural formulas of M1-M3.
M1
M2
M3
The unsaturated monoisocyanate M2 which is the only industrial Product at present and has the chemical name of methacryloyloxyethyl isocyanate MOI can be purchased from Japanese Showa Denko K.K., the Product code and the Product physical and chemical properties can be seen in the molar mass ratio of Karenz MOI/Product/Showa Denko group, the hydroxyl-containing acrylic monomer to the grafted active monoisocyanate MOI is 1:1, and the proportion of the hydroxyl-containing acrylic monomer copolymerized unit b in the multipolymer is 10 ~ 40 percent by weight.
The water-soluble polymer or low molecule of the water-soluble flexible plate is used for realizing water development by the water-soluble polymer or low molecule in the photosensitive elastomer, the water-soluble polymer or low molecule is required to contain hydrophilic groups, the selectable hydrophilic groups comprise acid or acid anhydride groups, carboxyl groups, sulfonic acid groups, phosphoric acid groups, carboxylic anhydride, maleic anhydride and the like, basic groups comprise amino groups, quaternary ammonium base and the like, ester groups and lactone groups, hydroxyl groups, phenolic hydroxyl groups, polyvinyl alcohol, cellulose and derivatives thereof, polyether groups comprise polyethylene glycol, polypropylene glycol and the like, active hydrogen-containing acid amides and the like, acid-based salts, alkali metal salts, quaternary ammonium salts and the like, and the groups can realize water development.
The water-soluble heat-crosslinked copolymer is synthesized by firstly synthesizing a parent copolymer and then grafting aminoesterification double bonds, the synthesized parent copolymer is synthesized by a solution copolymerization method or a bulk polymerization method, the copolymerization reaction can be random copolymerization or block copolymerization, preferably random copolymerization, a polymerization initiator comprises peroxides such as di-tert-butyl peroxide, benzoyl peroxide, persulfates such as potassium persulfate and ammonium persulfate, azo compounds such as azodiisobutyronitrile and the like, the copolymerization method is preferably solution polymerization, and the polymerization and grafting can be synthesized by a two-pot method or a one-pot method, the two-pot method is firstly synthesized into a parent resin, and the reaction solvents selected from water, methanol, ethanol, N-propanol, isopropanol, butanol, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, tetrahydrofuran, 1, 4-dioxane, N-dimethylformamide, dimethylacetamide acetone, methyl ethyl ketone, cyclohexane, ethylene dichloride, toluene, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol methyl ether, propylene glycol ethyl ether, acetylacetone, diacetone alcohol, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol ether acetate, ethylene glycol ether acetate, ethylene glycol ether, propylene glycol ether acetate, propylene glycol ether acetate, propylene glycol ether.
The weight average molecular weight of the water-soluble thermal cross-linking copolymer is 10000 ~ 100000, and the glass transition temperature is 90 ~ 130 ℃.
the water-soluble thermal crosslinking copolymer designed by the invention accounts for 45 ~ 77 percent of the total weight of the elastomer.
The liquid polybutadiene with the end grafted with the aminoesterification double bond has one or a mixture of 4 structures as shown in the following (I), (II), (III) and (IV):
（Ⅰ）
（Ⅱ）
（Ⅲ）
（Ⅳ）
Wherein, the dotted line in the 1, 4-bond repeating unit in the structural formula (III) and (IV) represents a trans-bond or a cis-bond; the molecular weight of the liquid polybutadiene with the tail end grafted with the amino esterification double bond is 1000-5000.
The elastomer composition for the water-washing flexible plate contains rubber elastic structure high molecules, can select high molecules with a butadiene skeleton or an isoprene skeleton in a molecular chain, preferably low-molecular-weight and liquid rubber elastic structure high molecules, preferably has a butadiene skeleton, a molecular weight of 1000-5000 and liquid polybutadiene, has an internal molecular structure of 1,2, or 1,4 or a mixture of the two, and has a three-dimensional structure of cis, trans or a mixture of the two. The elastomeric composition for water-washed flexographic plates of the present invention is preferably a liquid butadiene which is modified at the end of the molecule. Introducing a functional group of urethane double bonds at the tail end of a liquid butadiene molecule, enhancing the polymerization capability of the exposed part of the plate, and improving the printing resistance and the ink affinity of the plate. The functional group of urethane double bond introduced into the end of the liquid butadiene molecule can be obtained by urethane reaction of hydroxyl-terminated liquid butadiene and monoisocyanate acrylate. Such commercial products are available from companies home and abroad such as Satomer, Total, Nippon Soda, Dupont, Osaka organic chemistry, Nippon Soda, Hippon Zibo Zizipolon chemical, and the like.
The unsaturated monomer (C) containing at least more than 1 double bond is unsaturated acrylate or unsaturated polyurethane acrylate.
The elastomer composition for the water-washing flexible plate contains (C) unsaturated monomers containing at least more than 1 double bond, and improves the photosensitivity of the plate material, wherein the monomers comprise: pentaerythritol triacrylate, pentaerythritol diacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dimethylolpropane diacrylate, trimethylolpropane triacrylate, isobornyl acrylate, tetrahydrofurfuryl alcohol acrylate, glycidyl methacrylate, hydroxyethyl acrylate, 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, 1, 5-pentanediol diacrylate, 1, 5-pentanediol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, pentaethylene glycol dimethacrylate, dipropylene glycol diacrylate, pentaerythritol diacrylate, and mixtures thereof, Glycerol propoxylate triacrylate, lauryl methacrylate, stearyl methacrylate, Satomer366, Satomer399, and the like.
The photopolymerization initiator (D) is an alpha-cleaved compound, and the alpha-cleaved compound is preferably a benzoin derivative or a dehydrobenzophenone derivative. They may be benzoin-derived methyl ether, benzoin-derived ethyl ether, benzoin-derived propyl ether, benzoin-derived n-butyl ether, benzoin-derived isobutyl ether, α -hydroxymethylbenzoin-derived methyl ether, α -methoxybenzoin-derived methyl ether, benzoin ethyl ether, benzophenone, Michler's ketone, 4-acetoxy-4-diethylamine benzophenone, α -hydroxyisopropyl benzophenone, 2-phenyl-2, 2-dimethoxyacetophenone, 2-tert-butylanthraquinone, isopropyl thioxanthone, 4-bisdiethylaminobenzophenone, 4-dichlorobenzophenone and the like.
The (E) dye is preferably neutral red, basic red or rhodamine blue.
The elastomeric composition for water-washable flexographic plates according to the present invention further comprises (E) a dye selected from neutral Red, basic Red, rhodamine blue and the like dyes, such as Neozapon Red335, Neozapon Red395, Neozapon Red346, neutral Red CI50040, Red-base543, basic Red T-CI50240, rhodamine blue, solvent-Red 135, solvent-Red 52, solvent-Red 145, solvent-Red 179, solvent-Red 235, solvent-orange 235, Valifast-Red3320 and the like.
And the other additives (F) are an antioxidant, a thermal inhibitor, a release agent or a leveling agent.
Other additives such as antioxidant 264, antioxidant 1010; thermal polymerization inhibitors such as hydroquinone, nitroxide radical piperidinol, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4 '-thiobis- (3-methyl-6-t-butylphenol), 2' -methylenebis (4-methyl-16-t-butylphenol), and the primary cerium salt of N-nitrosophenylhydroxylamine, and the like; mold release agents such as methyl phthalate, ethyl phthalate, butyl phthalate polyvinyl chloride oligomer and the like; the leveling agent is tween-20, tween-30, tween-85, span-20, span-40, span-60, span-85, etc.
A water-washable flexographic plate having excellent press durability and ink affinity, wherein the above elastomer composition is present on the surface of a support. The water-washing flexible resin plate comprises a base material, an adhesive layer, an elastomer and a protective film or a laser ablation film from bottom to top in sequence. The substrates typically include paper-based substrates, polymeric substrates such as polyester film substrates, and metal-based substrates such as copper, steel, aluminum panels, and the like. The flexible resin plate with low printing times can adopt a high-strength paper base, such as long fiber paper, such as cotton fiber paper, linen paper, plastic-coated paper of the long fiber paper and the linen paper, reinforced paper and the like, and has low cost but poor dimensional stability; the flexible resin plate can also adopt a macromolecule film substrate, such as polyvinyl acetate, polyethylene, polystyrene, polyvinyl chloride, polyurethane, polycarbonate, polyamide and the like, and the most common is a terylene film substrate, which has low cost and good dimensional stability; compared with paper-based substrates and high polymer material substrates, the metal-based substrate has the advantages of easiness in fixation, good size stability, difficulty in deformation, repeated reciprocating use, good online shop reduction, high printing quality and the like, and is widely applied to development and production of high-grade flexible resin plates. The metal-based substrate may be selected from iron-based substrates such as galvanized iron, stainless steel, magnetizable and elastic steel, and metals such as aluminum, zinc, copper, manganese, chromium, nickel, and alloys thereof, which provide sufficient strength and flexibility. The invention preferably selects a polyester film base or a metal base substrate, 1, has enough strength, and ensures the dimensional stability of the brush; 2. the paper has certain flexibility, does not crack or deform during curling, and is easy to roll; 3. has good processability; 4. and (4) the cost is low. In the production of flexible resin plates, the high-temperature extrusion-molded photosensitive elastomer composition firmly adheres the elastomer to the substrate through the adhesive layer.
Compared with the prior art, the invention has the advantages that:
1. The water-soluble copolymer grafted with the active double bonds is a special water-based polymer, the hydrophilicity is realized by containing externally suspended polyether groups, the urethanization double bonds are introduced into the polymer through polyurethane reaction grafting, the urethane groups have good toughness and strong printing resistance and ink affinity, and the printing resistance and the ink affinity of the exposed part of the plate are improved by the solidification of the grafted double bonds;
2. The end of the component (B) is grafted with liquid polybutadiene with an amino-esterified double bond; contains aminoesterification double bond, and compared with common unmodified liquid polybutadiene, it can raise crosslinking density of exposed portion and raise the resistance of exposed portion of printing plate material
3. The elastomer composition for the water-washing flexible plate contains (C) unsaturated monomers containing at least more than 1 double bond, and improves the photosensitive printing force and the ink affinity of the plate material.
4. The elastomer composition for the water-washable flexible printing plate also comprises (D) a photopolymerization initiator, (E) a dye and (F) other additives, and the components are combined to jointly act to improve the printing resistance and the ink affinity of the printing plate.
Detailed Description
The following examples are intended to illustrate the present invention, but the present invention is not limited thereto.
in the examples, styrene St: from Yanshan petrochemical; hydroxyethyl methacrylate HEMA, hydroxyethyl acrylate HEA: are all from Mitsubishi yang of Japan; polyethylene glycol methacrylate PEGMA, polyethylene glycol acrylate PEGA: all from British-Sigma; methacryloyloxyethyl isocyanate MOI: from showa electrician, japan; azobisisobutyronitrile AIBN: from Foson chemistry; dimethylformamide DMF: chemistry of dicarbon; isopropyl alcohol IPA: from exxonmobil (china); nitroxide radical piperidinol ZJ 701: from carbofuran; dibutyl tin laurate DBTDL: from Tianjin chemical reagent plant.
Firstly, synthesizing a water-soluble copolymer A1-A17 grafted with activated double bonds:
Polymer A1 into a 500ml flask were charged St80.0g, HEMA10.0g, and PEGMA
(n =125)10.0g, AIBN1.0g, DMF300g, nitrogen protection, stirring for 200r/min, heating to 80 ℃, reacting for 6 hours, adding MOI11.9g, DBTDL0.10g and ZJ701-0.06g, continuing to react for 30 minutes, stopping reaction, cooling to 10 ℃, pouring the reaction liquid into 5 ℃ 500ml IPA for precipitation, sufficiently extruding and washing in 5 ℃ IPA, and then drying in vacuum.
polymer A2 was prepared by charging St20.0g, HEA40.0g, PEGMA (n =9)40.0g, AIBN1.0g, and DMF300g into a 500ml flask, stirring at 200r/min under nitrogen protection, heating to 80 ℃ for 6 hours, charging MOI53.4g, DBTDL0.5g, and ZJ701-0.25g, continuing the reaction for 30 minutes, cooling to 10 ℃, pouring the reaction mixture into 500ml IPA at 5 ℃ for precipitation, sufficiently extruding and washing with IPA at 5 ℃, and vacuum-drying.
Polymer A3 was prepared by charging St70.0g, HEMA20.0g, PEGMA (n =115)10.0g, AIBN1.0g, DMF300g into a 500ml flask, stirring at 200r/min under nitrogen protection, heating to 80 ℃ for 6 hours, charging MOI23.8g, DBTDL0.25g, ZJ701-0.12g, continuing the reaction for 30 minutes, cooling to 10 ℃, pouring the reaction mixture into 500ml IPA at 5 ℃ for precipitation, sufficiently extruding and washing in IPA at 5 ℃, and vacuum-drying.
polymer A4 was prepared by charging St70.0g, HEA10.0g, PEGMA (n =85)20.0g, AIBN1.0g, and DMF300g into a 500ml flask, stirring at 200r/min, heating to 80 ℃ for 6 hours, charging MOI13.4g, DBTDL0.13g, and ZJ701-0.067g, continuing the reaction for 30 minutes, cooling to 10 ℃, pouring the reaction mixture into 500ml IPA at 5 ℃ to precipitate, sufficiently squeezing and washing in IPA at 5 ℃, and vacuum-drying.
polymer A5 was prepared by charging St70.0g, HEMA15.0g, PEGA (n =105)15.0g, AIBN1.0g, and DMF300g into a 500ml flask, stirring at 200r/min under nitrogen protection, heating to 80 ℃ for 6 hours, charging MOI17.9g, DBTDL0.18g, and ZJ701-0.09g, continuing the reaction for 30 minutes, cooling to 10 ℃, pouring the reaction solution into 500ml IPA at 5 ℃ for precipitation, sufficiently extruding and washing with IPA at 5 ℃, and vacuum-drying.
Polymer A6 was prepared by charging St60.0g, HEMA30.0g, PEGMA (n =110)10.0g, AIBN1.0g, DMF300g into a 500ml flask, stirring at 200r/min under nitrogen protection, heating to 80 ℃ for 6 hours, charging MOI40.1g, DBTDL0.4g, ZJ701-0.2g, stopping the reaction for 30 minutes, cooling to 10 ℃, pouring the reaction mixture into 500ml IPA at 5 ℃ for precipitation, sufficiently squeezing and washing in IPA at 5 ℃, and vacuum-drying.
Polymer A7 was prepared by charging St60.0g, HEMA10.0g, PEGA (n =30)30.0g, AIBN1.0g, and DMF300g into a 500ml flask, stirring with nitrogen gas, heating to 80 ℃ for 6 hours, charging MOI11.9g, DBTDL0.1g, and ZJ701-0.06g, stopping the reaction for 30 minutes, cooling to 10 ℃, pouring the reaction solution into 500ml IPA at 5 ℃ for precipitation, sufficiently squeezing and washing in IPA at 5 ℃, and vacuum-drying.
Polymer A8 was prepared by charging St60.0g, HEMA25.0g, PEGMA (n =95)15.0g, AIBN1.0g, DMF300g into a 500ml flask, stirring at 200r/min under nitrogen protection, heating to 80 ℃ for 6 hours, charging MOI29.8g, DBTDL0.3g, ZJ701-0.15g, continuing the reaction for 30 minutes, cooling to 10 ℃, pouring the reaction mixture into 500ml IPA at 5 ℃ for precipitation, sufficiently extruding and washing in IPA at 5 ℃, and vacuum-drying.
Polymer A9 was prepared by charging St50.0g, HEA25.0g, PEGMA (n =65)25.0g, AIBN1.0g, and DMF300g into a 500ml flask, stirring at 200r/min under nitrogen protection, heating to 80 ℃ for 6 hours, charging MOI33.4g, DBTDL0.33g, and ZJ701-0.17g, stopping the reaction for 30 minutes, cooling to 10 ℃, pouring the reaction mixture into 500ml IPA at 5 ℃ for precipitation, sufficiently squeezing and washing in IPA at 5 ℃, and vacuum-drying.
Polymer A10 was prepared by charging St50.0g, HEMA20.0g, PEGA (n =55)30.0g, AIBN1.0g, and DMF300g into a 500ml flask, stirring at 200r/min under nitrogen protection, heating to 80 ℃ for 6 hours, charging MOI23.8g, DBTDL0.24g, and ZJ701-0.12g, stopping the reaction for 30 minutes, cooling to 10 ℃, pouring the reaction solution into 500ml IPA at 5 ℃ for precipitation, sufficiently squeezing and washing in IPA at 5 ℃, and vacuum-drying.
polymer A11 was prepared by charging St50.0g, HEA30.0g, PEGMA (n =70)20.0g, AIBN1.0g, and DMF300g into a 500ml flask, stirring at 200r/min under nitrogen protection, heating to 80 ℃ for 6 hours, charging MOI41.1g, DBTDL0.41g, and ZJ701-0.21g, continuing the reaction for 30 minutes, cooling to 10 ℃, pouring the reaction solution into 500ml IPA at 5 ℃ for precipitation, sufficiently squeezing and washing in IPA at 5 ℃, and vacuum-drying.
Polymer A12 was prepared by charging St40.0g, HEMA30.0g, PEGMA (n =45)30.0g, AIBN1.0g, DMF300g into a 500ml flask, stirring at 200r/min under nitrogen protection, heating to 80 ℃ for 6 hours, charging MOI35.8g, DBTDL0.36g, ZJ701-0.18g, continuing the reaction for 30 minutes, cooling to 10 ℃, pouring the reaction solution into 500ml IPA at 5 ℃ for precipitation, sufficiently extruding and washing in IPA at 5 ℃, and vacuum-drying.
polymer A13, adding St40.0g, HEA20.0g, PEGMA (n =20)40.0g, AIBN1.0g into a 500ml flask, stirring under nitrogen protection for 200r/min, heating to 80 ℃, reacting in bulk for 1 hour, adding MOI26.7g, DBTDL0.27g, and ZJ701-0.13g, continuing to perform thermal extrusion reaction for 30 minutes, stopping, and cooling to room temperature to obtain the target resin for later use.
Polymer A14 was prepared by charging St40.0g, HEMA40.0g, PEGA (n =75)20.0g, AIBN1.0g, and DMF300g into a 500ml flask, stirring with nitrogen gas, heating to 80 ℃ for 6 hours, charging MOI47.9g, DBTDL0.48g, and ZJ701-0.24g, stopping the reaction for 30 minutes, cooling to 10 ℃, pouring the reaction solution into 500ml IPA at 5 ℃ for precipitation, sufficiently squeezing and washing in IPA at 5 ℃, and vacuum-drying.
Polymer A15 was prepared by charging St30.0g, HEMA40.0g, PEGMA (n =40)30.0g, AIBN1.0g, DMF300g into a 500ml flask, stirring at 200r/min under nitrogen protection, heating to 80 ℃ for 6 hours, charging MOI47.9g, DBTDL0.48g, ZJ701-0.24g, continuing the reaction for 30 minutes, cooling to 10 ℃, pouring the reaction solution into 500ml IPA at 5 ℃ for precipitation, sufficiently extruding and washing in IPA at 5 ℃, and vacuum-drying.
Polymer A16 was prepared by charging St30.0g, HEMA30.0g, PEGMA (n =15)40.0g, AIBN1.0g, DMF300g into a 500ml flask, stirring at 200r/min under nitrogen protection, heating to 80 ℃ for 6 hours, charging MOI35.8g, DBTDL0.36g, ZJ701-0.18g, stopping the reaction for 30 minutes, cooling to 10 ℃, pouring the reaction solution into 500ml IPA at 5 ℃ for precipitation, sufficiently extruding and washing in IPA at 5 ℃, and vacuum-drying.
Polymer A17 was prepared by charging St30.0g, HEA35.0g, PEGMA (n =25)35.0g, AIBN1.0g, and DMF300g into a 500ml flask, stirring at 200r/min under nitrogen protection, heating to 80 ℃ for 6 hours, charging MOI46.8g, DBTDL0.47g, and ZJ701-0.23g, continuing the reaction for 30 minutes, cooling to 10 ℃, pouring the reaction mixture into 500ml IPA at 5 ℃ for precipitation, sufficiently extruding and washing with IPA at 5 ℃, and vacuum-drying.
Secondly, synthesizing a water-soluble copolymer A ' 1, A ' 4, A ' 7, A ' 12, A ' 16:
Polymer a' 1 to a 500ml flask were added st80.0g, hema10.0g, PEGMA
(n =125)10.0g, AIBN1.0g, DMF300g, nitrogen protection, stirring 200r/min, heating to 80 ℃, reacting for 6 hours, cooling to 10 ℃, pouring the reaction liquid into 5 ℃ 500ml IPA for precipitation, sufficiently extruding and washing in 5 ℃ IPA, and then drying in vacuum.
Adding St70.0g, HEA10.0g, PEGMA (n =85)20.0g, AIBN1.0g and DMF300g into a 500ml flask, stirring for 200r/min under the protection of nitrogen, heating to 80 ℃, reacting for 6 hours, cooling to 10 ℃, pouring the reaction liquid into 5 ℃ 500ml IPA for precipitation, sufficiently extruding and washing in 5 ℃ IPA, and then drying in vacuum.
Adding St60.0g, HEMA10.0g, PEGA (n =30)30.0g, AIBN1.0g and DMF300g into a 500ml flask, stirring for 200r/min under the protection of nitrogen, heating to 80 ℃, reacting for 6 hours, cooling to 10 ℃, pouring the reaction liquid into 5 ℃ 500ml IPA for precipitation, sufficiently extruding and washing in 5 ℃ IPA, and then drying in vacuum.
adding St40.0g, HEMA30.0g, PEGMA (n =45)30.0g, AIBN1.0g and DMF300g into a 500ml flask, stirring for 200r/min under the protection of nitrogen, heating to 80 ℃, reacting for 6 hours, cooling to 10 ℃, pouring the reaction liquid into 5 ℃ 500ml IPA for precipitation, sufficiently extruding and washing in 5 ℃ IPA, and then drying in vacuum.
Adding St30.0g, HEMA30.0g, PEGMA (n =15)40.0g, AIBN1.0g and DMF300g into a 500ml flask, stirring for 200r/min under the protection of nitrogen, heating to 80 ℃, reacting for 6 hours, cooling to 10 ℃, pouring the reaction liquid into 5 ℃ 500ml IPA for precipitation, sufficiently extruding and washing in 5 ℃ IPA, and then drying in vacuum.
Plate manufacturing: the elastomer composition is added into a mixing extruder in proportion, heated, mixed and extruded, an elastomer layer is hot-pressed on a 125-micron PET film support body (produced by Lekai group film company) coated with polyurethane adhesive by a hot-pressing machine at 100 ℃, and then a polyvinyl alcohol oxygen-resistant PET strippable protective film (produced by Lekai group film company) is sequentially coated on the elastomer layer to produce a conventional platemaking water-washing flexible plate, or the polyvinyl alcohol carbon black heat-ablative oxygen-resistant PET strippable protective film (produced by Lekai group film company) to produce a digital water-washing flexible plate.
Exposure of the plate material: performing common plate operation, namely performing back exposure for 20 seconds by using a Kyowa Kogyo KY1320 flexo plate making machine, removing a PET protective film, attaching a film, vacuumizing and performing positive exposure for 12 minutes; digital plate operation-use Guangzhou white cloud trade KY1320 flexible plate-making machine back exposure for 20 seconds, remove PET protective film, use ESKO laser ablation machine direct plate-making, then evacuation positive exposure for 12 minutes.
Developing the plate material: and (3) washing the exposed plate material for 5 minutes by using tap water on a KMPXH900 flexible plate washing machine, drying for 1.5 hours at the temperature of 60 ℃, and curing the lower surface of an ultraviolet lamp with the spacing of 280nm and 5cm for 5 minutes to obtain the printing plate material. And (3) water washing rating: 1-5 stars rating method, 1-2 stars are not qualified, 3 stars are qualified, 4 stars are good, 5 stars are good. Ink affinity index: and (3) making 10-grade exposure energy ladder ruler strips, testing printing ink affinity indexes, wherein 10 grades are optimal, 1 grade is worst, and 6 grades are qualified.
printing by a printing plate: printed by using an EKOFA1100N flexo printing machine, and properties such as plate dot reduction capability, inking property, printing resistance and the like are examined.
Example 1:
Polymer a1: 77g, urethanized double-bond polybutadiene (structure I, Mw =1000, Nippon Cauda) 10g, 1, 6-hexanediol diacrylate (Tianjiao) 2g, hydroxyethyl methacrylate (Mitsubishang Yang) 4g, dipentaerythritol triacrylate (sartomer) 5g, initiator 651 (Jingjiang Hongtai chemical industry) 1g, Neozapon-red395 (Pasff) 0.5g, 2, 6-ditert-butyl-p-cresol (Nanjing Jiulon Kakko chemical industry) 0.1g, t-alkylethoxyamine (dicarbon chemical industry) 0.1g, and Tween 20 (Fushan Kogaku gas chemical industry) 0.3 g.
The performance of the plate material is as follows: and (3) water washing rating: 3, star; an ink affinity index of 10; and (3) reducing a 125lpi net point: 2% -98%, independent points: 0.2 mm; independent line 0.1mm, print times: 42 ten thousand.
Example 2:
45g of polymer A2, 30g of urethanized double-bond polybutadiene (structure II, Mw =5000, Zibozilong), 12g of 1, 6-hexanediol diacrylate (Tianjiao), 5g of hydroxyethyl methacrylate (Mitsubishang Yang), 13g of dipentaerythritol triacrylate (Sadorma), 5g of initiator 651 (Jingjiang Hongtai chemical industry), 2g of Neozapon-red395 (Pasteff), 1g of 2, 6-ditert-butyl-p-cresol (Nanjing Jiulon Jiulong chemical industry), 1g of tert-alkyl ethoxyamine (Bicarbo chemical industry), and 1g of Tween 20 (Fushan chemical industry).
the performance of the plate material is as follows: and (3) water washing rating: 5 stars; an ink affinity index of 7; reduction of 122lpi net point: 2% -98%, independent points: 0.2 mm; independent line 0.1mm, print times: 28 ten thousand.
Example 3:
76g of polymer A3, 5g of urethanized double-bond polybutadiene (structure III, Mw =1500, Nippon soda), 5g of urethanized double-bond polybutadiene (structure I, Mw =2000, Nippon soda), 2g of 1, 6-hexanediol diacrylate (Tianjiao), 5g of hydroxyethyl methacrylate (Mitsubishang), 1g of Satomer399 (Sadoma), 1g of initiator 651 (Jingjiang macrochemical. RTM., Ltd.), 2g of Neozapon-red395 (Basff.), 2g of 2, 6-ditert-butyl-p-cresol (Nanjing nona Longji chemical Co., Ltd.), 1g of tert-alkyl ethoxy amine (Union carbide chemical Co., Ltd.), and 1g of Tween 20 (Fushan Ke gas chemical Co., Ltd.).
the performance of the plate material is as follows: and (3) water washing rating: 4 stars; and (3) reducing a 125lpi net point: 2% -98%, independent points: 0.2 mm; independent line 0.1mm, print times: 30 ten thousand.
Example 4:
70g of polymer A4, 20g of urethanized double-bond polybutadiene (structure III, Mw =1300, Total), 2g of 1, 6-hexanediol diacrylate (Tianjiao), 2g of hydroxyethyl methacrylate (Mitsubishang Yang), 1g of dipentaerythritol triacrylate (sartomer), 2g of initiator 651 (Jingjiang Hongtai chemical industry), 1g of Neozapon-red395 (Pasteff), 2g of 2, 6-ditert-butyl-p-cresol (Nanjing Jiulong chemical industry), 1g of tert-alkyl ethoxyamine (bicarbon chemical industry), and 2g of Tween 20 (Fushan chemical industry).
The performance of the plate material is as follows: and (3) water washing rating: 5 stars; an ink affinity index of 9; and (3) reducing a 125lpi net point: 2% -98%, independent points: 0.2 mm; independent line 0.1mm, print times: 29 ten thousand.
Example 5:
75g of polymer A5, 10g of urethanized double-bond polybutadiene (structure II, Mw =1400, Total), 2g of 1, 6-hexanediol diacrylate (Tianjiao), 2g of hydroxyethyl methacrylate (Mitsubishang Yang), 1g of dipentaerythritol triacrylate (sartomer), 2g of initiator 651 (Jingjiang Hongtai chemical industry), 3g of Neozapon-red395 (Pasteff), 2g of 2, 6-ditert-butyl-p-cresol (Nanjing Jiulong chemical industry), 2g of tert-alkyl ethoxyamine (dicarbonic chemical industry), and 3g of Tween 20 (Fushan's family gas chemical industry).
The performance of the plate material is as follows: and (3) water washing rating: 5 stars; an ink affinity index of 9; and (3) reducing a 128lpi net point: 2% -98%, independent points: 0.2 mm; independent line 0.1mm, print times: 35 ten thousand.
Example 6:
60g of polymer A6, 20g of urethanized double-bonded polybutadiene (structure IV, Mw =3000, Total), 5g of 1, 6-hexanediol diacrylate (Tianjiao), 2g of hydroxyethyl methacrylate (Mitsubishang Yang), 3g of dipentaerythritol triacrylate (sartomer), 5g of initiator 651 (Jingjiang Macrotai chemical), 3g of Neozapon-red395 (Pasff), 1g of 2, 6-ditert-butyl-p-cresol (Nanjing Jiulong chemical), 0.5g of tert-alkyl ethoxyamine (dicarbonic chemical), and 0.5g of Tween 20 (Fushan chemical).
The performance of the plate material is as follows: and (3) water washing rating: 4 stars; an ink affinity index of 10; and (3) reducing a 125lpi net point: 1% -99%, independent points: 0.2 mm; independent line 0.1mm, print times: 32 million.
Example 7:
50g of polymer A7, 30g of urethanized double-bond polybutadiene (structure III, Mw =2800, Nippon soda), 5g of 1, 6-hexanediol diacrylate (Tianjiao), 2g of hydroxyethyl methacrylate (Mitsubishang Yang), 3g of dipentaerythritol triacrylate (sartomer), 5g of initiator 651 (Jingjiang Hongtai chemical industry), 3g of Neozapon-red395 (Pasteff), 1g of 2, 6-ditert-butyl-p-cresol (Nanjing Jiulon chemical industry), 0.5g of tert-alkyl ethoxyamine (Bicarbo chemical industry), and 0.5g of Tween 20 (Fushan chemical industry).
The performance of the plate material is as follows: and (3) water washing rating: 5 stars; an ink affinity index of 8; and (3) 120lpi net point reduction: 2% -98%, independent points: 0.2 mm; independent line 0.1mm, print times: 34 ten thousand.
example 8:
60g of polymer A8, 20g of urethanized double-bond polybutadiene (structure I, Mw =1700, Nippon soda), 5g of 1, 6-hexanediol diacrylate (Tianjiao), 1g of hydroxyethyl methacrylate (Mitsubishang Yang), 5g of dipentaerythritol triacrylate (sartomer), 4g of initiator 651 (Jingjiang Hongtai chemical industry), 3g of Neozapon-red395 (Pasteff), 1g of 2, 6-ditert-butyl-p-cresol (Nanjing Jiulong Jiulon chemical industry), 0.5g of tert-alkyl ethoxyamine (Bicarbo chemical industry), and 0.5g of Tween 20 (Fushan chemical industry).
The performance of the plate material is as follows: and (3) water washing rating: 4 stars; an ink affinity index of 9; and (3) reducing a 125lpi net point: 2% -98%, independent points: 0.2 mm; independent line 0.1mm, print times: 33 ten thousand.
Example 9:
70g of polymer A9, 15g of urethanized double-bond polybutadiene (structure II, Mw =1600, Nippon soda), 5g of 1, 6-hexanediol diacrylate (Tianjiao), 1g of hydroxyethyl methacrylate (Mitsubishang Yang), 1g of dipentaerythritol triacrylate (sartomer), 3g of initiator 651 (Jingjiang Hongtai chemical industry), 3g of Neozapon-red395 (Pasteff), 1g of 2, 6-ditert-butyl-p-cresol (Nanjing Jiulong Jiulon chemical industry), 0.5g of tert-alkyl ethoxyamine (Bicarbo chemical industry), and 0.5g of Tween 20 (Fushan chemical industry).
The performance of the plate material is as follows: and (3) water washing rating: 5 stars; an ink affinity index of 8; reduction of 122lpi net point: 2% -98%, independent points: 0.2 mm; independent line 0.1mm, print times: 30 ten thousand.
Example 10:
50g of polymer A10, 30g of urethanized double-bond polybutadiene (structure I, Mw =2200, Nippon soda), 5g of 1, 6-hexanediol diacrylate (Tianjiao), 1g of hydroxyethyl methacrylate (Mitsubishang Yang), 4g of dipentaerythritol triacrylate (sartomer), 5g of initiator 651 (Jingjiang Hongtai chemical industry), 3g of Neozapon-red395 (Pasteff), 1g of 2, 6-ditert-butyl-p-cresol (Nanjing Jiulong Jiulon chemical industry), 0.5g of tert-alkyl ethoxyamine (Bicarbo chemical industry), and 0.5g of Tween 20 (Fushan chemical industry).
the performance of the plate material is as follows: and (3) water washing rating: 5 stars; an ink affinity index of 7; and (3) reducing a 125lpi net point: 2% -98%, independent points: 0.2 mm; independent line 0.1mm, print times: 29 ten thousand.
Example 11:
65g of polymer A11, 15g of urethanized double-bond polybutadiene (structure IV, Mw =1900, Nippon soda), 10g of urethanized double-bond polybutadiene (structure II, Mw =1100, Nippon soda), 2g of 1, 6-hexanediol diacrylate (Tianjiao), 1g of hydroxyethyl methacrylate (Mitsubishang), 1g of dipentaerythritol triacrylate (sartomer), 1g of initiator 651 (Jingjiang macrochemical), 3g of Neozapon-red395 (Basff) 1g, 1g of 2, 6-ditert-butyl-p-cresol (Nanjing nonalcon chemical), 0.5g of tert-alkyl ethoxyamine (Union chemical), and 0.5g of Tween 20 (Fushan's Cogasohol chemical).
The performance of the plate material is as follows: and (3) water washing rating: 5 stars; an ink affinity index of 8; and (3) reducing a 125lpi net point: 2% -98%, independent points: 0.2 mm; independent line 0.1mm, print times: 28 ten thousand.
Example 12:
45g of polymer A12, 30g of urethanized double-bond polybutadiene (structure II, Mw =1700, Nippon soda), 5g of 1, 6-hexanediol diacrylate (Tianjiao), 4g of hydroxyethyl methacrylate (Mitsubishang Yang), 5g of dipentaerythritol triacrylate (sartomer), 5g of initiator 651 (Jingjiang Hongtai chemical industry), 3g of Neozapon-red395 (Pasteff), 1g of 2, 6-ditert-butyl-p-cresol (Nanjing Jiulong Jiulon chemical industry), 0.5g of tert-alkyl ethoxyamine (Bicarbo chemical industry), and 0.5g of Tween 20 (Fushan chemical industry).
The performance of the plate material is as follows: and (3) water washing rating: 5 stars; an ink affinity index of 7; and (3) reducing a 125lpi net point: 2% -98%, independent points: 0.2 mm; independent line 0.1mm, print times: 37 ten thousand.
Example 13:
70g of polymer A13, 15g of urethanized double-bond polybutadiene (structure I, Mw =1300, Nippon soda), 3g of 1, 6-hexanediol diacrylate (Tianjiao), 3g of hydroxyethyl methacrylate (Mitsubishang Yang), 2g of dipentaerythritol triacrylate (sartomer), 3g of initiator 651 (Jingjiang Hongtai chemical industry), 2g of Neozapon-red395 (Pasteff), 1g of 2, 6-ditert-butyl-p-cresol (Nanjing Jiulong chemical industry), 0.5g of tert-alkyl ethoxyamine (Bicarbo chemical industry), and 0.5g of Tween 20 (Fushan chemical industry).
the performance of the plate material is as follows: and (3) water washing rating: 5 stars; an ink affinity index of 7; and (3) reducing a 128lpi net point: 2% -98%, independent points: 0.2 mm; independent line 0.1mm, print times: 38 ten thousand.
Example 14:
75g of polymer A14, 10g of urethanized double-bond polybutadiene (structure IV, Mw =2500, Nippon soda), 3g of 1, 6-hexanediol diacrylate (Tianjiao), 1g of hydroxyethyl methacrylate (Mitsubishang Yang), 1g of dipentaerythritol triacrylate (sartomer), 5g of initiator 651 (Jingjiang Hongtai chemical industry), 3g of Neozapon-red395 (Pasteff), 1g of 2, 6-ditert-butyl-p-cresol (Nanjing Jiulong Jiulon chemical industry), 0.5g of tert-alkyl ethoxyamine (Bicarbo chemical industry), and 0.5g of Tween 20 (Fushan chemical industry).
The performance of the plate material is as follows: and (3) water washing rating: 4 stars; an ink affinity index of 8; and (3) reducing a 125lpi net point: 2% -98%, independent points: 0.2 mm; independent line 0.2mm, print times: 35 ten thousand.
example 15:
60g of polymer A15, 20g of urethanized double-bond polybutadiene (structure II, Mw =3500, Dupont), 5g of 1, 6-hexanediol diacrylate (Tianjiao), 2g of hydroxyethyl methacrylate (Mitsubishang Yang), 3g of dipentaerythritol triacrylate (sartomer), 5g of initiator 651 (Jingjiang Hongtai chemical industry), 3g of Neozapon-red395 (Pasteff), 1g of 2, 6-ditert-butyl-p-cresol (Nanjing Jiulong chemical industry), 0.5g of tert-alkyl ethoxyamine (Bicarbo chemical industry), and 0.5g of Tween 20 (Fushan chemical industry).
The performance of the plate material is as follows: and (3) water washing rating: 5 stars; an ink affinity index of 8; and (3) 120lpi net point reduction: 1% -98%, independent points: 0.2 mm; independent line 0.1mm, print times: 31 ten thousand.
Example 16:
65g of polymer A16, 15g of urethanized double-bond polybutadiene (structure IV, Mw =3500, Nippon soda), 5g of 1, 6-hexanediol diacrylate (Tianjiao), 2g of hydroxyethyl methacrylate (Mitsubishang Yang), 3g of dipentaerythritol triacrylate (sartomer), 5g of initiator 651 (Jingjiang Hongtai chemical industry), 3g of Neozapon-red395 (Pasteff), 1g of 2, 6-ditert-butyl-p-cresol (Nanjing Jiulong Jiulon chemical industry), 0.5g of tert-alkyl ethoxyamine (Bicarbo chemical industry), and 0.5g of Tween 20 (Fushan chemical industry).
The performance of the plate material is as follows: and (3) water washing rating: 5 stars; an ink affinity index of 7; and (3) reducing a 125lpi net point: 2% -98%, independent points: 0.2 mm; independent line 0.1mm, print times: 33 ten thousand.
Example 17:
polymer a17:60g, urethanized double-bond polybutadiene (structure iii, Mw =4200, japan caoda) 10g, urethanized double-bond polybutadiene (structure iv, Mw =1200, japan caoda) 10g, 1, 6-hexanediol diacrylate (Tianjiao) 5g, hydroxyethyl methacrylate (mitsubishi yang) 2g, Satomer366 (sartomer) 3g, initiator 651 (jing jiang macrochemical) 5g, Neozapon-red395 (basf) 3g, 2, 6-ditert-butyl-p-cresol (nanjing nonalong chemical) 1g, t-alkylethoxyamine (allin chemical) 0.5g, tween 20 (bosch gas chemical of buddha) 0.5 g.
The performance of the plate material is as follows: and (3) water washing rating: 5 stars; inking index 7, 125lpi dot reduction: 2% -98%, independent points: 0.2 mm; independent line 0.1mm, print times: 30 ten thousand.
Comparative example 1
polymer a' 1: 77g, 10g of non-urethanized double-bond polybutadiene (structure I, Mw =1000, Nippon Cauda), 2g of 1, 6-hexanediol diacrylate (Tianjiao), 4g of hydroxyethyl methacrylate (Mitsubishang Yang), 5g of dipentaerythritol triacrylate (sartomer), 1g of initiator 651 (Jingjiang Macrotah chemical), 0.5g of Neozapon-red395 (Pasff), 0.1g of 2, 6-ditert-butyl-p-cresol (Nanjing Jiulon Jiulong chemical), 0.1g of tert-alkyl ethoxyamine (Bicarbo chemical), and 0.3g of Tween 20 (Fushan chemical).
The performance of the plate material is as follows: and (3) water washing rating: 3, star; an ink affinity index of 6; and (3) reducing a 125lpi net point: 5% -90%, independent points: 0.4 mm; independent line 0.3mm, print times: 22 ten thousand.
Comparative example 2:
Polymer a' 4:70g, non-urethanized double-bonded polybutadiene (structure iii, Mw =1300, Total) 20g, 1, 6-hexanediol diacrylate (Tianjiao) 2g, hydroxyethyl methacrylate (mitsubishi yang) 2g, dipentaerythritol triacrylate (sartomer) 1g, initiator 651 (jing jiang santita chemical) 2g, Neozapon-red395 (basf) 1g, 2, 6-ditert-butyl-p-cresol (nanjing nonalong chemical) 2g, tertiary alkyl ethoxyamine (dicarbon chemical) 1g, tween 20 (bosch chemical) 2 g.
The performance of the plate material is as follows: and (3) water washing rating: 5 stars; an ink affinity index of 6; and (3) reducing a 125lpi net point: 4% -94%, independent points: 0.3 mm; independent line 0.15mm, print times: 19 ten thousand.
Comparative example 3:
Polymer a' 7:50g, non-urethanized double-bonded polybutadiene (structure iii, Mw =2800, japan caoda) 30g, 1, 6-hexanediol diacrylate (Tianjiao) 5g, hydroxyethyl methacrylate (mitsubishi yang) 2g, dipentaerythritol triacrylate (sartomer) 3g, initiator 651 (jing jiang daita chemical) 5g, Neozapon-red395 (basf) 3g, 2, 6-ditert-butyl-p-cresol (nanjing nonalong chemical) 1g, t-alkyl ethoxyamine (dicarbon chemical) 0.5g, tween 20 (bosch chemical) 0.5 g.
the performance of the plate material is as follows: and (3) water washing rating: 5 stars; an ink affinity index of 5; and (3) 120lpi net point reduction: 5% -93%, independent points: 0.35 mm; independent line 0.2mm, print times: 23 ten thousand.
Comparison 4:
Polymer a' 12:45g, non-urethanized double-bonded polybutadiene (structure ii, Mw =1700, japan caoda) 30g, 1, 6-hexanediol diacrylate (Tianjiao) 5g, hydroxyethyl methacrylate (mitsubishi yang) 4g, dipentaerythritol triacrylate (sartomer) 5g, initiator 651 (jing jiang daita chemical), Neozapon-red395 (basf) 3g, 2, 6-ditert-butyl-p-cresol (nanjing nonalong chemical) 1g, t-alkyl ethoxyamine (dicarbon chemical) 0.5g, tween 20 (bosch chemical) 0.5 g.
The performance of the plate material is as follows: and (3) water washing rating: 5 stars; an ink affinity index of 4; and (3) reducing a 125lpi net point: 3% -96%, independent points: 0.4 mm; independent line 0.25mm, print times: 23 ten thousand.
Comparative example 5:
65g of polymer a', 15g of non-urethanized double-bonded polybutadiene (structure iv, Mw =3500, japan caoda), 5g of 1, 6-hexanediol diacrylate (Tianjiao), 2g of hydroxyethyl methacrylate (mitsubishi yang), 3g of dipentaerythritol triacrylate (sartomer), 5g of initiator 651 (jing jiang daita chemical), 3g of Neozapon-red395 (basf), 1g of 2, 6-ditert-butyl-p-cresol (nanjing nonalong chemical), 0.5g of tert-alkyl ethoxyamine (dicarbon chemical), and 0.5g of tween 20 (bosch chemical).
The performance of the plate material is as follows: and (3) water washing rating: 5 stars; an ink affinity index of 3; and (3) reducing a 125lpi net point: 3% -95%, independent points: 0.3 mm; independent line 0.15mm, print times: 24 ten thousand.
Comparative example 6:
polyvinyl alcohol PVA405 (Kuraray, Japan, saponification rate of about 82 mol): 45g, non-urethanized double-bond polybutadiene (structure II, Mw =5000, Zibozilong) 30g, 1, 6-hexanediol diacrylate (Tianjiao) 12g, hydroxyethyl methacrylate (Mitsubishi Yang) 5g, dipentaerythritol triacrylate (sartomera) 13g, initiator 651 (Jingjiang Hongtai chemical industry) 5g, Neozapon-red395 (Pasteur) 2g, 2, 6-ditert-butyl-p-cresol (Nanjing Jiulong chemical industry) 1g, tert-alkyl ethoxyamine (Bicarbo chemical industry) 1g, and Tween 20 (Fushan chemical industry) 1 g.
The performance of the plate material is as follows: and (3) water washing rating: 5 stars; an ink affinity index of 5; and (3) reducing a 128lpi net point: 2% -98%, independent points: 0.2 mm; independent line 0.1mm, print times: 11 ten thousand.
Comparative example 7:
60g of an acrylonitrile-butadiene latex copolymer Nipol SX1503 (Nippon Zeon Co.), 20g of non-urethanized double-bond polybutadiene (structure IV, Mw =3000, Total), 5g of 1, 6-hexanediol diacrylate (Tianjiao), 2g of hydroxyethyl methacrylate (Mitsubishi Yang), 3g of dipentaerythritol triacrylate (sartomer), 5g of an initiator 651 (Jingjiang Macrotai chemical), 3g of Neozapon-red395 (Basff), 1g of 2, 6-ditert-butyl-p-cresol (Nanjing Sepilon chemical), 0.5g of t-alkylethoxyamine (Union carbide chemical), and 0.5g of Tween 20 (Fushan Ke gas chemical).
The performance of the plate material is as follows: and (3) water washing rating: 4 stars; an ink affinity index of 6; reduction of 122lpi net point: 1% -99%, independent points: 0.3 mm; independent line 0.15mm, print times: 18 ten thousand.
Comparative example 8:
Styrene-methacrylic acid-polyethoxy acrylate copolymer SME220 (60: 7:33, n =42, Lekeka research institute): 70g, non-urethanized double-bond polybutadiene (structure II, Mw =1600, Nippon Caoda) 15g, 1, 6-hexanediol diacrylate (Tianjiao) 5g, hydroxyethyl methacrylate (Mitsubishi) 1g, dipentaerythritol triacrylate (sartomer) 1g, initiator 651 (Jingjiang Macrotai chemical) 3g, Neozapon-red395 (Basff) 3g, 2, 6-ditert-butyl-p-cresol (Nanjing nona chemical) 1g, t-alkylethoxyamine (Union chemical) 0.5g, and Tween 20 (Fushan gas chemical) 0.5 g.
the performance of the plate material is as follows: and (3) water washing rating: 5 stars; an ink affinity index of 6; reduction of 122lpi net point: 2% -98%, independent points: 0.2 mm; independent line 0.1mm, print times: 30 ten thousand.
Comparative example 9:
Kraton D1160 (Kraton corporation, USA) 45g, NipolLX111NF (Zeon, Japan) 30g, 1, 6-hexanediol diacrylate (Tianjiao) 5g, hydroxyethyl methacrylate (Mitsubishi Yang) 4g, dipentaerythritol triacrylate (saroman) 5g, initiator 651 (Jingjing Hongtai chemical industry) 5g, Neozapon-red395 (Pasov) 3g, 2, 6-ditert-butyl-p-cresol (Nanjing Jiulong chemical industry) 1g, tert-alkyl ethoxy amine (tetracarbon chemical industry) 0.5g, and Tween 20 (Fushan Ke gas chemical industry) 0.5 g.
The performance of the plate material is as follows: and (3) water washing rating: 5 stars; an ink affinity index of 7; and (3) 120lpi net point reduction: 2% -98%, independent points: 0.2 mm; independent line 0.1mm, print times: 25 thousands.
Comparative example 10:
Copolymer (49 mol% butadiene, 7.5 mol% methacrylic acid, 1.5 mol% ethylene glycol dimethacrylate and 42 mol% ethyl acrylate, synthesis process see US 5175076) 60g, urethanized double bond polybutadiene (structure ii, Mw =3500, Dupont) 20g, 1, 6-hexanediol diacrylate (Tianjiao) 5g, hydroxyethyl methacrylate (mitsubishi yang) 2g, dipentaerythritol triacrylate (sartomer) 3g, initiator 651 (Jingjiang macrocita chemical) 5g, Neozapon-red395 (basf) 3g, 2, 6-ditert-butyl-p-cresol (Nanjing jiulong chemical) 1g, t-alkylethoxyamine (dicarbon chemical) 0.5g, tween 20 (Fushan's family gas chemical) 0.5 g.
The performance of the plate material is as follows: and (3) water washing rating: 5 stars; an ink affinity index of 6; and (3) 120lpi net point reduction: 3% -97%, independent point: 0.3 mm; independent line 0.3mm, print times: 22 ten thousand.
The plate application detection results of the embodiment and the comparative example show that the elastomer composition for the water-washing flexible plate disclosed by the invention contains the urethane double bond in both the hydrophilic polymer and the liquid polybutadiene, an image part of the plate after exposure forms a urethane bond net-shaped cross-linking structure, the urethane bond has excellent toughness and lipophilicity, and the printing resistance and the ink affinity of the plate are improved.

Claims (9)

1. an elastomeric composition for water-washable flexographic plates, characterized in that it comprises: (A) water-soluble copolymers with branched, grafted, reactive urethanized double bonds; (B) liquid polybutadiene with a urethane double bond grafted at the end; (C) unsaturated monomer containing at least more than 1 double bond; (D) a photopolymerization initiator; (E) dyes and (F) other additives; the water-soluble copolymer (A) with branched grafted active aminoesterified double bonds has the following structure:
Wherein R 1 is H or CH 3, R 2 is H or CH 3, the mass percentages of the corresponding copolymerized units of a, b and c are respectively 20-80%, 10-40% and 10-40%, and the polymerization degree n of the polyether is 9 ~ 125.
2. The elastomer composition for water-washed flexographic plates according to claim 1, wherein said (A) water-soluble copolymer having branched-chain grafted active urethanized double bonds accounts for 45 ~ 77% of the total mass of the elastomer composition, (B) liquid polybutadiene having terminal-grafted urethanized double bonds accounts for 10 ~ 30% of the total mass of the elastomer composition, (C) unsaturated monomer having at least 1 or more double bonds accounts for 10 ~ 15% of the total mass of the elastomer composition, (D) photopolymerization initiator accounts for 1 ~ 5% of the total mass of the elastomer composition, (E) dye accounts for 1 ~ 5% of the total mass of the elastomer composition, and the others are (F) other additives.
3. The elastomeric composition for water-washable flexographic plates according to claim 1, characterized in that said (B) liquid polybutadiene terminally grafted with urethanized double bonds has one or a mixture of the following 4 structures (I), (II), (III), (IV):
（Ⅰ）
（Ⅱ）
（Ⅲ）
（Ⅳ）
Wherein, the dotted line in the 1, 4-bond repeating unit in the structural formula (III) and (IV) represents a trans-bond or a cis-bond; the molecular weight of the liquid polybutadiene with the tail end grafted with the amino esterification double bond is 1000-5000.
4. the elastomeric composition for water-washed flexographic plates according to claim 1, characterized in that: the unsaturated monomer (C) containing at least more than 1 double bond is unsaturated acrylate or unsaturated polyurethane acrylate.
5. The elastomeric composition for water-washed flexographic plates according to claim 1, characterized in that: the photopolymerization initiator (D) is a compound which is alpha-cleaved.
6. The elastomeric composition for water-washed flexographic plates according to claim 1, characterized in that: the dye (E) is neutral red.
7. The elastomeric composition for water-washed flexographic plates according to claim 1, characterized in that: and the other additives (F) are an antioxidant, a thermal inhibitor, a release agent or a leveling agent.
8. the elastomeric composition for water-washed flexographic plates according to claim 5, characterized in that: the alpha-cleaving compound is preferably a benzoin derivative or a dehydrobenzophenone derivative.
9. A water-washable flexographic plate characterized in that said elastomeric composition according to any one of claims 1 to 8 is present on the surface of a support.
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CN101770174A (en) * 2008-12-30 2010-07-07 乐凯集团第二胶片厂 Flexible photosensitive resin plate and preparation method thereof
CN102365585A (en) * 2009-04-10 2012-02-29 日本曹达株式会社 Photosensitive resin composition for flexographic printing having excellent solvent resistance
CN102540709A (en) * 2010-12-30 2012-07-04 乐凯华光印刷科技有限公司 Infrared sensitive chemistry-free light-sensing composition and lithographic printing plate made from same
CN102566283A (en) * 2011-12-23 2012-07-11 乐凯华光印刷科技有限公司 Washed flexible resin plate capable of achieving laser direct imaging

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Publication number Priority date Publication date Assignee Title
CN101770174A (en) * 2008-12-30 2010-07-07 乐凯集团第二胶片厂 Flexible photosensitive resin plate and preparation method thereof
CN102365585A (en) * 2009-04-10 2012-02-29 日本曹达株式会社 Photosensitive resin composition for flexographic printing having excellent solvent resistance
CN102540709A (en) * 2010-12-30 2012-07-04 乐凯华光印刷科技有限公司 Infrared sensitive chemistry-free light-sensing composition and lithographic printing plate made from same
CN102566283A (en) * 2011-12-23 2012-07-11 乐凯华光印刷科技有限公司 Washed flexible resin plate capable of achieving laser direct imaging

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