CN106188670A - A kind of bag coating compound of compound silica-based printing rubber roll and preparation method thereof - Google Patents

A kind of bag coating compound of compound silica-based printing rubber roll and preparation method thereof Download PDF

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CN106188670A
CN106188670A CN201610585576.8A CN201610585576A CN106188670A CN 106188670 A CN106188670 A CN 106188670A CN 201610585576 A CN201610585576 A CN 201610585576A CN 106188670 A CN106188670 A CN 106188670A
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周正红
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Tongling Hongzheng Network Technology Co Ltd
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Tongling Hongzheng Network Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00Compositions of natural rubber
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F112/00Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F112/02Monomers containing only one unsaturated aliphatic radical
    • C08F112/04Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F112/06Hydrocarbons
    • C08F112/08Styrene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/14Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/18Spheres

Abstract

nullThe invention discloses the bag coating compound of a kind of compound silica-based printing rubber roll,It is made up of the raw material of following weight parts: ureidopropyltriethoxysilane 0.7 dipropylene glycol 12、Graphene oxide 10 14、N N-Hydroxysuccinimide 67、1 ethyl (3 dimethylaminopropyl) carbodiimide hydrochloride 10 12、P-aminobenzene sulfonic acid 79、Styrene 30 40、Accelerant CZ 12、Antioxidant D 12、Potassium peroxydisulfate 0.1 0.2、Lanthanum chloride 0.3 0.4、Ethylenediaminetetraacetic acid 23、Carbon fiber 1.7 2、The ammonia 50 67 of 20 25%、Natural rubber 100 130、Phenethyl phenol polyethenoxy ether 0.8 1、Sodium potassium silicate 46、Wollastonite in powder 10 18、Adipic acid propanediol polyester 23、Dimethylethanolamine 12、Calcium fluoride 34、Lecithin 0.1 0.2、Sulfur 0.8 1.The sizing material of the present invention has fine intensity and weatherability, and combination property is superior, and service life is long.

Description

A kind of bag coating compound of compound silica-based printing rubber roll and preparation method thereof
Technical field
The present invention relates to printing rubber roll technical field, particularly relate to a kind of compound silica-based printing rubber roll bag coating compound and Its preparation method.
Background technology
Printing rubber roll be gum elastic with metal roller core through the complex of certain processes, be widely used in In various printing industries, and at present there is a lot of problems in the quality of printing rubber roll, and wearability is bad, often occur abrasion, The phenomenon of broken hole, has had a strong impact on press quality, the most how to improve wear resistence and the mechanical property thereof of printing rubber roll, just seems The most necessary;
The dilute raw material of graphite oxide is easy to get, cheap, is the ideal filler of polymer nanocomposites, in recent years, aoxidizes stone The research of the dilute/polymer nanocomposites of ink is one of currently dilute about graphite study hotspot, is especially preparing The dilute paper of unsupported graphite oxide and graphite dilute/polymer conductive nanometer compound material after, started to graphene oxide apply The upsurge of research.
At present, along with preparing the maturation of the dilute technology of graphite oxide, people oneself synthesized various graphene oxide/polymer nano Nano composite material, conventional polymeric matrix has polystyrene, polymethyl acrylate, polyaniline, polyacrylamide, poly-second Dilute alcohol etc..But, it has been found that prepare graphite oxide dilute/polymer complex process present in subject matter be oxidation stone Dilute being easy to of ink is reunited, and dispersibility inequality hooks in the polymer, the dilute combination interface situation with polymer of graphite oxide The best, ultimately result in graphite oxide dilute/combination property of polymer composites is the highest, thus it is the most industrial to limit it Application.The processing characteristics dilute for improving graphite oxide, people generally use the method that it is carried out functional modification, and achieve Noticeable achievement in research, this provides a good thinking for preparing Graphene/polymer composites.
Summary of the invention
The object of the invention is contemplated to make up the defect of prior art, it is provided that the cladding glue of a kind of compound silica-based printing rubber roll Sizing material and preparation method thereof.
The present invention is achieved by the following technical solutions:
A kind of bag coating compound of compound silica-based printing rubber roll, it is made up of the raw material of following weight parts:
Ureidopropyltriethoxysilane 0.7-dipropylene glycol 1-2, graphene oxide 10-14, N-hydroxy-succinamide 6-7,1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride 10-12, p-aminobenzene sulfonic acid 7-9, styrene 30-40, Accelerant CZ 1-2, antioxidant D 1-2, potassium peroxydisulfate 0.1-0.2, lanthanum chloride 0.3-0.4, ethylenediaminetetraacetic acid 2-3, carbon fiber The ammonia 50-67 of 1.7-2,20-25%, natural rubber 100-130, phenethyl phenol polyethenoxy ether 0.8-1, sodium potassium silicate 4-6, Wollastonite in powder 10-18, adipic acid propanediol polyester 2-3, dimethylethanolamine 1-2, calcium fluoride 3-4, lecithin 0.1-0.2, sulfur Sulphur 0.8-1.
The preparation method of the bag coating compound of a kind of described compound silica-based printing rubber roll, comprises the following steps:
(1) by dilute for above-mentioned graphite oxide DMF joining its weight 50-60 times, supersound process 20-30 Minute, add 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxy-succinamide, stirring mixing 1.7-2 hour, adding p-aminobenzene sulfonic acid, under room temperature, stirring reaction 23-24 hour, washes with water 3-4 time, the most ultrasonic 10- 15 minutes, obtain sulfonated graphite dilute;
(2) above-mentioned calcium fluoride is joined in the deionized water of its weight 6-10 times, stir, add lecithin, at 50-60 Insulated and stirred 2-3 minute at DEG C, obtains calcium emulsion;
(3) sulfonated graphite is dilute, styrene mixing, adds the deionized water of compound weight 40-50%, stirs, in addition State calcium emulsion, ultrasonic 10-15 minute, obtain sulfonation emulsion;
(4) above-mentioned ethylenediaminetetraacetic acid is joined in the ammonia of 20-25%, add lanthanum chloride, insulated and stirred 20-at 60-70 DEG C 30 minutes, add carbon fiber, heat-insulation soaking 1-2 hour, obtain rare earth modified carbon fiber solution;
(5) above-mentioned sodium potassium silicate is joined in its weight 10-13 times deionized water, stirs, add dimethylethanolamine, Adding sulphuric acid, regulation pH is 1-3, and insulation reaction 1-2 hour at 60-70 DEG C adds above-mentioned rare earth modified carbon fiber solution, stirs Mix to room temperature, obtain rare earth modified silicon solution;
(6) in above-mentioned sulfonation emulsion, add potassium peroxydisulfate, stir, under nitrogen protection, 70-80 DEG C of insulated and stirred 5-6 Hour, it is cooled to room temperature, adds above-mentioned rare earth modified silicon solution, supersound process 10-15 minute, sucking filtration, remove filtrate, at 60- It is vacuum dried 2-3 hour at 70 DEG C, obtains polymer modification compounded mix;
(7) by above-mentioned wollastonite in powder, the mixing of polymer modification compounded mix, ball milling is uniform, adds going of compound weight 4-6 times Ionized water, adds ureidopropyltriethoxysilane, and 200-300 rev/min is stirred 10-14 minute, be heated to water at 80-90 DEG C Dry, obtain modified filler;
(8) being mixed with natural rubber by above-mentioned modified filler, send in banbury, banburying 40-50s at 65-90 DEG C, addition removes Each raw material beyond sulfur, mixing 10-12 minute, binder removal, it is cooled to less than 50 DEG C, puts in mill, add residue each Raw material, thin logical 3-5 time, to obtain final product.
The invention have the advantage that the sizing material of the present invention has a good wear resistence:
The edge of stannic oxide/graphene nano sheet contains substantial amounts of carboxylic group, at condensation reagent 1-ethyl-(3-dimethylamino third Base) carbodiimide hydrochloride effect under, 1-ethyl-(3-dimethylaminopropyl) carbodiimide is first counter with carboxyl to be formed The 0-acyl isourea intermediate product that can react with amine, N-hydroxy-succinamide plays the effect improving its stability, in the middle of this Product generates amide with the p-aminobenzene sulfonic acid generation coupling reaction containing primary amine group further, obtains sulfonated graphene, sulphur The state that functionalized graphene is peeled off in height is evenly distributed in polystyrene microsphere, and the graphite oxide after sulfonation modifying is dilute Having stronger hydrophilic, improve the dispersibility in its water, the negative charge that sulfonate ion band is stronger simultaneously, in polymerization process In, the reunion of himself can be effectively prevented, then initiator (potassium peroxydisulfate) first passes through electrostatic interaction and is adsorbed onto sulfonation The surface of Graphene, then there is polyreaction in trigger monomer on its surface, when, after the many oligomers of deposition, hydrophobicity improves, And reunite in aqueous phase, hydrophobic polymer then interacts after formation primary nuclei, the styrene list being dissolved in aqueous phase Body is diffused into continuously in primary nuclei and participates in further polyreaction, and along with the carrying out of polyreaction, growth core is straight Footpath constantly increases, and the coverage rate that graphite is dilute declines, and Stabilization declines, and now free in aqueous phase sulfonated graphite is dilute stronger Under π-π the most often acts on, it is adsorbed on polystyrene surface, ultimately forms finely dispersed complex;
The sizing material of the present invention has a good mechanical property:
The present invention is also added into rare earth fiber, and the most surface treated carbon fiber is low due to its surface activity, it is difficult to formed effectively Interfacial adhesion, therefore composite materials property is very poor, rubber matrix because of frictional heat effect be easy to produce adhesive wear, with Carbon fiber produce and loosen, crack on interface produces stress and concentrates, and fatigue crack generates, and easily induction composite is further Abrasion, the present invention uses rare earth modified carbon fiber to be combined in polymeric matrix so that combine tight between carbon fiber and polymeric matrix Close, in friction process, major part load born by carbon fiber, and load is delivered to carbon fiber, carbon by interface effectively Fiber effectively acts as the effect of support loads, and composite material surface entirety bears frrction load, and excellent interface cohesion makes it Coefficient of friction and wear extent are affected little by the frequency that reciprocatingly slides.Rare earth element can occur with C, O, N of carbon fiber surface Coordination chemistry, and be bonded, when carbon fiber and polystyrene with the organic active group generation chemical coordination in earth solution Compound tense, can form strong high tenacity interface, thus improve finished product elastomeric material between carbon fiber surface and polystyrene Mechanical property.
The sizing material of the present invention has fine intensity and weatherability, and combination property is superior, and service life is long.
Detailed description of the invention
A kind of bag coating compound of compound silica-based printing rubber roll, it is made up of the raw material of following weight parts:
Ureidopropyltriethoxysilane 0.7 dipropylene glycol 1, graphene oxide 10, N N-Hydroxysuccinimide 6,1 ethyl (3 dimethylaminopropyl) carbodiimide hydrochloride 10, p-aminobenzene sulfonic acid 7, styrene 30, accelerant CZ 1, antioxidant D 1, Potassium peroxydisulfate 0.1, lanthanum chloride 0.3, ethylenediaminetetraacetic acid 2, the ammonia 50 of carbon fiber 1.7,20%, natural rubber 100, phenethyl Phenol polyethenoxy ether 0.8, sodium potassium silicate 4, wollastonite in powder 10, adipic acid propanediol polyester 2, dimethylethanolamine 1, calcium fluoride 3, Lecithin 0.1, sulfur 0.8.
The preparation method of the bag coating compound of a kind of described compound silica-based printing rubber roll, comprises the following steps:
(1) by dilute for above-mentioned graphite oxide DMF joining its weight 50 times, supersound process 20 minutes, add Entering 1 ethyl (3 dimethylaminopropyl) carbodiimide hydrochloride, N N-Hydroxysuccinimide, stirring mixing 1.7 hours, it is right to add Aminobenzenesulfonic acid, under room temperature, stirring reaction 23 hours, wash with water 3 times, the most ultrasonic 10 minutes, obtain sulfonated graphite dilute;
(2) above-mentioned calcium fluoride is joined in the deionized water of its weight 6 times, stir, add lecithin, protect at 50 DEG C Temperature stirring 2 minutes, obtains calcium emulsion;
(3) sulfonated graphite is dilute, styrene mixing, adds the deionized water of compound weight 40%, stirs, add above-mentioned Calcium emulsion, ultrasonic 10 minutes, obtains sulfonation emulsion;
(4) being joined by above-mentioned ethylenediaminetetraacetic acid in the ammonia of 20%, add lanthanum chloride, at 60 DEG C, insulated and stirred 20 minutes, add Enter carbon fiber, heat-insulation soaking 1 hour, obtain rare earth modified carbon fiber solution;
(5) above-mentioned sodium potassium silicate is joined in 10 times of deionized waters of its weight, stir, add dimethylethanolamine, add Entering sulphuric acid, regulation pH is 1, and insulation reaction 1 hour at 60 DEG C adds above-mentioned rare earth modified carbon fiber solution, stirs to room temperature, Obtain rare earth modified silicon solution;
(6) in above-mentioned sulfonation emulsion, add potassium peroxydisulfate, stir, under nitrogen protection, 70 DEG C of insulated and stirred 5 hours, Being cooled to room temperature, add above-mentioned rare earth modified silicon solution, supersound process 10 minutes, sucking filtration, remove filtrate, at 60 DEG C, vacuum is done Dry 2 hours, obtain polymer modification compounded mix;
(7) by above-mentioned wollastonite in powder, the mixing of polymer modification compounded mix, ball milling is uniform, add compound weight 4 times go from Sub-water, adds ureidopropyltriethoxysilane, and 200 revs/min are stirred 10 minutes, are heated to water and do, obtain modified filling out at 80 DEG C Material;
(8) above-mentioned modified filler is mixed with natural rubber, send in banbury, banburying 40s at 65 DEG C, add except sulfur Each raw material in addition, mixing 10 minutes, binder removal, it is cooled to less than 50 DEG C, puts in mill, add and remain each raw material, thin logical 3 Time, to obtain final product.
Performance test:
Hot strength: 14.8Mpa;
Elongation at break: 434.6%;
70 DEG C × 22h × 20% compression set: 16.6%;
70 DEG C × 70h air oven aging test:
Breaking strength reduction rate: 5.2%, elongation at break reduction rate: 8.4%.

Claims (2)

1. the bag coating compound of a compound silica-based printing rubber roll, it is characterised in that it is made up of the raw material of following weight parts :
Ureidopropyltriethoxysilane 0.7-1, dipropylene glycol 1-2, graphene oxide 10-14, N-hydroxysuccinimidyl acyl are sub- Amine 6-7,1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride 10-12, p-aminobenzene sulfonic acid 7-9, styrene 30- 40, accelerant CZ 1-2, antioxidant D 1-2, potassium peroxydisulfate 0.1-0.2, lanthanum chloride 0.3-0.4, ethylenediaminetetraacetic acid 2-3, carbon fibre Dimension the ammonia 50-67 of 1.7-2,20-25%, natural rubber 100-130, phenethyl phenol polyethenoxy ether 0.8-1, sodium potassium silicate 4- 6, wollastonite in powder 10-18, adipic acid propanediol polyester 2-3, dimethylethanolamine 1-2, calcium fluoride 3-4, lecithin 0.1-0.2, Sulfur 0.8-1.
2. the preparation method of the bag coating compound of the most compound silica-based printing rubber roll, it is characterised in that Comprise the following steps:
(1) by dilute for above-mentioned graphite oxide DMF joining its weight 50-60 times, supersound process 20-30 Minute, add 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxy-succinamide, stirring mixing 1.7-2 hour, adding p-aminobenzene sulfonic acid, under room temperature, stirring reaction 23-24 hour, washes with water 3-4 time, the most ultrasonic 10- 15 minutes, obtain sulfonated graphite dilute;
(2) above-mentioned calcium fluoride is joined in the deionized water of its weight 6-10 times, stir, add lecithin, at 50-60 Insulated and stirred 2-3 minute at DEG C, obtains calcium emulsion;
(3) sulfonated graphite is dilute, styrene mixing, adds the deionized water of compound weight 40-50%, stirs, in addition State calcium emulsion, ultrasonic 10-15 minute, obtain sulfonation emulsion;
(4) above-mentioned ethylenediaminetetraacetic acid is joined in the ammonia of 20-25%, add lanthanum chloride, insulated and stirred 20-at 60-70 DEG C 30 minutes, add carbon fiber, heat-insulation soaking 1-2 hour, obtain rare earth modified carbon fiber solution;
(5) above-mentioned sodium potassium silicate is joined in its weight 10-13 times deionized water, stirs, add dimethylethanolamine, Adding sulphuric acid, regulation pH is 1-3, and insulation reaction 1-2 hour at 60-70 DEG C adds above-mentioned rare earth modified carbon fiber solution, stirs Mix to room temperature, obtain rare earth modified silicon solution;
(6) in above-mentioned sulfonation emulsion, add potassium peroxydisulfate, stir, under nitrogen protection, 70-80 DEG C of insulated and stirred 5-6 Hour, it is cooled to room temperature, adds above-mentioned rare earth modified silicon solution, supersound process 10-15 minute, sucking filtration, remove filtrate, at 60- It is vacuum dried 2-3 hour at 70 DEG C, obtains polymer modification compounded mix;
(7) by above-mentioned wollastonite in powder, the mixing of polymer modification compounded mix, ball milling is uniform, adds going of compound weight 4-6 times Ionized water, adds ureidopropyltriethoxysilane, and 200-300 rev/min is stirred 10-14 minute, be heated to water at 80-90 DEG C Dry, obtain modified filler;
(8) being mixed with natural rubber by above-mentioned modified filler, send in banbury, banburying 40-50s at 65-90 DEG C, addition removes Each raw material beyond sulfur, mixing 10-12 minute, binder removal, it is cooled to less than 50 DEG C, puts in mill, add residue each Raw material, thin logical 3-5 time, to obtain final product.
CN201610585576.8A 2016-07-25 2016-07-25 A kind of bag coating compound of compound silica-based printing rubber roll and preparation method thereof Withdrawn CN106188670A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1807496A (en) * 2006-01-12 2006-07-26 上海交通大学 Preparation method of rare earth modified carbon fiber/ polypropylene composite material
CN1886451A (en) * 2003-10-20 2006-12-27 尤尼罗亚尔化学公司 Rubber compositions and methods for decreasing the tangent delta value and abrasion index

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1886451A (en) * 2003-10-20 2006-12-27 尤尼罗亚尔化学公司 Rubber compositions and methods for decreasing the tangent delta value and abrasion index
CN1807496A (en) * 2006-01-12 2006-07-26 上海交通大学 Preparation method of rare earth modified carbon fiber/ polypropylene composite material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
张丽园: ""磺化石墨烯和磺化碳纳米管为稳定剂的乳液聚合和分散聚合研究"", 《中国博士学位论文全文数据库 工程科技I辑》 *

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