CN106349804A - Preparation method of low-poison UV (ultraviolet)-curing ink composition - Google Patents
Preparation method of low-poison UV (ultraviolet)-curing ink composition Download PDFInfo
- Publication number
- CN106349804A CN106349804A CN201610682400.4A CN201610682400A CN106349804A CN 106349804 A CN106349804 A CN 106349804A CN 201610682400 A CN201610682400 A CN 201610682400A CN 106349804 A CN106349804 A CN 106349804A
- Authority
- CN
- China
- Prior art keywords
- solution
- cellulose
- quality
- liquid
- ink composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention relates to the field of UV ink and discloses a preparation method of a low-poison UV (ultraviolet)-curing ink composition. The preparation method includes the steps of 1), weighing, by weight, 50-70 parts of natural water-based polyurethane acrylate polymers, 4-8 parts of double(2-(methyl) acryloyl oxygen radicals ethoxy) dimethyl silane, 2-6 parts of photoinitiator, 2-8 parts of cellulose aerogels, 5-15 parts of pigment, 1-3 parts of defoamer and 10-16 parts of water; 2), mixing the natural water-based polyurethane acrylate polymers, the double(2-(methyl) acryloyl oxygen radicals ethoxy) dimethyl silane, the cellulose aerogels with the water to obtain a connecting substance solution and then heating to evenly stir; 3), adding the rest components to the connecting substance solution, and heating and stirring to obtain the low-poison UV-curing ink composition. The low-poison UV-curing ink composition has the advantages of good abrasion resistance, low viscosity, low poison and bacterial resistance.
Description
Technical field
The present invention relates to uv ink area, especially, it is related to a kind of preparation method of low toxicity evil uv cured printing ink composition.
Background technology
Ultraviolet light polymerization (uv) ink refers to that the ultraviolet light using different wave length and energy makes ink under ultraviolet irradiates
Film forming and the ink being dried.Using different ultraviolet spectras, different-energy can be produced, by the monomer polymerization in different ink vehicles
Become polymer, so the color film of uv ink has good mechanically and chemically performance.The major advantage of uv ink has: rate of drying
Hurry up, power consumption is few；Good luster, bright in luster；Water-fast, solvent resistance is good.
In uv ink, light trigger is that one kind is easily subject to light activated compound, is excited into free radical, energy after absorbing light is shone
Amount is transferred to photonasty molecule or photocrosslinking agent, makes uv ink that photocuring reaction to occur.Uv ink has become a kind of more ripe ink
Technology, its pollutant emission is almost nil.In addition, also just like being difficult scumming, site is clear, the bright-coloured light of mass colour for uv ink,
Chemical-resistance is excellent, the advantages of low-consuming.
Application with uv cured printing ink gradually expands, particularly in packaging for foodstuff, medical packaging field, people couple
There has also been new requirement in the environmentally friendly performance of uv cured printing ink and other functions characteristic (such as antibiotic property etc.).But
In current uv cured printing ink, the binder of employing still has certain zest and toxicity to human body it is therefore necessary to research and develop
A kind of employing natural material, the uv cured printing ink of low toxicity evil.
Content of the invention
It is an object of the invention to provide a kind of low toxicity is harmful, wearability is good, viscosity is low and has antibacterial functions uv solidified oil
Ink composition.
To achieve these goals, the concrete technical scheme of the present invention is: a kind of low toxicity does harm to uv cured printing ink composition
Preparation method, step is as follows:
Step 1: weigh the component of following weight portion: natural aqueouss polyurethane acrylate prepolymer 50-70 part, double [2-
(methacryloxy) ethyoxyl] dimethylsilane 4-8 part, light trigger 2-6 part, cellulose aerogels 2-8 part, pigment 5-
15 parts, defoamer 1-3 part, water 10-16 part.
Step 2: by aqueouss polyurethane acrylate prepolymer natural in step 1, double [2- (methacryloxy) ethoxy
Base] dimethylsilane, cellulose aerogels, water add container in mix homogeneously be obtained binder solution, be then heated to 35-55
DEG C and stir.
Step 3: add remaining component in binder solution, stir under conditions of 30-40 DEG C, 800-2000r/min
1-2h, fineness controls in 5-10 micron, and prepared low toxicity does harm to uv cured printing ink composition.
In the uv cured printing ink composition of the present invention, natural aqueouss polyurethane acrylate prepolymer is as main purple
Outer photocuring binder composition, not only curing rate is fast, and good film-forming property is good with stock adhesion, and it adopts natural material
Material synthesis, low toxicity does harm to, and stimulates little, environmental protection to human body.Double [2- (methacryloxy) ethyoxyl] dimethylsilane has
Have relatively low molecular weight, the viscosity of uv ink can be reduced, simultaneously its also to contain (methyl) acrylate-based, thus also having purple
Outer photocuring function, can participate in curing reaction in ultraviolet light polymerization, increase the degree of cross linking of film forming matter, improve the resistance to of film forming matter
Mill property.Cellulose aerogels have the characteristics that light weight, specific surface area are big, compound with natural aqueouss polyurethane acrylate prepolymer
The rate of drying of ink as the auxiliary binder of uv ink, can be further speeded up afterwards and improve the wear-resisting of ink film forming matter
Property, toughness.The uv cured printing ink of the present invention is adopted and is used water as solvent, without the organic solvent of volatilization, more environmental protection.
In the preparation process of ink composite, first by natural aqueouss polyurethane acrylate prepolymer, double [2- (methyl
Acryloxy) ethyoxyl] dimethylsilane, cellulose aerogels are mixed with water so that material dispersion uniformly, and makes cellulose
Aeroge is fully dispersed and is wrapped.Then binder solution and other components are carried out mix and blend, control ink composite
Fineness so as to have preferable dispersibility, levelability and suitable viscosity.
Further, described natural aqueouss polyurethane acrylate prepolymer is obtained by following methods:
A, take lignin and be added in the phenol of 80-120 times of quality, be heated to 170-180 DEG C, stirring reaction
40-50min, the mass concentration that before reaction, 30min at the uniform velocity drips 150-170 times of lignin quality be 10% sodium hydroxide molten
Liquid, adjusts ph to neutral with buffer solution after reaction, then naturally cools to 55-60 DEG C, add phenol quality 0.8-1.2 times
Furfural, the natural polyols of phenol quality 0.2-0.3 times, under heat-retaining condition, continue stirring reaction 80-100min, are obtained natural
Polyether polyol；Described natural polyols are xylitol or maltose alcohol；
B, under nitrogen atmosphere, by neutral polyether polyhydric alcohol, polycaprolactone glycol, diisocyanate, catalyst mixing,
50-55 DEG C, stirring reaction 2-3h under conditions of 150-170r/min, obtain polyurethane liquid；Wherein, neutral polyether polyhydric alcohol, poly-
Caprolactone diol, the mol ratio of diisocyanate are 1:0.2-0.4:3-4:0.004-0.006, and catalyst quality is remaining material
The 0.08-0.12% of gross mass.
C, in polyurethane liquid add dihydromethyl propionic acid, acetone, at 60-70 DEG C react 2-3h；Then continue to add
2-Hydroxy ethyl acrylate, is warming up to 70-80 DEG C of reaction 1-2h；Wherein, dihydromethyl propionic acid quality is the 4- of polyurethane liquid
8%, the quality of acetone is the 10-18% of polyurethane liquid, and the quality of 2-Hydroxy ethyl acrylate is the 2- of neutral polyether polyhydric alcohol
3 times.
D, solution is cooled to 45-50 DEG C, triethylamine react be added batch-wise in solution, stirring reaction, until solution ph
For 6.5-7.5；After last vacuum topping goes out acetone, natural aqueouss polyurethane acrylate prepolymer is obtained.
The natural aqueouss polyurethane acrylate prepolymer that said method is obtained, using the lignin of natural extraction, sky
So polyhydric alcohol etc., as raw material, poisons little, environmental protection.
Further, described catalyst is selected from dibutyl tin laurate, triethylene diamine or stannous octoate.
Further, described light trigger is 2- hydroxy-2-methyl -1- phenylacetone, 1- hydroxy cyclohexyl phenylketone, 2-
Hydroxy-2-methyl -1- is at least one in hydroxyl ether phenylacetone.
Further, being obtained by following methods of described cellulose aerogels:
Take timber and the wood powder that granularity is 100-300 mesh is obtained by pulverizer, it is 4- that wood powder is added to mass concentration
In 6% alkali liquor and carry out heating under evacuation environment to discongest, temperature is 140-180 DEG C, the time is 3-5h；Then carried out
Filter, the wood powder after discongesting is added in the alcoholic solution that mass concentration is 60-70%, is heated to seething with excitement and maintains 1.5- under normal pressure
2.5h；After filtering out liquid, insoluble matter is put in beater and is pulled an oar, wash after making beating, fiber after being dried, is obtained
Element, standby；The weight of wherein wood powder and alkali liquor is than for 1:6-8；The weight of the wood powder after discongesting and alcoholic solution is than for 1:10-20.
Prepared mass concentration soluble in water for shitosan is the chitosan solution of 3-5%, then adds in chitosan solution
Plus quality is the silver nitrate of 0.5-1 times of shitosan, after being uniformly dispersed, Deca acid solution makes the ph value of chitosan solution control in 3-5,
In transfer dark surrounds, heat 4h at 45-55 DEG C, then carry out centrifugal treating, obtain insoluble matter, after cleaning and being dried, will
Insoluble matter is dissolved in alkali liquor, adds the reducing agent that quality is insoluble matter 1-3%, adjust ph to 7-8, then stirred in alkali liquor
Mix, recentrifuge is obtained after processing and being dried and carries silver-colored shitosan, be 4-6%'s by carrying silver-colored shitosan and be dissolved in water mass concentration being obtained
Suspension, adding quality in suspension is to carry the halloysite nanotubes of silver-colored 2-4 times of shitosan, after water-bath vibration, room temperature
Lower standing 12-24h, after centrifugal treating, is obtained the silver-colored shitosan-halloysite nanotubes of load multiple after Solid separate is cleaned and is dried
Compound.
Standby cellulose is dissolved in cellulose solution that mass concentration be 3-5% in ionic liquid, is obtained, to cellulose
Add load silver shitosan-halloysite nanotubes complex that quality is cellulose 40-60% in liquid, be stirred disperseing, then
Cellulose solution is put in refrigerating plant and is freezed, take out after freezing 20-30h, flowing water thaws, prepared cellulose aquagel
Liquid, carries out solvent displacement, prepared cellulose alcogel liquid with excessive absolute alcohol to cellulose aquagel liquid；Finally carry out vacuum
After being dried and grinding, prepared cellulose aerogels.
The cellulose aerogels that said method is obtained are different from conventional cellulose aerogels, and it is cellulose and carries silver-colored shell
The composite of polysaccharide-halloysite nanotubes complex, carries silver-colored shitosan-halloysite nanotubes complex and imparts fiber simultaneously
The outstanding antibiotic property of plain aeroge and wearability.In the preparation process carrying silver-colored shitosan-halloysite nanotubes complex, first make
Then shitosan is combined by chitosan loaded upper silver with halloysite nanotubes, when the silver-colored shitosan-halloysite nanotubes complex of load
After mixing with cellulose, carry the intensity that silver-colored shitosan-halloysite nanotubes complex can improve aeroge.Additionally, above-mentioned side
The cellulose that method is obtained, it has preferable bridging property, can be with mutual crosslinking, thus stability is preferably, specific surface area is big.
Further, described timber is Masson Pine.
Further, described cellulose aerogels are in granular form, and its particle diameter is 0.5-2 micron.
The present invention has following beneficial effect: the uv cured printing ink composition that the inventive method is obtained, and has outstanding
Wearability, while relatively low viscosity, also has the characteristics that low toxicity evil and antibacterial.
Specific embodiment
With reference to embodiment, the invention will be further described.Raw materials used in the present invention, equipment, if no especially say
Bright, it is conventional raw material, the equipment of this area；Method therefor in the present invention, unless otherwise noted, is the routine side of this area
Method.
Embodiment one: a kind of preparation method of low toxicity evil uv cured printing ink composition, step is as follows:
Step 1: weigh the component of following weight portion: 60 parts of natural aqueouss polyurethane acrylate prepolymer, double [2- (first
Base acryloxy) ethyoxyl] 6 parts of dimethylsilane, 4 parts of light trigger, 5 parts of cellulose aerogels, 10 parts of pigment, defoamer
2 parts, 13 parts of water.
Step 2: by aqueouss polyurethane acrylate prepolymer natural in step 1, double [2- (methacryloxy) ethoxy
Base] dimethylsilane, cellulose aerogels, water add container in mix homogeneously be obtained binder solution, be then heated to 45 DEG C
And stir.
Step 3: add remaining component in binder solution, stir 1.5h under conditions of 35 DEG C, 1400r/min, carefully
Degree controls in 5-10 micron, and prepared low toxicity does harm to uv cured printing ink composition.
Above-mentioned natural aqueouss polyurethane acrylate prepolymer is obtained by following methods:
A, take lignin and be added in the phenol of 100 times of quality, be heated to 175 DEG C, stirring reaction 45min, instead
The mass concentration that before answering, 30min at the uniform velocity drips 160 times of lignin quality is 10% sodium hydroxide solution, with buffering after reaction
Solution adjusts ph to neutral, then naturally cools to 58 DEG C, adds furfural, the wood of 0.25 times of phenol quality of 1 times of phenol quality
Sugar alcohol or maltose alcohol, under heat-retaining condition, continue stirring reaction 90min, prepared neutral polyether polyhydric alcohol.
B, under nitrogen atmosphere, by neutral polyether polyhydric alcohol, polycaprolactone glycol, diisocyanate, tin dilaurate two fourth
Ji Xi, triethylene diamine or stannous octoate mixing, stirring reaction 2.5h under conditions of 52 DEG C, 160r/min, obtain polyurethane
Liquid；Wherein, neutral polyether polyhydric alcohol, polycaprolactone glycol, the mol ratio of diisocyanate are 1:0.3:3.5:0.005, February
Dilaurylate, triethylene diamine or stannous octoate quality is remaining material gross mass 0.1%.
C, in polyurethane liquid add dihydromethyl propionic acid, acetone, at 65 DEG C react 2.5h；Then continue to add propylene
Acid -2- hydroxy methacrylate, is warming up to 75 DEG C of reaction 1.5h；Wherein, dihydromethyl propionic acid quality is the 6% of polyurethane liquid, acetone
Quality is the 14% of polyurethane liquid, and the quality of 2-Hydroxy ethyl acrylate is 2.5 times of neutral polyether polyhydric alcohol.
D, solution is cooled to 48 DEG C, triethylamine react, stirring reaction are added batch-wise in solution, until solution ph is
6.5-7.5；After last vacuum topping goes out acetone, natural aqueouss polyurethane acrylate prepolymer is obtained.
Being obtained by following methods of above-mentioned cellulose aerogels: take Masson Pine and granularity to be obtained by pulverizer be 200 mesh
Wood powder, wood powder is added in the sodium hydroxide solution that mass concentration is 5% and carries out heating under evacuation environment and discongests,
Temperature is 160 DEG C, and the time is 4h；Then filtered, the wood powder after discongesting is added to the ethanol that mass concentration is 65% molten
In liquid, it is heated to seething with excitement under normal pressure and maintains 2h；After filtering out liquid, insoluble matter is put in beater and is pulled an oar, making beating
After wash, be dried after be obtained cellulose, standby；The weight of wherein wood powder and sodium hydroxide solution is than for 1:7；After discongesting
The weight of wood powder and alcoholic solution is than for 1:15.
The chitosan solution that prepared mass concentration soluble in water for shitosan is 4%, then adds in chitosan solution
Quality is the silver nitrate of 0.75 times of shitosan, and after being uniformly dispersed, Deca acid solution makes the ph value of chitosan solution control in 3-5, turns
Move in dark surrounds, heat 4h at 50 DEG C, then carry out centrifugal treating, obtain insoluble matter, after cleaning and being dried, by insoluble matter
It is dissolved in sodium hydroxide solution, adds the sodium borohydride that quality is insoluble matter 2% in sodium hydroxide solution, adjust ph to 7-8,
Then it is stirred, recentrifuge is prepared after processing and being dried to carry silver-colored shitosan, silver-colored for load shitosan is dissolved in the prepared quality of water dense
Spend the suspension for 5%, adding quality in suspension is to carry the halloysite nanotubes of silver-colored 3 times of shitosan, through water-bath vibration
Afterwards, stand 18h under room temperature, after centrifugal treating, be obtained after Solid separate is cleaned and is dried and carry silver-colored shitosan-galapectite nanometer
Pipe complex.
Standby cellulose is dissolved in cellulose solution that mass concentration be 4% in ionic liquid, is obtained, to cellulose solution
Middle interpolation quality is the load silver shitosan-halloysite nanotubes complex of cellulose 50%, is stirred disperseing, then by fiber
Plain liquid is put in refrigerating plant and is freezed, and freezes to take out after 24h, flowing water thaws, prepared cellulose aquagel liquid, with excessive
Dehydrated alcohol carries out solvent displacement, prepared cellulose alcogel liquid to cellulose aquagel liquid；Finally it is vacuum dried and ground
After mill, prepared particle diameter is the cellulose aerogels of 0.5-0.9 micron.
Embodiment two: a kind of preparation method of low toxicity evil uv cured printing ink composition, step is as follows:
Step 1: weigh the component of following weight portion: 50 parts of natural aqueouss polyurethane acrylate prepolymer, double [2- (first
Base acryloxy) ethyoxyl] 8 parts of dimethylsilane, 2 parts of light trigger, 8 parts of cellulose aerogels, 15 parts of pigment, defoamer
1 part, 16 parts of water.
Step 2: by aqueouss polyurethane acrylate prepolymer natural in step 1, double [2- (methacryloxy) ethoxy
Base] dimethylsilane, cellulose aerogels, water add container in mix homogeneously be obtained binder solution, be then heated to 35 DEG C
And stir.
Step 3: add remaining component in binder solution, stir 2h, fineness under conditions of 30 DEG C, 2000r/min
Control in 5-10 micron, prepared low toxicity does harm to uv cured printing ink composition.
Above-mentioned natural aqueouss polyurethane acrylate prepolymer is obtained by following methods:
A, take lignin and be added in the phenol of 80 times of quality, be heated to 170 DEG C, stirring reaction 50min, reaction
The mass concentration that front 30min at the uniform velocity drips 150 times of lignin quality is 10% sodium hydroxide solution, molten with buffering after reaction
Liquid adjusts ph to neutral, then naturally cools to 55 DEG C, adds furfural, the xylose of 0.2 times of phenol quality of 0.8 times of phenol quality
Alcohol or maltose alcohol, under heat-retaining condition, continue stirring reaction 100min, prepared neutral polyether polyhydric alcohol.
B, under nitrogen atmosphere, by neutral polyether polyhydric alcohol, polycaprolactone glycol, diisocyanate, tin dilaurate two fourth
Ji Xi, triethylene diamine or stannous octoate mixing, stirring reaction 3h under conditions of 50 DEG C, 170r/min, obtain polyurethane liquid；
Wherein, neutral polyether polyhydric alcohol, polycaprolactone glycol, the mol ratio of diisocyanate are 1:0.2:3:0.004, tin dilaurate two
Butyl tin, triethylene diamine or stannous octoate quality is remaining material gross mass 0.08%.
C, in polyurethane liquid add dihydromethyl propionic acid, acetone, at 60 DEG C react 3h；Then continue to add propylene
Acid -2- hydroxy methacrylate, is warming up to 70 DEG C of reaction 2h；Wherein, dihydromethyl propionic acid quality is the 4% of polyurethane liquid, the matter of acetone
Measure 10% for polyurethane liquid, the quality of 2-Hydroxy ethyl acrylate is 2 times of neutral polyether polyhydric alcohol.
D, solution is cooled to 45 DEG C, triethylamine react, stirring reaction are added batch-wise in solution, until solution ph is
6.5-7.5；After last vacuum topping goes out acetone, natural aqueouss polyurethane acrylate prepolymer is obtained.
Being obtained by following methods of above-mentioned cellulose aerogels: take Masson Pine and granularity to be obtained by pulverizer be 100 mesh
Wood powder, wood powder is added in the potassium hydroxide solution that mass concentration is 4% and carries out heating under evacuation environment and discongests,
Temperature is 140 DEG C, and the time is 5h；Then filtered, the wood powder after discongesting is added to the ethanol that mass concentration is 60% molten
In liquid, it is heated to seething with excitement under normal pressure and maintains 1.5h；After filtering out liquid, insoluble matter is put in beater and is pulled an oar, beat
Wash after slurry, cellulose after being dried, is obtained, standby；The weight of wherein wood powder and potassium hydroxide solution is than for 1:6-8；Discongest
The weight of wood powder afterwards and ethanol solution is than for 1:10.
The chitosan solution that prepared mass concentration soluble in water for shitosan is 3%, then adds in chitosan solution
Quality is the silver nitrate of 0.5 times of shitosan, and after being uniformly dispersed, Deca acid solution makes the ph value of chitosan solution control in 3-5, transfer
In dark surrounds, heat 4h at 45 DEG C, then carry out centrifugal treating, obtain insoluble matter, after cleaning and being dried, insoluble matter is molten
In potassium hydroxide solution, add the reducing agent that quality is insoluble matter 1% in potassium hydroxide solution, adjust ph to 7-8, then
It is stirred, recentrifuge is prepared after processing and being dried to carry silver-colored shitosan, silver-colored for load shitosan is dissolved in the prepared mass concentration of water and is
4% suspension, adding quality in suspension is to carry the halloysite nanotubes of silver-colored 2 times of shitosan, after water-bath vibration, often
Temperature is lower to stand 12h, after centrifugal treating, load silver-colored shitosan-halloysite nanotubes is obtained multiple after Solid separate is cleaned and is dried
Compound.
Standby cellulose is dissolved in cellulose solution that mass concentration be 3% in ionic liquid, is obtained, to cellulose solution
Middle interpolation quality is the load silver shitosan-halloysite nanotubes complex of cellulose 40%, is stirred disperseing, then by fiber
Plain liquid is put in refrigerating plant and is freezed, and freezes to take out after 20h, flowing water thaws, prepared cellulose aquagel liquid, with excessive
Absolute methanol carries out solvent displacement, prepared cellulose alcogel liquid to cellulose aquagel liquid；Finally it is vacuum dried and ground
After mill, prepared particle diameter is the cellulose aerogels of 1-2 micron.
Embodiment three: a kind of preparation method of low toxicity evil uv cured printing ink composition, step is as follows:
Step 1: weigh the component of following weight portion: 70 parts of natural aqueouss polyurethane acrylate prepolymer, double [2- (first
Base acryloxy) ethyoxyl] 4 parts of dimethylsilane, 6 parts of light trigger, 2 parts of cellulose aerogels, 5 parts of pigment, defoamer 3
Part, 10 parts of water.
Step 2: by aqueouss polyurethane acrylate prepolymer natural in step 1, double [2- (methacryloxy) ethoxy
Base] dimethylsilane, cellulose aerogels, water add container in mix homogeneously be obtained binder solution, be then heated to 55 DEG C
And stir.
Step 3: add remaining component in binder solution, stir 1h, fineness control under conditions of 40 DEG C, 800r/min
System does harm to uv cured printing ink composition in 5-10 micron, prepared low toxicity.
Above-mentioned natural aqueouss polyurethane acrylate prepolymer is obtained by following methods:
A, take lignin and be added in the phenol of 120 times of quality, be heated to 180 DEG C, stirring reaction 40min, instead
The mass concentration that before answering, 30min at the uniform velocity drips 170 times of lignin quality is 10% sodium hydroxide solution, with buffering after reaction
Solution adjusts ph to neutral, then naturally cools to 60 DEG C, adds furfural, the wood of 0.3 times of phenol quality of 1.2 times of phenol quality
Sugar alcohol or maltose alcohol, under heat-retaining condition, continue stirring reaction 80min, prepared neutral polyether polyhydric alcohol.
B, under nitrogen atmosphere, by neutral polyether polyhydric alcohol, polycaprolactone glycol, diisocyanate, tin dilaurate two fourth
Ji Xi, triethylene diamine or stannous octoate mixing, stirring reaction 2h under conditions of 55 DEG C, 150r/min, obtain polyurethane liquid；
Wherein, neutral polyether polyhydric alcohol, polycaprolactone glycol, the mol ratio of diisocyanate are 1:0.4:4:0.006, tin dilaurate two
Butyl tin, triethylene diamine or stannous octoate quality is remaining material gross mass 0.12%.
C, in polyurethane liquid add dihydromethyl propionic acid, acetone, at 70 DEG C react 2h；Then continue to add propylene
Acid -2- hydroxy methacrylate, is warming up to 80 DEG C of reaction 1h；Wherein, dihydromethyl propionic acid quality is the 8% of polyurethane liquid, the matter of acetone
Measure 18% for polyurethane liquid, the quality of 2-Hydroxy ethyl acrylate is 3 times of neutral polyether polyhydric alcohol.
D, solution is cooled to 50 DEG C, triethylamine react, stirring reaction are added batch-wise in solution, until solution ph is
6.5-7.5；After last vacuum topping goes out acetone, natural aqueouss polyurethane acrylate prepolymer is obtained.
Being obtained by following methods of above-mentioned cellulose aerogels:
Take Masson Pine and the wood powder that granularity is 300 mesh is obtained by pulverizer, wood powder is added to the hydrogen that mass concentration is 6%
In sodium hydroxide solution and carry out heating under evacuation environment to discongest, temperature is 180 DEG C, the time is 3h；Then filtered, will
Wood powder after discongesting is added in the ethanol solution that mass concentration is 70%, is heated to seething with excitement and maintains 2.5h under normal pressure；Filter
After falling liquid, insoluble matter is put in beater and is pulled an oar, wash after making beating, cellulose after being dried, is obtained, standby；Its
The weight of middle wood powder and alkali sodium hydroxide solution is than for 1:8；The weight of the wood powder after discongesting and ethanol solution is than for 1:20.
The chitosan solution that prepared mass concentration soluble in water for shitosan is 5%, then adds in chitosan solution
Quality is the silver nitrate of 1 times of shitosan, and after being uniformly dispersed, Deca acid solution makes the ph value of chitosan solution control in 3-5, and transfer is black
In dark situation, heat 4h at 55 DEG C, then carry out centrifugal treating, obtain insoluble matter, after cleaning and being dried, insoluble matter is dissolved in
In sodium hydroxide solution, add the reducing agent that quality is insoluble matter 3% in sodium hydroxide solution, adjust ph to 7-8, Ran Houjin
Row stirring, recentrifuge is obtained after processing and being dried and carries silver-colored shitosan, is 6% by carrying silver-colored shitosan and be dissolved in water mass concentration being obtained
Suspension, adding quality in suspension is to carry the halloysite nanotubes of silver-colored 4 times of shitosan, after water-bath vibration, room temperature
Lower standing 24h, after centrifugal treating, is obtained the silver-colored shitosan-halloysite nanotubes of load and is combined after Solid separate is cleaned and is dried
Thing.
Standby cellulose is dissolved in cellulose solution that mass concentration be 5% in ionic liquid, is obtained, to cellulose solution
Middle interpolation quality is the load silver shitosan-halloysite nanotubes complex of cellulose 60%, is stirred disperseing, then by fiber
Plain liquid is put in refrigerating plant and is freezed, and freezes to take out after 30h, flowing water thaws, prepared cellulose aquagel liquid, with excessive
Absolute methanol carries out solvent displacement, prepared cellulose alcogel liquid to cellulose aquagel liquid；Finally it is vacuum dried and ground
After mill, prepared particle diameter is the cellulose aerogels of 1-2 micron.
Above example is only the section Example of the present invention, not the present invention is imposed any restrictions, every according to this
Any simple modification, change and equivalent transformation that bright technical spirit is made to above example, all still fall within the technology of the present invention
The protection domain of scheme.
Claims (7)
1. a kind of preparation method of low toxicity evil uv cured printing ink composition, is characterized in that step is as follows:
Step 1: weigh the component of following weight portion: natural aqueouss polyurethane acrylate prepolymer 50-70 part, double [2- (methyl
Acryloxy) ethyoxyl] dimethylsilane 4-8 part, light trigger 2-6 part, cellulose aerogels 2-8 part, pigment 5-15 part,
Defoamer 1-3 part, water 10-16 part；
Step 2: by aqueouss polyurethane acrylate prepolymer natural in step 1, double [2- (methacryloxy) ethyoxyls]
Dimethylsilane, cellulose aerogels, water add mix homogeneously in container and binder solution are obtained, and are then heated to 35-55 DEG C
And stir；
Step 3: add remaining component in binder solution, under conditions of 30-40 DEG C, 800-2000r/min, stir 1-2h,
Fineness controls in 5-10 micron, and prepared low toxicity does harm to uv cured printing ink composition.
2. a kind of preparation method of low toxicity evil uv cured printing ink composition according to claim 1, is characterized in that: described sky
So aqueous polyurethane acrylate performed polymer is obtained by following methods:
A, take lignin and be added in the phenol of 80-120 times of quality, be heated to 170-180 DEG C, stirring reaction 40-
50min, the mass concentration that before reaction, 30min at the uniform velocity drips 150-170 times of lignin quality is 10% sodium hydroxide solution,
Adjust ph to neutral with buffer solution after reaction, then naturally cool to 55-60 DEG C, add the bran of phenol quality 0.8-1.2 times
Aldehyde, the natural polyols of phenol quality 0.2-0.3 times, under heat-retaining condition, continue stirring reaction 80-100min, are obtained natural poly-
Ethoxylated polyhydric alcohol；Described natural polyols are xylitol or maltose alcohol；
B, under nitrogen atmosphere, by neutral polyether polyhydric alcohol, polycaprolactone glycol, diisocyanate, catalyst mixing, in 50-
55 DEG C, stirring reaction 2-3h under conditions of 150-170r/min, obtain polyurethane liquid；Wherein, neutral polyether polyhydric alcohol, poly- in oneself
Esterdiol, the mol ratio of diisocyanate are 1:0.2-0.4:3-4:0.004-0.006, and catalyst quality is the total matter of remaining material
The 0.08-0.12% of amount；
C, in polyurethane liquid add dihydromethyl propionic acid, acetone, at 60-70 DEG C react 2-3h；Then continue to add propylene
Acid -2- hydroxy methacrylate, is warming up to 70-80 DEG C of reaction 1-2h；Wherein, dihydromethyl propionic acid quality is the 4-8% of polyurethane liquid, third
The quality of ketone is the 10-18% of polyurethane liquid, and the quality of 2-Hydroxy ethyl acrylate is 2-3 times of neutral polyether polyhydric alcohol；
D, solution is cooled to 45-50 DEG C, triethylamine react, stirring reaction are added batch-wise in solution, until solution ph is
6.5-7.5；After last vacuum topping goes out acetone, natural aqueouss polyurethane acrylate prepolymer is obtained.
3. the preparation method of a kind of low toxicity evil uv cured printing ink composition according to claim 2, is characterized in that: described urges
Agent is selected from dibutyl tin laurate, triethylene diamine or stannous octoate.
4. a kind of preparation method of low toxicity evil uv cured printing ink composition according to claim 1, is characterized in that: described light
Initiator is 2- hydroxy-2-methyl -1- phenylacetone, 1- hydroxy cyclohexyl phenylketone, 2- hydroxy-2-methyl -1- to hydroxy ether
At least one in base phenylacetone.
5. the preparation method of a kind of low toxicity evil uv cured printing ink composition according to one of claim 1-4, is characterized in that:
Being obtained by following methods of described cellulose aerogels:
Take timber and the wood powder that granularity is 100-300 mesh is obtained by pulverizer, it is 4-6%'s that wood powder is added to mass concentration
In alkali liquor and carry out heating under evacuation environment to discongest, temperature is 140-180 DEG C, the time is 3-5h；Then filtered, will
Wood powder after discongesting is added in the alcoholic solution that mass concentration is 60-70%, is heated to seething with excitement and maintains 1.5-2.5h under normal pressure；
After filtering out liquid, insoluble matter is put in beater and is pulled an oar, wash after making beating, cellulose after being dried, is obtained, standby
With；The weight of wherein wood powder and alkali liquor is than for 1:6-8；The weight of the wood powder after discongesting and alcoholic solution is than for 1:10-20；
Prepared mass concentration soluble in water for shitosan is the chitosan solution of 3-5%, in chitosan solution, then adds matter
Measure the silver nitrate for 0.5-1 times of shitosan, after being uniformly dispersed, Deca acid solution makes the ph value of chitosan solution control in 3-5, transfer
In dark surrounds, heat 4h at 45-55 DEG C, then carry out centrifugal treating, obtain insoluble matter, after cleaning and being dried, will be insoluble
Thing is dissolved in alkali liquor, adds the reducing agent that quality is insoluble matter 1-3%, adjust ph to 7-8, be then stirred in alkali liquor,
Recentrifuge is obtained after processing and being dried and carries silver-colored shitosan, is the outstanding of 4-6% by carrying silver-colored shitosan and be dissolved in water mass concentration being obtained
Supernatant liquid, adding quality in suspension is to carry the halloysite nanotubes of silver-colored 2-4 times of shitosan, after water-bath vibration, under room temperature
Standing 12-24h, after centrifugal treating, is obtained the silver-colored shitosan-halloysite nanotubes of load and is combined after Solid separate is cleaned and is dried
Thing；
Standby cellulose is dissolved in cellulose solution that mass concentration be 3-5% in ionic liquid, is obtained, in cellulose solution
Add load silver shitosan-halloysite nanotubes complex that quality is cellulose 40-60%, be stirred disperseing, then by fibre
The plain liquid of dimension is put in refrigerating plant and is freezed, and takes out, flowing water thaws, prepared cellulose aquagel liquid, use after freezing 20-30h
Excessive absolute alcohol carries out solvent displacement, prepared cellulose alcogel liquid to cellulose aquagel liquid；Finally it is vacuum dried
And after grinding, prepared cellulose aerogels.
6. a kind of preparation method of low toxicity evil uv cured printing ink composition according to claim 5, is characterized in that: described wood
Material is Masson Pine.
7. a kind of preparation method of low toxicity evil uv cured printing ink composition according to claim 5, is characterized in that: described fibre
The plain aeroge of dimension is in granular form, and its particle diameter is 0.5-2 micron.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610682400.4A CN106349804A (en) | 2016-08-17 | 2016-08-17 | Preparation method of low-poison UV (ultraviolet)-curing ink composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610682400.4A CN106349804A (en) | 2016-08-17 | 2016-08-17 | Preparation method of low-poison UV (ultraviolet)-curing ink composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106349804A true CN106349804A (en) | 2017-01-25 |
Family
ID=57845031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610682400.4A Pending CN106349804A (en) | 2016-08-17 | 2016-08-17 | Preparation method of low-poison UV (ultraviolet)-curing ink composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106349804A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113652076A (en) * | 2021-05-26 | 2021-11-16 | 袁望平 | Dustproof sound insulation plate with buffering function and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702566A (en) * | 2012-06-20 | 2012-10-03 | 东北林业大学 | Method for preparing lignocellulose aerogel by using ionic liquid |
| CN102977684A (en) * | 2012-12-07 | 2013-03-20 | 武汉大学 | Water-soluble (Ultra Violet) curing ink and preparation method thereof |
| CN104725956A (en) * | 2015-02-11 | 2015-06-24 | 长兴艾飞特塑料科技有限公司 | Preparation method of antibacterial water-soluble varnish used for package printing |
| CN105053007A (en) * | 2015-08-06 | 2015-11-18 | 北京科技大学 | Preparation method of novel high performance antibacterial nano-cellulose carbon aerogel |
| CN105418286A (en) * | 2015-12-30 | 2016-03-23 | 民勤县巴腾生物有机肥料有限公司 | Wolfberry dedicated fertilizer and preparation method thereof |
| CN105542694A (en) * | 2016-01-18 | 2016-05-04 | 陈茂清 | Double-component resin type elastic joint mixture and preparation method thereof |
-
2016
- 2016-08-17 CN CN201610682400.4A patent/CN106349804A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702566A (en) * | 2012-06-20 | 2012-10-03 | 东北林业大学 | Method for preparing lignocellulose aerogel by using ionic liquid |
| CN102977684A (en) * | 2012-12-07 | 2013-03-20 | 武汉大学 | Water-soluble (Ultra Violet) curing ink and preparation method thereof |
| CN104725956A (en) * | 2015-02-11 | 2015-06-24 | 长兴艾飞特塑料科技有限公司 | Preparation method of antibacterial water-soluble varnish used for package printing |
| CN105053007A (en) * | 2015-08-06 | 2015-11-18 | 北京科技大学 | Preparation method of novel high performance antibacterial nano-cellulose carbon aerogel |
| CN105418286A (en) * | 2015-12-30 | 2016-03-23 | 民勤县巴腾生物有机肥料有限公司 | Wolfberry dedicated fertilizer and preparation method thereof |
| CN105542694A (en) * | 2016-01-18 | 2016-05-04 | 陈茂清 | Double-component resin type elastic joint mixture and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113652076A (en) * | 2021-05-26 | 2021-11-16 | 袁望平 | Dustproof sound insulation plate with buffering function and preparation method thereof |
| CN113652076B (en) * | 2021-05-26 | 2022-12-27 | 苏州鱼得水电气科技有限公司 | Dustproof sound insulation plate with buffering function and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101003715A (en) | Method for preparing modified aqueous adhesion agent of polyurethane | |
| CN106752850B (en) | It can solidify rapidly, waterproof, high-low temperature resistant, low VOC polyurethane coating | |
| CN106046924B (en) | A kind of preparation method of wear-resisting type UV cured printing ink composition | |
| DE4318094A1 (en) | Superabsorbents and a process for their preparation | |
| CN101429282A (en) | Plant fiber based polyether polyol and preparation method thereof | |
| CN107236109A (en) | Citrated chitin modified water polyurethane and preparation method thereof | |
| CN106221362A (en) | A kind of low murder by poisoning UV cured printing ink composition | |
| CN110483165B (en) | Coated slow-control fertilizer and preparation method thereof | |
| CN102993406A (en) | Preparation method of high-transparency UV resistant curing polyurethane-zinc oxide nano composite resin | |
| CN104987516A (en) | Preparation method for pH intelligent response membrane with nano-crystalline cellulose for enhancing tara gum substrate | |
| CN106349804A (en) | Preparation method of low-poison UV (ultraviolet)-curing ink composition | |
| CN111808518A (en) | High-stability single-component polyurethane waterproof coating and preparation method thereof | |
| CN107778767B (en) | Preparation method of lignin phenolic resin foam material | |
| CN113264805A (en) | Cellulose modified polyurethane coated fertilizer and preparation method and application thereof | |
| EP3070131A1 (en) | Aqueous ink composition for writing tools | |
| CN103923523B (en) | Multi-arm star-shaped acrylate copolymer-modified polyurethane printing ink and preparation method thereof | |
| CN111647306B (en) | In situ generation of organized SiO 2 Environment-friendly enhanced waterborne polyurethane ink and preparation method thereof | |
| CN111013506B (en) | Microcapsule emulsion of micromolecular anti-aging agent with degradable capsule wall and preparation method and application thereof | |
| CN111826064A (en) | Green environment-friendly coating and preparation method thereof | |
| CN107200853A (en) | A kind of dendrimer/carboxymethyl cellulose superabsorbent hydrogel and its preparation and application | |
| CN103588934A (en) | Method for preparing salt tolerant super absorbent resin by bentonite | |
| CN106543485A (en) | Novel degradable plastic bag and preparation method thereof | |
| CN111234602A (en) | High-adhesion color water-based ink for plastics and preparation method thereof | |
| CN106318020A (en) | Wear-proof UV solidification ink composition | |
| CN101735420B (en) | Preparation method and application method of biomass liquid agricultural membrane material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170125 |