CN101348541A - Self-crosslinking acrylic ester composition emulsion for plastic printing ink and preparation thereof - Google Patents
Self-crosslinking acrylic ester composition emulsion for plastic printing ink and preparation thereof Download PDFInfo
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Abstract
A self-crosslink acrylic ester compound emulsion for plastic ink and a preparation method thereof belong to the technical field of macromolecular synthesis. In order to solve the problems of the'ink shrinking' of the plastic ink on the surface of plastics and the adhesion force, the invention provides the self-crosslink acrylic ester compound emulsion for the plastic ink. The latex is a product obtained through emulsion polymerization which is carried out by a functional monomer with low polymerization shrinkage, low surface tension and higher permeability and other vinyl monomers. The invention also discloses the preparation method for the emulsion. The preparation method which is carried out through the pre-emulsification nucleocapsid emulsion technology mainly comprises the following two steps: 1. preparing a seed nucleus emulsion; and 2. preparing the nucleocapsid emulsion based on the seed nucleus emulsion to finally obtain the self-crosslink acrylic ester compound emulsion for the plastic ink. The emulsion which is bright and transparent after film forming has good adhesion force to a plastic base material, and the adhesion force to PP, PE films is particularly excellent.
Description
Technical field
The present invention relates to self-crosslinking acrylic ester composition emulsion for plastic printing ink and preparation method thereof, belong to the macromolecule synthesising technology field.
Background technology
Paper printing is in the history of the existing more than one thousand years of China, and plastic film printing is in China's history of decades only.Along with the petrochemical complex industrial expansion, the mass production and the widespread use of polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC) have promoted the development of plastic printing and corresponding printing ink.Paper is a porous substrate, and the plastics film slick base material that is surface compact, this has just highlighted the different requirements to printing ink, and sticking power is the most tangible problem.Since the last century the eighties, the bonding material that ink used for plastic is used all is oil-soluble resin basically.Common have Chlorinated Polypropylene III, chlorinatedpolyethylene, Atactic Polypropelene, alkyl vinyl ether polymer, vinyl-acetic ester-ethylene copolymer, terpine resin, petroleum resin etc.Therefrom select a kind of or two to three kinds make resin liquid with toluene or dimethylbenzene, N-BUTYL ACETATE equal solvent, in order to preparation printing ink, we also once used acrylic ester grafted to Chlorinated Polypropylene III, made the toluene solution of sticking power excellence, but the gloss of filming is unstable sometimes.We select extraordinary monomer again subsequently, are that main body has been carried out solution polymerization with the acrylate monomer, make all good resin liquid of sticking power, gloss.Problem is that a large amount of organic solvent volatilizations cause the pollution of environment and the infringement of HUMAN HEALTH in the use.Unit such as Beijing Printing Institute released the preparation that spirit-soluble resin liquid is used for ink used for plastic afterwards.It has alleviated the infringement to human body, but organism still exists the influence of environment.We since the beginning of this century working foundation in the past be the research that medium (solvent) is used for the ink used for plastic bonding material with water.This has just broken away from the influence of organic solvent, for environment-friendly and green printing ink has been created condition.But the technical barrier that water brings is many: the surface tension of water is big, and frosting tension force is little, and hydrophobicity is strong, thus be that medium just must solve " oil contracts " and the sticking power problem at frosting with water, and sticking power is the very corn of a subject.With water is that medium can have two kinds of selections: a kind of is preparation water-soluble acrylic ester copolymer resins, and another kind then is preparation water miscible liquid or aqueous dispersion resin liquid.The former general poor adhesive force, the latter is big to the composition adjustable of resin, helps obtaining good emulsion of sticking power or aqueous dispersion resin liquid.
Summary of the invention
In order to solve " oil contract " and the sticking power problem of ink used for plastic at frosting, the present invention has adopted emulsion polymerization technology, select performance suitable monomer composition to make that the solubility parameter of its polymer dissolution parameter and plastics is close, be beneficial to and interpenetrate, spread and improve sticking power, take into account the own internal stress of emulsion resin little (particularly the shrinking percentage in film process is little) on the other hand, to be reduced in the film process destruction to sticking power.In line with this idea and environment protection requirement, prepared and can be used for polypropylene and poly printing ink emulsion.
The invention provides a kind of self-crosslinking acrylic ester composition emulsion for plastic printing ink, this emulsion is to have selected polymerization shrinkage little (for 7-8%), and surface tension is little and the function monomer of higher permeability and the product that other vinyl monomer gets by letex polymerization arranged; Wherein,
Described function monomer is selected following 1 to 4 kind of compound for use:
(methyl) isobornyl acrylate, (methyl) vinylformic acid double cyclopentenyl ester, (methyl) vinylformic acid three cyclopentenyl esters, tertiary ethylene carbonate, ethylene glycol bisthioglycolate (methyl) acrylate, butyleneglycol two (methyl) acrylate, pentaerythritol triacrylate, Viscoat 295
The diacetone-acryloamide(DAA) of ketocarbonyl-containing, acetoacetyl oxygen ethyl (methyl) acrylate,
Adipic dihydrazide, carbonic acid hydrazides;
Described other vinyl monomer is selected 2 to 5 kinds of compounds in methyl methacrylate, (methyl) butyl acrylate, (methyl) vinylformic acid, ethyl propenoate, ethyl acrylate, acrylamide, the vinylbenzene for use.
Emulsion preparation method of the present invention is to produce with pre-emulsification core-shell emulsion technology, mainly comprises for two steps: the preparation of the first step nucleus of the seed emulsion, in second step, on the basis of nucleus of the seed emulsion, carry out the preparation of core-shell emulsion.Finally obtain the self-crosslinking acrylic ester polymer emulsion that plastics of the present invention (particularly PP, PE) printing ink is used.Concrete steps are as follows:
The first step, the preparation of nucleus of the seed emulsion:
In reactor, add deionized water, emulsifying agent, the buffer reagent of a part, be warming up to 70 ℃-85 ℃, and it is standby to prepare a part of initiator solution;
The function monomer that the nucleus of the seed emulsion is used and other vinyl monomer are made the nuclear pre-emulsion with emulsifying agent, initiator, the deionized water of remaining part in pre-emulsor;
When treating that above-mentioned temperature of reactor rises to 70 ℃-85 ℃, earlier the above-mentioned initiator solution for preparing is added in the reactor, to examine 10% of pre-emulsion again adds in the reactor, react after 20-50 minute, again 90% nuclear pre-emulsion of remainder is splashed into and continue reaction 1.5-4.5 hour in the described reactor, get the nucleus of the seed emulsion, the weight % content of each component of reactant of nucleus of the seed emulsion is as follows:
The function monomer 0-10% that the nucleus of the seed emulsion is used
Other vinyl monomer 15%-30% that the nucleus of the seed emulsion is used
Emulsifying agent 0.5%-1.2%
Initiator 0.25%-0.7%
Deionized water 60%-75%
Buffer reagent 0.08%-0.15%
Second step, the preparation of core-shell emulsion:
The function monomer that shell is used, other vinyl monomer, and shell pre-emulsion and above-mentioned nucleus of the seed emulsion that emulsifying agent, initiator, molecular weight regulator, deionized water are made are carried out letex polymerization, 70 ℃-90 ℃ of temperature of reaction, after reaction times 2-6 hour, add the PH conditioning agent, promptly make self-crosslinking acrylic ester composition emulsion for plastic printing ink of the present invention, each composition weight % content of its reactant is as follows:
Other vinyl monomer 18%-27% that shell is used
The function monomer 2%-8% that shell is used
Emulsifying agent 0.1%-0.55%
Initiator 0.06%-0.15%
Molecular weight regulator 0.02%-0.18%
Deionized water 12%-21%
Above-mentioned nucleus of the seed emulsion 50%-65%
Wherein,
What the nucleus of the seed emulsion was used selects following 1 to 4 kind of compound for use with the used function monomer of shell:
(methyl) isobornyl acrylate, (methyl) vinylformic acid double cyclopentenyl ester, (methyl) vinylformic acid three cyclopentenyl esters, tertiary ethylene carbonate, ethylene glycol bisthioglycolate (methyl) acrylate, butyleneglycol two (methyl) acrylate, pentaerythritol triacrylate, Viscoat 295
The diacetone-acryloamide(DAA) of ketocarbonyl-containing, acetoacetyl oxygen ethyl (methyl) acrylate,
Adipic dihydrazide, carbonic acid hydrazides;
What the nucleus of the seed emulsion was used selects 2 to 5 kinds of compounds in methyl methacrylate, (methyl) butyl acrylate, (methyl) vinylformic acid, ethyl propenoate, ethyl acrylate, acrylamide, the vinylbenzene for use with other used vinyl monomer of shell.
In the present invention, described emulsifying agent is selected in alkylphenol polyoxyethylene vitriol, the alkylphenol polyoxyethylene one or both mixture for use; Described initiator is selected one or both the mixture in Potassium Persulphate, Sodium Persulfate, the ammonium persulphate for use.Described buffer reagent is selected a kind of in Sodium phosphate dibasic or the sodium bicarbonate for use; Described molecular weight regulator is selected dodecyl mercaptans or the different monooctyl ester of thiohydracrylic acid for use; Described PH conditioning agent is selected one or both the mixture in sodium hydroxide (potassium), 2-methyl-2-aminopropanol, the ammoniacal liquor for use.
The salient features technical indicator such as the following table of self-crosslinking acrylic ester composition emulsion for plastic printing ink of the present invention:
| Test item | The method of inspection and condition | The result |
| Outward appearance | Range estimation | The milky white liquid of little blueness |
| PH | The PH test paper | 6.5-8.5 |
| Viscosity mPas | The rotor viscosity apparatus | 35-350 |
| Tg℃ | Calculated value | -33℃-35℃ |
| Calcium ion stability | 48h, 0.5% calcium chloride solution | No layering, nothing precipitation, nothing flocculation |
| Mechanical stability | 30min, 2500 commentaries on classics/min | No layering, nothing precipitation, nothing flocculation |
| Solids content | 1h、120℃±2℃ | 40％-50％ |
Behind the emulsion film forming of the present invention, clear transparent, plastic basis material there is good adhesive, particularly, PVC, PET, ABS etc. is also had good adhesive the sticking power excellence of PP, PE film.Adopt self-crosslinking acrylic ester composition emulsion of the present invention, can be mixed with the good aqueous, environmental protective printing ink that is used for plastic films such as PP, PE, PVC, PET, ABS of sticking power.
Embodiment
Self-crosslinking acrylic ester composition emulsion for plastic printing ink of the present invention is to have selected polymerization shrinkage little (for 7-8%), and surface tension is little and the function monomer of higher permeability and the product that other vinyl monomer gets by letex polymerization arranged; Wherein,
Described function monomer is selected following 1 to 4 kind of compound for use:
(methyl) isobornyl acrylate, (methyl) vinylformic acid double cyclopentenyl ester, (methyl) vinylformic acid three cyclopentenyl esters, tertiary ethylene carbonate, ethylene glycol bisthioglycolate (methyl) acrylate, butyleneglycol two (methyl) acrylate, pentaerythritol triacrylate, Viscoat 295
The diacetone-acryloamide(DAA) of ketocarbonyl-containing, acetoacetyl oxygen ethyl (methyl) acrylate,
Adipic dihydrazide, carbonic acid hydrazides;
Described other vinyl monomer is selected 2 to 5 kinds of compounds in methyl methacrylate, (methyl) butyl acrylate, (methyl) vinylformic acid, ethyl propenoate, ethyl acrylate, acrylamide, the vinylbenzene for use.
As example of the present invention, the required function monomer of described letex polymerization can be selected isobornyl acrylate, diacetone-acryloamide(DAA), adipic dihydrazide (or carbonic acid hydrazides) for use, wherein, adipic dihydrazide (or carbonic acid hydrazides) consumption is the 35-48% of diacetone-acryloamide(DAA) mole number.
As example of the present invention, the required function monomer of letex polymerization of the present invention can be selected isobornyl acrylate, vinylformic acid double cyclopentenyl ester, diacetone-acryloamide(DAA), adipic dihydrazide (or carbonic acid hydrazides) for use, wherein, adipic dihydrazide (or carbonic acid hydrazides) consumption is the 35-48% of diacetone-acryloamide(DAA) mole number.
As example of the present invention, the required function monomer of letex polymerization of the present invention can be selected tertiary ethylene carbonate, diacetone-acryloamide(DAA), adipic dihydrazide (or carbonic acid hydrazides) for use, wherein, adipic dihydrazide (or carbonic acid hydrazides) consumption is the 35-48% of diacetone-acryloamide(DAA) mole number.
Emulsion preparation method of the present invention is to produce with pre-emulsification core-shell emulsion technology, mainly comprises for two steps: the preparation of the first step nucleus of the seed emulsion, in second step, on the basis of nucleus of the seed emulsion, carry out the preparation of core-shell emulsion.Finally obtain the self-crosslinking acrylic ester polymer emulsion that plastics of the present invention (particularly PP, PE) printing ink is used.
Embodiment 1
Self-crosslinking acrylic ester composition emulsion for plastic printing ink among the embodiment 1 adopts following two big step preparations:
The first step, the preparation of nucleus of the seed emulsion:
In reactor, add deionized water, emulsifying agent (adopting alkylphenol polyoxyethylene ammonium sulfate (58%) in this example), buffer reagent (adopting sodium bicarbonate in this example) is warming up to 70 ℃-85 ℃, and prepares initiator (adopting ammonium persulphate in this example) solution for standby.Each composition weight is as follows:
Alkylphenol polyoxyethylene ammonium sulfate (58%) 1 gram
Sodium bicarbonate 0.2 gram
Deionized water 137 grams
Ammonium persulphate 10% aqueous solution 3.6 grams
The function monomer that the nucleus of the seed emulsion is used (adopting isobornyl acrylate, butylene glycol dimethacrylate in this example) and other vinyl monomer (adopting butyl acrylate, ethyl propenoate, vinylformic acid in this example) are made the nuclear pre-emulsion with emulsifying agent (adopting alkylphenol polyoxyethylene ammonium sulfate (58%) in this example), initiator (adopting ammonium persulphate in this example), deionized water in pre-emulsor.
When treating that above-mentioned temperature of reactor rises to 70 ℃-85 ℃, earlier the above-mentioned initiator solution for preparing is added in the reactor, to examine 10% of pre-emulsion again adds in the reactor, react after 20-50 minute, again 90% nuclear pre-emulsion of remainder is splashed into and continue reaction 1.5-4.5 hour in the reactor, get the nucleus of the seed emulsion, the weight of its each component of reactant is as follows:
Butyl acrylate 40 grams
Ethyl propenoate 20 grams
Isobornyl acrylate 6 grams
Vinylformic acid 2 grams
Butylene glycol dimethacrylate 3 grams
Ammonium persulphate 0.48 gram
Alkylphenol polyoxyethylene ammonium sulfate (58%) 1.56 gram
Deionized water 34 grams
Second step, the preparation of core-shell emulsion:
The function monomer that shell is used (adopting isobornyl acrylate, diacetone-acryloamide(DAA), butylene glycol dimethacrylate in this example), other vinyl monomer (adopting butyl acrylate, vinylformic acid in this example), and the shell pre-emulsion made of emulsifying agent (in this example adopt alkylphenol polyoxyethylene ammonium sulfate (58%)), initiator (adopting ammonium persulphate in this example), molecular weight regulator (adopting dodecyl mercaptans in this example), deionized water splashes into above-mentioned nucleus of the seed emulsion and carries out letex polymerization, 70 ℃-90 ℃ of temperature of reaction dripped time spent 2-4 hour.Drip off the back and be incubated 2-3 hour to reacting completely, cooling is transferred PH=7-8 with ammoniacal liquor, adds the aqueous solution of adipic dihydrazide, and the after-filtration discharging stirs.Promptly make self-crosslinking acrylic ester composition emulsion for plastic printing ink of the present invention, each composition weight of its reactant is as follows:
Butyl acrylate 100 grams
Vinylformic acid 4 grams
Isobornyl acrylate 20 grams
Diacetone-acryloamide(DAA) 8 grams
Butylene glycol dimethacrylate 1 gram
Dodecyl mercaptans 1 gram
Ammonium persulphate 0.36 gram
Alkylphenol polyoxyethylene ammonium sulfate (58%) 0.96 gram
Deionized water 68 grams
Adipic dihydrazide 3.5 grams
Deionized water 32 grams
Getting emulsion solid content is 44 ± 2%, PH=7.5, second-order transition temperature Tg
1=-33 ℃, second-order transition temperature Tg
2=-28 ℃, viscosity 35mpas.Emulsion all has fine sticking power to polypropylene screen, polyester film, polychloroethylene film.
Embodiment 2:
Self-crosslinking acrylic ester composition emulsion for plastic printing ink among the embodiment 2 adopts following two big step preparations:
The first step, the preparation of nucleus of the seed emulsion:
In reactor, add deionized water, emulsifying agent (adopting alkylphenol polyoxyethylene ammonium sulfate (58%), alkylphenol polyoxyethylene in this example), buffer reagent (adopting Sodium phosphate dibasic in this example) is warming up to 70 ℃-85 ℃, and prepares initiator (adopting ammonium persulphate in this example) solution for standby.Each composition weight is as follows:
Alkylphenol polyoxyethylene ammonium sulfate (58%) 2.88 gram
Alkylphenol polyoxyethylene 0.84 gram
Sodium phosphate dibasic 0.6 gram
Deionized water 397 grams
Ammonium persulphate 10% aqueous solution 3.2 grams
The function monomer that the nucleus of the seed emulsion is used (adopt in this example glycol diacrylate) and other vinyl monomer (adopting butyl acrylate, ethyl propenoate, methyl methacrylate in this example) are being made the nuclear pre-emulsion with emulsifying agent (adopting alkylphenol polyoxyethylene ammonium sulfate (58%), alkylphenol polyoxyethylene in this example), initiator (adopting ammonium persulphate in this example), deionized water in pre-emulsor.
When treating that above-mentioned temperature of reactor rises to 70 ℃-85 ℃, the above-mentioned initiator solution for preparing is added in the above-mentioned reactor, to examine 10% of pre-emulsion again adds in the described reactor, react after 20-50 minute, again 90% nuclear pre-emulsion of remainder is splashed into and continue reaction 1.5-4.5 hour in the described reactor, get the nucleus of the seed emulsion, the weight of its each component of reactant is as follows:
Butyl acrylate 90 grams
Ethyl propenoate 60 grams
Methyl methacrylate 54 grams
Glycol diacrylate 3 grams
Ammonium persulphate 1.56 grams
Alkylphenol polyoxyethylene 1.35 grams
Alkylphenol polyoxyethylene ammonium sulfate (58%) 4.68 gram
Deionized water 102 grams
Second step, the preparation of core-shell emulsion:
The function monomer that shell is used (adopts isobornyl acrylate in this example, glycol diacrylate, diacetone-acryloamide(DAA), acrylamide), other vinyl monomer (adopts butyl acrylate in this example, vinylformic acid, methyl methacrylate), and emulsifying agent (adopts alkylphenol polyoxyethylene ammonium sulfate (58%) in this example, alkylphenol polyoxyethylene), initiator (adopting ammonium persulphate in this example), molecular weight regulator (adopting dodecyl mercaptans in this example), the shell pre-emulsion that deionized water is made splashes into above-mentioned nucleus of the seed emulsion and carries out letex polymerization, 70 ℃-90 ℃ of temperature of reaction dripped time spent 2-4 hour.Drip off the back and be incubated 2-3 hour to reacting completely, cooling is transferred PH=7-8 with 2-methyl-2-aminopropanol, adds the aqueous solution of adipic dihydrazide, and the after-filtration discharging stirs.Promptly make self-crosslinking acrylic ester composition emulsion for plastic printing ink of the present invention, each composition weight of its reactant is as follows:
Butyl acrylate 200 grams
Vinylformic acid 12 grams
Methyl methacrylate 100 grams
Isobornyl acrylate 54 grams
Glycol diacrylate 1 gram
Diacetone-acryloamide(DAA) 24 grams
Acrylamide 6 grams
Dodecyl mercaptans 0.78 gram
Ammonium persulphate 1.08 grams
Alkylphenol polyoxyethylene ammonium sulfate (58%) 2.88 gram
Alkylphenol polyoxyethylene 0.84 gram
Deionized water 148 grams
Adipic dihydrazide 10 grams
Deionized water 82 grams
Getting emulsion solid content is 46%, PH=7.5, second-order transition temperature Tg
1=-16 ℃, second-order transition temperature Tg
2=12 ℃, viscosity 40mpas.Emulsion is good to PP, PVC, PET sticking power.
Embodiment 3:
Self-crosslinking acrylic ester composition emulsion for plastic printing ink among the embodiment 3 adopts following two big step preparations:
The first step, the preparation of nucleus of the seed emulsion:
In reactor, add deionized water, emulsifying agent (adopting alkylphenol polyoxyethylene ammonium sulfate (58%), alkylphenol polyoxyethylene in this example), buffer reagent (adopting sodium bicarbonate in this example) is warming up to 70 ℃-85 ℃, and prepares initiator (adopting ammonium persulphate in this example) solution for standby.Each composition weight is as follows:
Alkylphenol polyoxyethylene ammonium sulfate (58%) 0.96 gram
Alkylphenol polyoxyethylene 0.28 gram
Sodium bicarbonate 0.2 gram
Deionized water 137 grams
Ammonium persulphate 10% aqueous solution 3.2 grams
The function monomer that the nucleus of the seed emulsion is used (adopting pentaerythritol triacrylate in this example) and other vinyl monomer (adopting butyl acrylate, ethyl propenoate, methyl methacrylate in this example) are made the shell pre-emulsion with emulsifying agent (adopting alkylphenol polyoxyethylene ammonium sulfate (58%), alkylphenol polyoxyethylene in this example), initiator (adopting ammonium persulphate in this example), deionized water in pre-emulsor.
When treating that above-mentioned temperature of reactor rises to 70 ℃-85 ℃, earlier the above-mentioned initiator solution for preparing is added in the reactor, to examine 10% of pre-emulsion again adds in the reactor, react after 20-50 minute, again 90% nuclear pre-emulsion of remainder is splashed into and continue reaction 1.5-4.5 hour in the reactor, get the nucleus of the seed emulsion, the weight of its each component of reactant is as follows:
Butyl acrylate 30 grams
Ethyl propenoate 20 grams
Methyl methacrylate 18 grams
Pentaerythritol triacrylate 1.5 grams
Ammonium persulphate 0.52 gram
Alkylphenol polyoxyethylene 0.45 gram
Alkylphenol polyoxyethylene ammonium sulfate (58%) 1.56 gram
Deionized water 34 grams
Second step, the preparation of core-shell emulsion:
The function monomer that shell is used (adopts the vinylformic acid double cyclopentenyl ester in this example, isobornyl acrylate, pentaerythritol triacrylate, diacetone-acryloamide(DAA)), other vinyl monomer (adopts butyl methacrylate in this example, vinylformic acid, acrylamide), and emulsifying agent (adopts alkylphenol polyoxyethylene ammonium sulfate (58%) in this example, alkylphenol polyoxyethylene), initiator (adopting ammonium persulphate in this example), molecular weight regulator (adopting the different monooctyl ester of thiohydracrylic acid in this example), the pre-emulsion that deionized water is made splashes into above-mentioned nucleus of the seed emulsion and carries out letex polymerization, 70 ℃-90 ℃ of temperature of reaction dripped time spent 2-4 hour.Drip off the back and be incubated 2-3 hour to reacting completely, cooling is transferred PH=7-8 with sodium hydroxide, adds the aqueous solution of carbonic acid two hydrazides, and the after-filtration discharging stirs.Promptly make self-crosslinking acrylic ester composition emulsion for plastic printing ink of the present invention, each composition weight of its reactant is as follows:
Diacetone-acryloamide(DAA) 8 grams
Pentaerythritol triacrylate 0.8 gram
Vinylformic acid double cyclopentenyl ester 4 grams
Isobornyl acrylate 14 grams
Vinylformic acid 4 grams
Butyl methacrylate 100 grams
Acrylamide 2 grams
Different monooctyl ester 0.26 gram of thiohydracrylic acid
Ammonium persulphate 1.08 grams
Alkylphenol polyoxyethylene ammonium sulfate (58%) 0.96 gram
Alkylphenol polyoxyethylene 0.28 gram
Deionized water 58 grams
Carbonic acid hydrazides 3.5 grams
Deionized water 18 grams
Get emulsion solid content 45 ± 2%, PH=7.5, second-order transition temperature Tg
1=-15.6 ℃, second-order transition temperature Tg
2=34 ℃, viscosity 45mpas.
Embodiment 4:
Self-crosslinking acrylic ester composition emulsion for plastic printing ink among the embodiment 4 adopts following two big step preparations:
The first step, the preparation of nucleus of the seed emulsion:
In reactor, add deionized water, emulsifying agent (adopting alkylphenol polyoxyethylene ammonium sulfate (58%) in this example), buffer reagent (adopting sodium bicarbonate in this example) is warming up to 70 ℃-85 ℃, and prepares initiator (adopting ammonium persulphate in this example) solution for standby.Each composition weight is as follows:
Alkylphenol polyoxyethylene ammonium sulfate (58%) 1.94 gram
Sodium bicarbonate 0.3 gram
Deionized water 143 grams
Ammonium persulphate 10% aqueous solution 5.2 grams
The function monomer that the nucleus of the seed emulsion is used (adopting butylene glycol diacrylate, tertiary ethylene carbonate in this example) and other vinyl monomer (adopting butyl acrylate, ethyl propenoate, methyl methacrylate, vinylformic acid in this example) are made the nuclear pre-emulsion with emulsifying agent (adopting alkylphenol polyoxyethylene ammonium sulfate (58%) in this example), initiator (adopting ammonium persulphate in this example), deionized water in pre-emulsor.
When treating that above-mentioned temperature of reactor rises to 70 ℃-85 ℃, earlier the above-mentioned initiator solution for preparing is added in the reactor, to examine 10% of pre-emulsion again adds in the reactor, react after 20-50 minute, again 90% nuclear pre-emulsion of remainder is splashed into and continue reaction 1.5-4.5 hour in the reactor, get the nucleus of the seed emulsion, the weight of its each component of reactant is as follows:
Butyl acrylate 34.5 grams
Ethyl propenoate 36.5 grams
Methyl methacrylate 17.5 grams
Tertiary ethylene carbonate 10.5 grams
Vinylformic acid 3 grams
Butylene glycol diacrylate 3 grams
Ammonium persulphate 0.72 gram
Alkylphenol polyoxyethylene ammonium sulfate (58%) 2.34 gram
Deionized water 51 grams
Second step, the preparation of core-shell emulsion:
The function monomer that shell is used (adopting butylene glycol diacrylate, diacetone-acryloamide(DAA) in this example), other vinyl monomer (adopting butyl acrylate, ethyl propenoate, methyl methacrylate, vinylformic acid in this example), and the shell pre-emulsion made of emulsifying agent (in this example adopt alkylphenol polyoxyethylene ammonium sulfate (58%)), initiator (adopting ammonium persulphate in this example), deionized water splashes into above-mentioned nucleus of the seed emulsion and carries out letex polymerization, 70 ℃-90 ℃ of temperature of reaction dripped time spent 2-4 hour.Drip off the back and be incubated 2-3 hour to reacting completely, cooling is transferred PH=7-8 with ammoniacal liquor, adds the aqueous solution of adipic dihydrazide, and the after-filtration discharging stirs.Promptly make self-crosslinking acrylic ester composition emulsion for plastic printing ink of the present invention, each composition weight of its reactant is as follows:
Butyl acrylate 30 grams
Ethyl propenoate 13 grams
Methyl methacrylate 48.5 grams
Vinylformic acid 3.2 grams
Butylene glycol diacrylate 0.7 gram
Diacetone-acryloamide(DAA) 6.3 grams
Ammonium persulphate 0.72 gram
Alkylphenol polyoxyethylene ammonium sulfate (58%) 2.34 gram
Deionized water 51 grams
Adipic dihydrazide 2.5 grams
Deionized water 10 grams
Get emulsion solid content 43 ± 2%, second-order transition temperature Tg
1=-15.3 ℃, second-order transition temperature Tg
2=20.7 ℃, PH=8, viscosity 50mpas.Emulsion has good sticking power to polypropylene screen.
Above-mentioned embodiment has just exemplified exemplary embodiments of the present invention; can only think explanation of the present invention rather than restriction the present invention; those skilled in the art can do corresponding changes and improvements under the prompting of specification sheets, but should think in claims protection domain of the present invention.
Claims (10)
1, self-crosslinking acrylic ester composition emulsion for plastic printing ink is characterized in that, this emulsion is to have selected polymerization shrinkage little, the little and product that has the function monomer of higher permeability and other vinyl monomer to get by letex polymerization of surface tension;
Wherein,
Described function monomer is selected following 1 to 4 kind of compound for use:
(methyl) isobornyl acrylate, (methyl) vinylformic acid double cyclopentenyl ester, (methyl) vinylformic acid three cyclopentenyl esters, tertiary ethylene carbonate, ethylene glycol bisthioglycolate (methyl) acrylate, butyleneglycol two (methyl) acrylate, pentaerythritol triacrylate, Viscoat 295
The diacetone-acryloamide(DAA) of ketocarbonyl-containing, acetoacetyl oxygen ethyl (methyl) acrylate,
Adipic dihydrazide, carbonic acid hydrazides;
Described other vinyl monomer is selected 2 to 5 kinds of compounds in methyl methacrylate, (methyl) butyl acrylate, (methyl) vinylformic acid, ethyl propenoate, ethyl acrylate, acrylamide, the vinylbenzene for use.
2, according to the described self-crosslinking acrylic ester composition emulsion for plastic printing ink of claim 1, it is characterized in that, described function monomer is selected isobornyl acrylate, diacetone-acryloamide(DAA) and adipic dihydrazide for use, wherein, the adipic dihydrazide consumption is the 35-48% of diacetone-acryloamide(DAA) mole number.
3, according to the described self-crosslinking acrylic ester composition emulsion for plastic printing ink of claim 1, it is characterized in that, described function monomer is selected isobornyl acrylate, diacetone-acryloamide(DAA) and carbonic acid hydrazides for use, and wherein, carbonic acid hydrazides consumption is the 35-48% of diacetone-acryloamide(DAA) mole number.
4, according to the described self-crosslinking acrylic ester composition emulsion for plastic printing ink of claim 1, it is characterized in that, described function monomer is selected isobornyl acrylate, vinylformic acid double cyclopentenyl ester, diacetone-acryloamide(DAA) and adipic dihydrazide for use, wherein, the adipic dihydrazide consumption is the 35-48% of diacetone-acryloamide(DAA) mole number.
5, according to the described self-crosslinking acrylic ester composition emulsion for plastic printing ink of claim 1, it is characterized in that, described function monomer is selected isobornyl acrylate, vinylformic acid double cyclopentenyl ester, diacetone-acryloamide(DAA) and carbonic acid hydrazides for use, wherein, carbonic acid hydrazides consumption is the 35-48% of diacetone-acryloamide(DAA) mole number.
6, according to the described self-crosslinking acrylic ester composition emulsion for plastic printing ink of claim 1, it is characterized in that, described function monomer is selected tertiary ethylene carbonate, diacetone-acryloamide(DAA) and adipic dihydrazide for use, and wherein, the adipic dihydrazide consumption is the 35-48% of diacetone-acryloamide(DAA) mole number.
7, according to the described self-crosslinking acrylic ester composition emulsion for plastic printing ink of claim 1, it is characterized in that, described function monomer is selected tertiary ethylene carbonate, diacetone-acryloamide(DAA) and carbonic acid hydrazides for use, and wherein, carbonic acid hydrazides consumption is the 35-48% of diacetone-acryloamide(DAA) mole number.
8, the preparation method of the described self-crosslinking acrylic ester composition emulsion for plastic printing ink of a kind of claim 1 is characterized in that, described method comprises following two steps:
The first step, the preparation of nucleus of the seed emulsion:
In reactor, add deionized water, emulsifying agent, the buffer reagent of a part, be warming up to 70 ℃-85 ℃, and it is standby to prepare a part of initiator solution;
The function monomer that the nucleus of the seed emulsion is used and other vinyl monomer are made the nuclear pre-emulsion with emulsifying agent, initiator, the deionized water of remaining part in pre-emulsor;
When treating that above-mentioned temperature of reactor rises to 70 ℃-85 ℃, earlier the above-mentioned initiator solution for preparing is added in the reactor, to examine 10% of pre-emulsion again adds in the reactor, react after 20-50 minute, again 90% nuclear pre-emulsion of remainder is splashed into and continue reaction 1.5-4.5 hour in the described reactor, get the nucleus of the seed emulsion, the weight % content of each component of reactant of nucleus of the seed emulsion is as follows:
The function monomer 0-10% that the nucleus of the seed emulsion is used
Other vinyl monomer 15%-30% that the nucleus of the seed emulsion is used
Emulsifying agent 0.5%-1.2%
Initiator 0.25%-0.7%
Deionized water 60%-75%
Buffer reagent 0.08%-0.15%
Second step, the preparation of core-shell emulsion:
The function monomer that shell is used, other vinyl monomer, and shell pre-emulsion and above-mentioned nucleus of the seed emulsion that emulsifying agent, initiator, molecular weight regulator, deionized water are made are carried out letex polymerization, 70 ℃-90 ℃ of temperature of reaction, after reaction times 2-6 hour, add the PH conditioning agent, promptly make self-crosslinking acrylic ester composition emulsion for plastic printing ink of the present invention, each composition weight % content of its reactant is as follows:
Other vinyl monomer 18%-27% that shell is used
The function monomer 2%-8% that shell is used
Emulsifying agent 0.1%-0.55%
Initiator 0.06%-0.15%
Molecular weight regulator 0.02%-0.18%
Deionized water 12%-21%
Above-mentioned nucleus of the seed emulsion 50%-65%
Wherein,
What the nucleus of the seed emulsion was used selects following 1 to 4 kind of compound for use with the used function monomer of shell:
(methyl) isobornyl acrylate, (methyl) vinylformic acid double cyclopentenyl ester, (methyl) vinylformic acid three cyclopentenyl esters, tertiary ethylene carbonate, ethylene glycol bisthioglycolate (methyl) acrylate, butyleneglycol two (methyl) acrylate, pentaerythritol triacrylate, Viscoat 295
The diacetone-acryloamide(DAA) of ketocarbonyl-containing, acetoacetyl oxygen ethyl (methyl) acrylate,
Adipic dihydrazide, carbonic acid hydrazides;
What the nucleus of the seed emulsion was used selects 2 to 5 kinds of compounds in methyl methacrylate, (methyl) butyl acrylate, (methyl) vinylformic acid, ethyl propenoate, ethyl acrylate, acrylamide, the vinylbenzene for use with other used vinyl monomer of shell.
9, the preparation method of described self-crosslinking acrylic ester composition emulsion for plastic printing ink according to Claim 8 is characterized in that: described emulsifying agent is selected in alkylphenol polyoxyethylene vitriol, the alkylphenol polyoxyethylene one or both mixture for use; Described initiator is selected one or both the mixture in Potassium Persulphate, Sodium Persulfate, the ammonium persulphate for use.
10, the preparation method of described self-crosslinking acrylic ester composition emulsion for plastic printing ink according to Claim 8 is characterized in that: described buffer reagent is selected a kind of in Sodium phosphate dibasic or the sodium bicarbonate for use; Described molecular weight regulator is selected dodecyl mercaptans or the different monooctyl ester of thiohydracrylic acid for use; Described PH conditioning agent is selected one or both the mixture in sodium hydroxide (potassium), 2-methyl-2-aminopropanol, the ammoniacal liquor for use.
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