CN101348541B - 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 Vilaterm (PE), Vestolen PP 7052 (PP), SE (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, and this has just highlighted the demands of different 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 OSR 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 process resin liquid with toluene or YLENE, N-BUTYL ACETATE equal solvent; In order to preparation printing ink; We also once used acrylic ester grafted to Chlorinated Polypropylene III, made the excellent toluene solution of sticking power, 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 compsn 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 sticking power.In line with this idea and environment protection requirement, prepared and can be used for Vestolen PP 7052 and poly printing ink is used 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%), the product that little and the function monomer that higher permeability arranged of surface tension and other vinyl monomer get through letex polymerization; Wherein,
Said function monomer is selected following 1 to 4 kind of compound for use:
(methyl) IBOA, (methyl) vinylformic acid double cyclopentenyl ester, (methyl) vinylformic acid three cyclopentenyl esters, tertiary ethylene carbonate, ethylene glycol bisthioglycolate (methyl) propenoate, butyleneglycol two (methyl) propenoate, pentaerythritol triacrylate, Viscoat 295
The diacetone-acryloamide(DAA) of ketocarbonyl-containing, acetoacetyl oxygen ethyl (methyl) propenoate,
Adipic dihydrazide, carbonic acid hydrazides;
Described other vinyl monomer is selected 2 to 5 kinds of compounds in TEB 3K, (methyl) Bing Xisuandingzhi, (methyl) vinylformic acid, ethyl propenoate, ethyl acrylate, acrylic amide, the vinylbenzene for use.
Emulsion preparation method of the present invention is to produce with preparatory 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 following:
The first step, the preparation of nucleus of the seed emulsion:
In reactor drum, add deionized water, emulsifying agent, the buffer reagent of a part, be warming up to 70 ℃-85 ℃, and it is subsequent use to prepare a part of initiator solution;
The function monomer that the nucleus of the seed emulsion is used and other vinyl monomer are being processed the nuclear pre-emulsion in the emulsor in advance with emulsifying agent, initiator, the deionized water of remaining part;
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 drum; To examine 10% of pre-emulsion again and add in the reactor drum, react after 20-50 minute, and 90% nuclear pre-emulsion of remainder splashed into continue in the said reactor drum to react 1.5-4.5 hour again; Get the nucleus of the seed emulsion, the weight % content of each component of reactant of nucleus of the seed emulsion is following:
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 processed are carried out letex polymerization; 70 ℃-90 ℃ of temperature of reaction after reaction times 2-6 hour, add the PH regulator; Promptly make self-crosslinking acrylic ester composition emulsion for plastic printing ink of the present invention, each composition weight % content of its reactant is following:
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) IBOA, (methyl) vinylformic acid double cyclopentenyl ester, (methyl) vinylformic acid three cyclopentenyl esters, tertiary ethylene carbonate, ethylene glycol bisthioglycolate (methyl) propenoate, butyleneglycol two (methyl) propenoate, pentaerythritol triacrylate, Viscoat 295
The diacetone-acryloamide(DAA) of ketocarbonyl-containing, acetoacetyl oxygen ethyl (methyl) propenoate,
Adipic dihydrazide, carbonic acid hydrazides;
What the nucleus of the seed emulsion was used selects 2 to 5 kinds of compounds in TEB 3K, (methyl) Bing Xisuandingzhi, (methyl) vinylformic acid, ethyl propenoate, ethyl acrylate, acrylic amide, the vinylbenzene for use with other used vinyl monomer of shell.
In the present invention, described emulsifying agent is selected in TX10 vitriol, the TX10 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 hydrogencarbonate for use; Described molecular weight regulator is selected dodecyl mercaptans or the different monooctyl ester of thiohydracrylic acid for use; Described PH regulator 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 deposition, nothing flocculation |
| Mechanical stability | 30min, 2500 commentaries on classics/min | No layering, nothing deposition, 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 excellent to the sticking power of PP, PE film, PVC, PET, ABS etc. also there are good adhesive.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%), the product that little and the function monomer that higher permeability arranged of surface tension and other vinyl monomer get through letex polymerization; Wherein, said function monomer is selected following 1 to 4 kind of compound for use:
(methyl) IBOA, (methyl) vinylformic acid double cyclopentenyl ester, (methyl) vinylformic acid three cyclopentenyl esters, tertiary ethylene carbonate, ethylene glycol bisthioglycolate (methyl) propenoate, butyleneglycol two (methyl) propenoate, pentaerythritol triacrylate, Viscoat 295
The diacetone-acryloamide(DAA) of ketocarbonyl-containing, acetoacetyl oxygen ethyl (methyl) propenoate,
Adipic dihydrazide, carbonic acid hydrazides;
Described other vinyl monomer is selected 2 to 5 kinds of compounds in TEB 3K, (methyl) Bing Xisuandingzhi, (methyl) vinylformic acid, ethyl propenoate, ethyl acrylate, acrylic amide, the vinylbenzene for use.
As instance of the present invention; The required function monomer of said letex polymerization can be selected IBOA, 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 instance of the present invention; The required function monomer of letex polymerization according to the invention can be selected IBOA, 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 instance of the present invention; The required function monomer of letex polymerization according to the 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 preparatory 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 drum, add deionized water, emulsifying agent (adopting TX10 ammonium sulfate (58%) in this example), buffer reagent (adopting sodium hydrogencarbonate 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 following:
TX10 ammonium sulfate (58%) 1 gram
Sodium hydrogencarbonate 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 IBOA, butylene glycol dimethacrylate in this example) and other vinyl monomer (adopting Bing Xisuandingzhi, ethyl propenoate, vinylformic acid in this example) are being processed the nuclear pre-emulsion in the emulsor in advance with emulsifying agent (adopting TX10 ammonium sulfate (58%) in this example), initiator (adopting ammonium persulphate in this example), deionized water.
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 drum; To examine 10% of pre-emulsion again and add in the reactor drum, react after 20-50 minute, and 90% nuclear pre-emulsion of remainder splashed into continue in the reactor drum to react 1.5-4.5 hour again; Get the nucleus of the seed emulsion, the weight of its each component of reactant is following:
Bing Xisuandingzhi 40 grams
Ethyl propenoate 20 grams
IBOA 6 grams
Vinylformic acid 2 grams
Butylene glycol dimethacrylate 3 grams
Ammonium persulphate 0.48 gram
TX10 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 IBOA, diacetone-acryloamide(DAA), butylene glycol dimethacrylate in this example), other vinyl monomer (adopting Bing Xisuandingzhi, vinylformic acid in this example); And the shell pre-emulsion processed of emulsifying agent (in this example adopt TX10 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 following:
Bing Xisuandingzhi 100 grams
Vinylformic acid 4 grams
IBOA 20 grams
Diacetone-acryloamide(DAA) 8 grams
Butylene glycol dimethacrylate 1 gram
Dodecyl mercaptans 1 gram
Ammonium persulphate 0.36 gram
TX10 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 drum, add deionized water; Emulsifying agent (adopting TX10 ammonium sulfate (58%), TX10 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 following:
TX10 ammonium sulfate (58%) 2.88 gram
TX10 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 Bing Xisuandingzhi, ethyl propenoate, TEB 3K in this example) are being processed the nuclear pre-emulsion in the emulsor in advance with emulsifying agent (adopting TX10 ammonium sulfate (58%), TX10 in this example), initiator (adopting ammonium persulphate in this example), deionized water.
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 drum; To examine 10% of pre-emulsion again and add in the said reactor drum, react after 20-50 minute, and 90% nuclear pre-emulsion of remainder splashed into continue in the said reactor drum to react 1.5-4.5 hour again; Get the nucleus of the seed emulsion, the weight of its each component of reactant is following:
Bing Xisuandingzhi 90 grams
Ethyl propenoate 60 grams
TEB 3K 54 grams
Glycol diacrylate 3 grams
Ammonium persulphate 1.56 grams
TX10 1.35 grams
TX10 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 (adopting IBOA, glycol diacrylate, diacetone-acryloamide(DAA), acrylic amide in this example), other vinyl monomer (adopting Bing Xisuandingzhi, vinylformic acid, TEB 3K in this example); And the shell pre-emulsion processed of emulsifying agent (in this example adopt TX10 ammonium sulfate (58%), TX10), 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 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 following:
Bing Xisuandingzhi 200 grams
Vinylformic acid 12 grams
TEB 3K 100 grams
IBOA 54 grams
Glycol diacrylate 1 gram
Diacetone-acryloamide(DAA) 24 grams
Acrylic amide 6 grams
Dodecyl mercaptans 0.78 gram
Ammonium persulphate 1.08 grams
TX10 ammonium sulfate (58%) 2.88 gram
TX10 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 drum, add deionized water; Emulsifying agent (adopting TX10 ammonium sulfate (58%), TX10 in this example); Buffer reagent (adopting sodium hydrogencarbonate 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 following:
TX10 ammonium sulfate (58%) 0.96 gram
TX10 0.28 gram
Sodium hydrogencarbonate 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 Bing Xisuandingzhi, ethyl propenoate, TEB 3K in this example) are being processed the shell pre-emulsion in the emulsor in advance with emulsifying agent (adopting TX10 ammonium sulfate (58%), TX10 in this example), initiator (adopting ammonium persulphate in this example), deionized water.
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 drum; To examine 10% of pre-emulsion again and add in the reactor drum, react after 20-50 minute, and 90% nuclear pre-emulsion of remainder splashed into continue in the reactor drum to react 1.5-4.5 hour again; Get the nucleus of the seed emulsion, the weight of its each component of reactant is following:
Bing Xisuandingzhi 30 grams
Ethyl propenoate 20 grams
TEB 3K 18 grams
Pentaerythritol triacrylate 1.5 grams
Ammonium persulphate 0.52 gram
TX10 0.45 gram
TX10 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 vinylformic acid double cyclopentenyl ester, IBOA, pentaerythritol triacrylate, diacetone-acryloamide(DAA) in this example), other vinyl monomer (adopting NSC 20956, vinylformic acid, acrylic amide in this example); And the pre-emulsion processed of emulsifying agent (in this example adopt TX10 ammonium sulfate (58%), TX10), initiator (adopting ammonium persulphate in this example), molecular weight regulator (adopting the different monooctyl ester of thiohydracrylic acid 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 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 following:
Diacetone-acryloamide(DAA) 8 grams
Pentaerythritol triacrylate 0.8 gram
Vinylformic acid double cyclopentenyl ester 4 grams
IBOA 14 grams
Vinylformic acid 4 grams
NSC 20956 100 grams
Acrylic amide 2 grams
Different monooctyl ester 0.26 gram of thiohydracrylic acid
Ammonium persulphate 1.08 grams
TX10 ammonium sulfate (58%) 0.96 gram
TX10 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 drum, add deionized water, emulsifying agent (adopting TX10 ammonium sulfate (58%) in this example), buffer reagent (adopting sodium hydrogencarbonate 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 following:
TX10 ammonium sulfate (58%) 1.94 gram
Sodium hydrogencarbonate 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 Bing Xisuandingzhi, ethyl propenoate, TEB 3K, vinylformic acid in this example) are being processed the nuclear pre-emulsion in the emulsor in advance with emulsifying agent (adopting TX10 ammonium sulfate (58%) in this example), initiator (adopting ammonium persulphate in this example), deionized water.
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 drum; To examine 10% of pre-emulsion again and add in the reactor drum, react after 20-50 minute, and 90% nuclear pre-emulsion of remainder splashed into continue in the reactor drum to react 1.5-4.5 hour again; Get the nucleus of the seed emulsion, the weight of its each component of reactant is following:
Bing Xisuandingzhi 34.5 grams
Ethyl propenoate 36.5 grams
TEB 3K 17.5 grams
Tertiary ethylene carbonate 10.5 grams
Vinylformic acid 3 grams
Butylene glycol diacrylate 3 grams
Ammonium persulphate 0.72 gram
TX10 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 Bing Xisuandingzhi, ethyl propenoate, TEB 3K, vinylformic acid in this example); And the shell pre-emulsion processed of emulsifying agent (in this example adopt TX10 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 following:
Bing Xisuandingzhi 30 grams
Ethyl propenoate 13 grams
TEB 3K 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
TX10 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.
The above-mentioned embodiment exemplary embodiments of the present invention of just having given an example; Can only think explanation of the present invention rather than restriction the present invention; Those skilled in the art can do corresponding variation and improvement 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; It is characterized in that; This emulsion is to have selected polymerization shrinkage little, and surface tension is little and the function monomer of higher permeability and the product that other vinyl monomer gets through letex polymerization are arranged, and concrete preparation method comprises following two steps:
The first step, the preparation of nucleus of the seed emulsion:
In reactor drum, add deionized water, emulsifying agent, the buffer reagent of a part, be warming up to 70 ℃-85 ℃, and it is subsequent use to prepare a part of initiator solution;
The function monomer that the nucleus of the seed emulsion is used and other vinyl monomer are being processed the nuclear pre-emulsion in the emulsor in advance with emulsifying agent, initiator, the deionized water of remaining part;
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 drum; To examine 10% of pre-emulsion again and add in the reactor drum, react after 20-50 minute, and 90% nuclear pre-emulsion of remainder splashed into continue in the said reactor drum to react 1.5-4.5 hour again; Get the nucleus of the seed emulsion, the weight % content of each component of reactant of nucleus of the seed emulsion is following:
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 processed are carried out letex polymerization; 70 ℃-90 ℃ of temperature of reaction after reaction times 2-6 hour, add the PH regulator; Promptly make self-crosslinking acrylic ester composition emulsion for plastic printing ink, each composition weight % content of its reactant is following:
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) IBOA, (methyl) vinylformic acid double cyclopentenyl ester, (methyl) vinylformic acid three cyclopentenyl esters, tertiary ethylene carbonate, ethylene glycol bisthioglycolate (methyl) propenoate, butyleneglycol two (methyl) propenoate, pentaerythritol triacrylate, Viscoat 295;
The diacetone-acryloamide(DAA) of ketocarbonyl-containing, acetoacetyl oxygen ethyl (methyl) propenoate;
Adipic dihydrazide, carbonic acid hydrazides;
What the nucleus of the seed emulsion was used selects 2 to 5 kinds of compounds in TEB 3K, (methyl) Bing Xisuandingzhi, (methyl) vinylformic acid, ethyl propenoate, ethyl acrylate, acrylic amide, the vinylbenzene for use with other used vinyl monomer of shell.
2. according to the said self-crosslinking acrylic ester composition emulsion for plastic printing ink of claim 1; It is characterized in that; Said function monomer is selected IBOA, 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 said self-crosslinking acrylic ester composition emulsion for plastic printing ink of claim 1; It is characterized in that; Said function monomer is selected IBOA, 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 said self-crosslinking acrylic ester composition emulsion for plastic printing ink of claim 1; It is characterized in that; Said function monomer is selected IBOA, 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 said self-crosslinking acrylic ester composition emulsion for plastic printing ink of claim 1; It is characterized in that; Said function monomer is selected IBOA, 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 said self-crosslinking acrylic ester composition emulsion for plastic printing ink of claim 1; It is characterized in that; Said 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 said self-crosslinking acrylic ester composition emulsion for plastic printing ink of claim 1; It is characterized in that; Said 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 a self-crosslinking acrylic ester composition emulsion for plastic printing ink is characterized in that, said method comprises following two steps:
The first step, the preparation of nucleus of the seed emulsion:
In reactor drum, add deionized water, emulsifying agent, the buffer reagent of a part, be warming up to 70 ℃-85 ℃, and it is subsequent use to prepare a part of initiator solution;
The function monomer that the nucleus of the seed emulsion is used and other vinyl monomer are being processed the nuclear pre-emulsion in the emulsor in advance with emulsifying agent, initiator, the deionized water of remaining part;
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 drum; To examine 10% of pre-emulsion again and add in the reactor drum, react after 20-50 minute, and 90% nuclear pre-emulsion of remainder splashed into continue in the said reactor drum to react 1.5-4.5 hour again; Get the nucleus of the seed emulsion, the weight % content of each component of reactant of nucleus of the seed emulsion is following:
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 processed are carried out letex polymerization; 70 ℃-90 ℃ of temperature of reaction after reaction times 2-6 hour, add the PH regulator; Promptly make self-crosslinking acrylic ester composition emulsion for plastic printing ink, each composition weight % content of its reactant is following:
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) IBOA, (methyl) vinylformic acid double cyclopentenyl ester, (methyl) vinylformic acid three cyclopentenyl esters, tertiary ethylene carbonate, ethylene glycol bisthioglycolate (methyl) propenoate, butyleneglycol two (methyl) propenoate, pentaerythritol triacrylate, Viscoat 295;
The diacetone-acryloamide(DAA) of ketocarbonyl-containing, acetoacetyl oxygen ethyl (methyl) propenoate;
Adipic dihydrazide, carbonic acid hydrazides;
What the nucleus of the seed emulsion was used selects 2 to 5 kinds of compounds in TEB 3K, (methyl) Bing Xisuandingzhi, (methyl) vinylformic acid, ethyl propenoate, ethyl acrylate, acrylic amide, the vinylbenzene for use with other used vinyl monomer of shell.
9. the preparation method of said self-crosslinking acrylic ester composition emulsion for plastic printing ink according to Claim 8 is characterized in that: described emulsifying agent is selected in TX10 vitriol, the TX10 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 said 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 hydrogencarbonate for use; Described molecular weight regulator is selected dodecyl mercaptans or the different monooctyl ester of thiohydracrylic acid for use; Described PH regulator is selected one or both the mixture in sodium hydroxide, Pottasium Hydroxide, 2-methyl-2-aminopropanol, the ammoniacal liquor for use.
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