CN103739785B - The preparation method of PVC heat shrink films alcohol water-based ink resin - Google Patents
The preparation method of PVC heat shrink films alcohol water-based ink resin Download PDFInfo
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- CN103739785B CN103739785B CN201210392250.5A CN201210392250A CN103739785B CN 103739785 B CN103739785 B CN 103739785B CN 201210392250 A CN201210392250 A CN 201210392250A CN 103739785 B CN103739785 B CN 103739785B
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- heat shrink
- shrink films
- pvc heat
- acrylate
- resin
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- 239000011347 resin Substances 0.000 title claims abstract description 49
- 229920005989 resin Polymers 0.000 title claims abstract description 49
- 229920006300 shrink film Polymers 0.000 title claims abstract description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 21
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229940117958 vinyl acetate Drugs 0.000 claims abstract description 19
- DLZPQJDDVWPHNU-UHFFFAOYSA-N C(C)(=O)OC=C.OC=CCl Chemical compound C(C)(=O)OC=C.OC=CCl DLZPQJDDVWPHNU-UHFFFAOYSA-N 0.000 claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 150000003254 radicals Chemical class 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000003999 initiator Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 10
- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- 238000004806 packaging method and process Methods 0.000 claims description 6
- 230000006641 stabilisation Effects 0.000 claims description 6
- 238000011105 stabilization Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical class COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 2
- 238000010559 graft polymerization reaction Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 2
- 239000013557 residual solvent Substances 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims 1
- 239000011976 maleic acid Substances 0.000 claims 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 7
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 229920000578 graft copolymer Polymers 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 37
- 239000004800 polyvinyl chloride Substances 0.000 description 37
- 235000019441 ethanol Nutrition 0.000 description 27
- 235000019439 ethyl acetate Nutrition 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 5
- 125000005909 ethyl alcohol group Chemical group 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 3
- 229920001470 polyketone Polymers 0.000 description 3
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- -1 acrylic ester Chemical class 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- CGZZMOTZOONQIA-UHFFFAOYSA-N cycloheptanone Chemical compound O=C1CCCCCC1 CGZZMOTZOONQIA-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
Abstract
The present invention relates to PVC heat shrink films resin for printing ink, particularly alcohol water-based ink resin and preparation method thereof.The present invention is a kind of preparation method of PVC heat shrink films alcohol water-based ink resin, be with hydroxyl vinyl chloride-vinyl acetate resin,（Methyl）Acrylate, vinylacetate and active function monomer are raw material, are obtained by Solution Free Radical graft copolymerization.Since hydroxyl vinyl chloride-vinyl acetate resin has the chemical constitution similar with PVC heat shrink films so that prepared graft copolymer has good adhesive force to PVC heat shrink films, and percent thermal shrinkage matching degree is good；And participate in other monomers of graft copolymerization, then provide alcohol-soluble and water-soluble for graft copolymer.PVC heat shrink films of the present invention are simple with the preparation method of alcohol water-based ink resin, the ink printing effect of preparation is good, strong adhesive force, and percent thermal shrinkage matching degree is good, and is alcohol-soluble and water-soluble, it is economic and environment-friendly, have broad application prospects in PVC heat shrink films printing ink area.
Description
Technical field
The present invention relates to PVC heat shrink films resin for printing ink, particularly alcohol water-based ink resin and preparation method thereof.
Technical background
As a kind of secondary package material, PVC shrinks Membrane cover mark and has been widely adopted, and will apply more and more
Into beverage packaging industry.The label being fabricated to PVC heat shrink films, the word and pattern enriched in printing, is contracted in container
The whole body, constitute one of beautiful scenery in dazzling commodity.So-called heat shrink films are to use high-polymer molecular chain
Stretch orientation principle designs, a kind of plastic film shaped in the method for chilling sizing.By made of blown film or casting technique
PVC heat shrink films, when being heated to certain temperature, its lateral shrinkage is up to 50~60%, and longitudinal contraction then very little, can
To meet the packing instructions of existing container well.PVC heat shrink films are a kind of most widely used heat-shrinkage materials at present, its
Dosage ranks first in beverage industry.
The printing of heat-shrinkable PVC film belongs in film and prints frequently with intaglio printing, thus is shunk in shrink film heat
Afterwards, picture and text can obtain effective protection in internal layer., it is necessary to could be realized pair through overheat contraction after being printed due to heat-shrinkable PVC film
The packaging of container, therefore the ink special being adapted with this characteristic must be used during printing, to ensure ink not only to PVC base
With good adhesive force, while also there is the percent thermal shrinkage to match with PVC base, be allowed to be unlikely to during thermal contraction
There is printing ink layer and the disadvantage such as rupture, come off.
Current heat-shrinkable PVC film ink special is typically to be prepared using polyvinyl chloride or vinyl chloride-vinyl acetate resin as resin binder
, it is good attached possess using the similitude of above-mentioned polymer and heat-shrinkable PVC film chemical constitution, prepared ink
The percent thermal shrinkage puted forth effort and matched with PVC base, as number of patent application CN200910032638.2 discloses a kind of polychlorostyrene second
Alkene ink.
However, the dissolubility of polyvinyl chloride and vinyl chloride-vinyl acetate resin determines that the ink prepared by it must be with ketone（Such as hexamethylene
Ketone, methyl cyclohexanone, methyl iso-butyl ketone (MIBK) etc.）And ink is prepared based on esters solvent, and due to the glass of above-mentioned two resinoid
Change transition temperature is higher, and hardness is larger, thus usually requires addition O-phthalic ester dibutyl ester etc. in actual use and increase
Mould agent.It is well known that ketone（Such as cyclohexanone, methyl cyclohexanone, methyl iso-butyl ketone (MIBK)）And esters solvent smell is big, stink and
Peculiar smell sense weight, the feature of environmental protection is poor, and then harm to the human body is larger for the plasticizer such as O-phthalic ester dibutyl ester.
In view of ink is made of resin binder, pigment, auxiliary agent and solvent, and the basic performance of ink, such as solvent body
System's selection, base material adhesive force, percent thermal shrinkage etc. are mainly provided by the resin binder in its component, therefore, on avoiding
In place of stating the deficiencies in the prior art, the present invention provides a kind of preparation method of PVC heat shrink films alcohol water-based ink resin, with it
Not only printing effect is good for the ink prepared for resin binder, strong adhesive force, percent thermal shrinkage matching degree are good, and is alcohol-soluble and water-soluble,
It is economic and environment-friendly, it is expected to meet modern packaging industry to PVC heat shrink films printing ink in terms of application performance and environmental protection increasingly
Strict requirements.
The content of the invention
It is an object of the invention to provide a kind of PVC heat shrink films preparation method of alcohol water-based ink resin, pass through hydroxyl
Base vinyl chloride-vinyl acetate resin,（Methyl）The Solution Free Radical graft copolymerization of acrylate, vinylacetate and active function monomer, is made master
Chain is hydroxyl vinyl chloride-vinyl acetate resin, and side chain is the graft copolymer of acrylate copolymer, its main chain is had and PVC heat shrink films
Similar chemical constitution, there is provided the adhesive force good to PVC heat shrink films and percent thermal shrinkage matching degree, and polyacrylate is copolymerized
Thing side chain also assigns the graft copolymer more preferably pliability and cold resistance, so as to prevent to increase while alcohol-soluble and water-soluble is provided
Mould the use of agent.
The purpose of the present invention is by the following technical solutions to realize：
With hydroxyl vinyl chloride-vinyl acetate resin,（Methyl）Acrylate, vinylacetate and active function monomer are raw material, pass through solution
Free radical grafting copolymerization and obtain, wherein the weight proportion respectively formed is：
Hydroxyl vinyl chloride-vinyl acetate resin 50~70
（Methyl）Acrylate 5~20
Vinylacetate 5~20
Active function monomer 5~10
Initiator 0.1~2.0
Solvent 20~200
Solution Free Radical graft polymerization process is specific solution used by PVC heat shrink films alcohol water-based ink resins
Polymerization technique, its specific solution polymerization process are as follows：
1）The initiator of 50wt% and 50wt% solvents are first added into reaction kettle, after stirring evenly, are warming up to 50~85 DEG C；
2）After temperature stabilization, by hydroxyl vinyl chloride-vinyl acetate resin,（Methyl）Acrylate, vinylacetate, active function monomer
It is uniformly mixed, it is interior when 3~6 is small to drop evenly into reaction kettle, while be added dropwise and mixed by the initiator and 30wt% solvents of 50wt%
The initiator solution being combined into；
3）After being added dropwise, keep 50~85 DEG C of temperature, continue stirring 3~8 it is small when, then cool down, add residual solvent
Dilution；
4）Wait to be cooled to room temperature, pack, that is, PVC heat shrink films alcohol water-based ink resin is made.
Wherein：The weight average molecular weight of hydroxyl vinyl chloride-vinyl acetate resin is 5,000~50,000, vinyl acetate segment content for 12~
16wt%, hydroxy radical content are 0.5~3wt%；Active function monomer is acrylic acid, acrylamide, methacrylic acid, maleic two
Acid, hydroxy-ethyl acrylate, hydroxypropyl acrylate, glycidyl acrylate, hydroxyethyl methacrylate, methacrylic acid hydroxypropyl
Ester, the mixture of one or more of compositions of the above；（Methyl）Acrylate is methyl acrylate, ethyl acrylate, acrylic acid
Butyl ester, methyl methacrylate, ethyl methacrylate, butyl methacrylate, the mixing of one or more of compositions of the above
Thing；Initiator is azodiisobutyronitrile or benzoyl peroxide；Solvent is not higher than the ethanol of 5 wt%, ethyl acetate for water content
Or both mixture.
Biggest advantage of the present invention is the graft copolymerization by vinyl chloride-vinyl acetate resin and acrylic ester monomer, on chlorine vinegar main chain
Flexible acrylate copolymer side chain is introduced, obtained graft copolymer is being kept good to PVC heat shrink films attached
Put forth effort, with the basis of percent thermal shrinkage matching degree, to be provided with alcohol-soluble and water-soluble, so as to use the alcohol such as hydrous ethanol/water class environmental protection
Solvent prepares PVC heat shrink films printing ink, has also prevented the use of poisonous and hazardous plasticizer, can effectively meet packaging industry
To requirement of the PVC heat shrink films printing ink in terms of application performance and environmental protection.
PVC heat shrink films of the present invention are simple with the preparation method of alcohol water-based ink resin, the ink printing of preparation
Effect is good, strong adhesive force, and percent thermal shrinkage matching degree is good, and is alcohol-soluble and water-soluble, economic and environment-friendly without adding plasticizer, in PVC heat
Shrink film printing ink area has broad application prospects.
PVC heat shrink films are with the composition of alcohol water-based ink（Weight proportion）：
PVC heat shrink films alcohol water-based ink resin 30~35, solvent 30~35, pigment 10~35, auxiliary agent 1~5.Prepare
Using conventional method, or the following techniques of selection：
1）Ethanol of the water content not higher than 5 wt% is pressed 9 with water：1~2：Mixed solvent is made in 1 ratio；
2）PVC heat shrink films alcohol water-based ink resins and pigment, dispersant, polyketone resin solution and mixed solvent are added
Enter measurer, stirred 20~30 minutes with high speed dispersor, be uniformly mixed it；
3）Uniformly mixed material is taken out, sand mill is sent into and is sanded, is taken out after fineness is less than 10 microns, mistake
Filter；
4）Through after the assay was approved, packing.
Embodiment:
Embodiment one
The azodiisobutyronitrile of 2.5g, 120 g ethyl acetates and 130 g absolute ethyl alcohols are added into reaction kettle, are stirred evenly
Afterwards, 75 DEG C are warming up to；After temperature stabilization, start to drop evenly monomer mixture（By 350 vinyl chloride-vinyl acetate resins（Weight average molecular weight
10,000, vinyl acetate segment content is 12 wt%, and hydroxy radical content is 1.0 wt%）, the butyl acrylate of 75g, 50g
Vinylacetate, the hydroxy-ethyl acrylate of 25g are uniformly mixed）And initiator solution（By the azodiisobutyronitrile of 2.5g,
The ethyl acetate of 150g is uniformly mixed）；When the time for adding of monomer mixture and initiator solution is 3 small, during dropwise addition
It is 75 DEG C to keep temperature；After being added dropwise, keep 75 DEG C of temperature, continue stirring 4 it is small when, then cool down, at the same add 100g without
Water-ethanol dilutes；Wait to be cooled to room temperature, pack, that is, the PVC heat shrink films alcohol water-based ink trees that solid content is 50wt% are made
Fat.
Embodiment two
The benzoyl peroxide of 2.0g, 100g ethyl acetates and 60 g absolute ethyl alcohols are added into reaction kettle, are stirred evenly
Afterwards, 80 DEG C are warming up to；After temperature stabilization, start to drop evenly monomer mixture（By the vinyl chloride-vinyl acetate resin of 320g（Weight-average molecular
Amount 10,000, vinyl acetate segment content is 12 wt%, and hydroxy radical content is 1.0 wt%）, the ethyl acrylate of 50g, 60g
Vinylacetate, the acrylamide of 30g are uniformly mixed）And initiator solution（By the benzoyl peroxide of 2.0g, 64g
Benzoyl peroxide be uniformly mixed）；When the time for adding of monomer mixture and initiator solution is 4 small, during dropwise addition
It is 80 DEG C to keep temperature；After being added dropwise, keep 80 DEG C of temperature, continue stirring 4 it is small when, then cool down, while it is anhydrous to add 64g
Ethanol dilutes；Wait to be cooled to room temperature, pack, that is, the PVC heat shrink films alcohol water-based ink resins that solid content is 60wt% are made.
Embodiment three
The azodiisobutyronitrile of 1.2g, 200 g ethyl acetates and 100 g absolute ethyl alcohols are added into reaction kettle, are stirred evenly
Afterwards, 80 DEG C are warming up to；After temperature stabilization, start to drop evenly monomer mixture（By the vinyl chloride-vinyl acetate resin of 220g（Weight-average molecular
Amount 20,000, vinyl acetate segment content is 16 wt%, and hydroxy radical content is 2.0 wt%）, the butyl acrylate of 80g, 60g
Vinylacetate, the acrylic acid of 40g is uniformly mixed）And initiator solution（By the azodiisobutyronitrile of 1.2g, 180g
Ethyl acetate be uniformly mixed）；When the time for adding of monomer mixture and initiator solution is 5 small, kept during dropwise addition
Temperature is 80 DEG C；After being added dropwise, keep 80 DEG C of temperature, continue stirring 3 it is small when, then cool down, while add the anhydrous second of 120g
Alcohol dilutes；Wait to be cooled to room temperature, pack, that is, the PVC heat shrink films alcohol water-based ink resins that solid content is 40wt% are made.
Example IV
The azodiisobutyronitrile of 1.75g, 150 g ethyl acetates and 100 g absolute ethyl alcohols are added into reaction kettle, stirring is equal
After even, 75 DEG C are warming up to；After temperature stabilization, start to drop evenly monomer mixture（By the vinyl chloride-vinyl acetate resin of 250g（Divide equally again
Son amount 20,000, vinyl acetate segment content is 16 wt%, and hydroxy radical content is 2.0 wt%）, 100g butyl acrylate, 100g
Vinylacetate, the hydroxypropyl acrylate of 50g is uniformly mixed）And initiator solution（It is different by the azo two of 1.75g
Butyronitrile, the ethyl acetate of 150g are uniformly mixed）；When the time for adding of monomer mixture and initiator solution is 4 small, drop
It is 75 DEG C that temperature is kept during adding；After being added dropwise, keep 75 DEG C of temperature, continue stirring 5 it is small when, then cool down, add at the same time
100g absolute ethyl alcohols dilute；Wait to be cooled to room temperature, pack, that is, it is water-based that the PVC heat shrink films alcohol that solid content is 50wt% is made
Ink resin.
Embodiment five
Absolute ethyl alcohol and water are pressed 9：Mixed solvent 35kg is made in 1 ratio；By PVC heat shrink films with alcohol water-based ink tree
Fat 35kg, pigment titanium white 35kg, polyketone resin solution（It is uniformly mixed by 2kg polyketone resins and 10 kg mixed solvents）、
BYK-191 dispersants 3kg and mixed solvent 25kg adds measurer, is stirred 20 minutes with high speed dispersor, makes its mixing equal
It is even；Uniformly mixed material is taken out, sand mill is sent into and is sanded, takes out, filters after fineness is less than 10 microns；Through examining
After qualification, packaging, that is, be made PVC heat shrink films alcohol water-based ink.
Obtained PVC heat shrink films are as shown in the table with the key technical indexes of alcohol water-based ink：
| Detection project | National standard | Detected value | As a result |
| Fineness（μm）（Scraper plate instrument） | ≤25 | ≤10 | It is qualified |
| Tinting strength, tinting power（%） | 95~110 | 98~105 | It is qualified |
| Viscosity（s）（4# glasss/25 DEG C） | 25~70 | 28~50 | It is qualified |
| It is just dry（mm）（30s/25℃） | 25~50 | 28~38 | It is qualified |
| Attachment fastness（%）（Adhesive tape method） | ≥85 | 93~98 | It is qualified |
| Ketones solvent content（ppm） | / | Nothing | It is qualified |
| Plasticizer loading（ppm） | / | Nothing | It is qualified |
Above testing result is according to QB/T2024-1994 standard testings.
Claims (2)
1. a kind of preparation method of PVC heat shrink films alcohol water-based ink resin, is with hydroxyl vinyl chloride-vinyl acetate resin, (methyl) acrylic acid
Ester, vinylacetate and active function monomer are raw material, are obtained by Solution Free Radical graft copolymerization, it is characterised in that raw material master
It is hydroxyl vinyl chloride-vinyl acetate resin to want component, contains (methyl) acrylate, vinylacetate and active function monomer, wherein each group at the same time
Into weight proportion be：
Hydroxyl vinyl chloride-vinyl acetate resin 50~70
(methyl) acrylate 5~20
Vinylacetate 5~20
Active function monomer 5~10
Initiator 0.1~2.0
Solvent 20~200
Solution Free Radical graft polymerization process is specific polymerisation in solution used by PVC heat shrink films alcohol water-based ink resins
Technique, its specific solution polymerization process are as follows：
The initiator of 50wt% and 50wt% solvents are first added into reaction kettle, after stirring evenly, are warming up to 50~85 DEG C；
After temperature stabilization, hydroxyl vinyl chloride-vinyl acetate resin, (methyl) acrylate, vinylacetate, active function monomer are mixed equal
It is even, it is interior when 3~6 is small to drop evenly into reaction kettle, while be added dropwise and be made of initiator and 30wt% the solvents mixing of 50wt%
Initiator solution；
After being added dropwise, keep 50~85 DEG C of temperature, continue stirring 3~8 it is small when, then cool down, add residual solvent dilution；Treat
After being cooled to room temperature, packaging, that is, be made PVC heat shrink films alcohol water-based ink resin；The initiator is azodiisobutyronitrile
Or benzoyl peroxide.
2. the preparation method of PVC heat shrink films alcohol water-based ink resin according to claim 1, it is characterised in that：Hydroxyl
The weight average molecular weight of base vinyl chloride-vinyl acetate resin is 5000~50000, and vinyl acetate segment content is 12~16wt%, and hydroxy radical content is
0.5~3wt%；Active function monomer for acrylic acid, acrylamide, methacrylic acid, maleic acid, hydroxy-ethyl acrylate,
Hydroxypropyl acrylate, glycidyl acrylate, hydroxyethyl methacrylate, hydroxy propyl methacrylate, one kind of the above or
The mixture of several compositions；(methyl) acrylate is methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid
Methyl esters, ethyl methacrylate, butyl methacrylate, the mixture of one or more of compositions of the above；Solvent is water content
The mixture of ethanol not higher than 5wt%, ethyl acetate or both.
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| CN107266623B (en) * | 2017-07-25 | 2019-10-01 | 杭州海维特化工科技有限公司 | A kind of PVC floor film water inkwood rouge and preparation method thereof |
| CN108659173A (en) * | 2018-06-08 | 2018-10-16 | 常熟国和新材料有限公司 | A kind of preparation method of water-based ink resin |
| CN111269346A (en) * | 2020-03-22 | 2020-06-12 | 苏州欧纳克纳米科技有限公司 | Vinyl chloride-vinyl acetate copolymer resin with dispersing aid function and coating thereof |
| JP7177963B1 (en) * | 2022-08-31 | 2022-11-24 | サカタインクス株式会社 | Aqueous ink composition for shrink label |
| CN117447638A (en) * | 2023-11-07 | 2024-01-26 | 珠海市铠信科技有限公司 | Vinegar-modified resin and preparation method and application thereof |
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| CN101255297A (en) * | 2007-02-26 | 2008-09-03 | 北京高盟化工有限公司 | Environment-friendly type joining material resin for printing ink |
| CN101260259A (en) * | 2008-04-18 | 2008-09-10 | 中国科学院化学研究所 | Ink resin used for intaglio printing and preparation method thereof |
| CN102010485A (en) * | 2010-06-03 | 2011-04-13 | 成都市新津托展油墨有限公司 | Preparation method of integrated plastic gravure alcohol-soluble aqueous composite ink resin |
| CN102040726A (en) * | 2010-10-15 | 2011-05-04 | 成都市新津托展油墨有限公司 | Preparation method of high-performance printing ink resin |
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| CN101255297A (en) * | 2007-02-26 | 2008-09-03 | 北京高盟化工有限公司 | Environment-friendly type joining material resin for printing ink |
| CN101260259A (en) * | 2008-04-18 | 2008-09-10 | 中国科学院化学研究所 | Ink resin used for intaglio printing and preparation method thereof |
| CN102010485A (en) * | 2010-06-03 | 2011-04-13 | 成都市新津托展油墨有限公司 | Preparation method of integrated plastic gravure alcohol-soluble aqueous composite ink resin |
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