CN1161390C - Potential hydrophilic resin and composition containing said resin - Google Patents
Potential hydrophilic resin and composition containing said resin Download PDFInfo
- Publication number
- CN1161390C CN1161390C CNB001043579A CN00104357A CN1161390C CN 1161390 C CN1161390 C CN 1161390C CN B001043579 A CNB001043579 A CN B001043579A CN 00104357 A CN00104357 A CN 00104357A CN 1161390 C CN1161390 C CN 1161390C
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- China
- Prior art keywords
- weight
- overlay film
- resin
- printing
- article
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920005989 resin Polymers 0.000 title claims abstract description 132
- 239000011347 resin Substances 0.000 title claims abstract description 132
- 239000000203 mixture Substances 0.000 title claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 43
- 229920003023 plastic Polymers 0.000 claims abstract description 23
- 239000004033 plastic Substances 0.000 claims abstract description 23
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 238000007639 printing Methods 0.000 claims description 82
- 239000003795 chemical substances by application Substances 0.000 claims description 59
- -1 hydroxyalkyl acrylates Chemical class 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 29
- 238000007127 saponification reaction Methods 0.000 claims description 25
- 230000015572 biosynthetic process Effects 0.000 claims description 19
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 18
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
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- 239000005056 polyisocyanate Substances 0.000 claims description 9
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229920003180 amino resin Polymers 0.000 claims description 3
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- 239000002202 Polyethylene glycol Substances 0.000 claims 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims 2
- 229920001223 polyethylene glycol Polymers 0.000 claims 2
- JJBFVQSGPLGDNX-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)COC(=O)C(C)=C JJBFVQSGPLGDNX-UHFFFAOYSA-N 0.000 claims 1
- VFZKVQVQOMDJEG-UHFFFAOYSA-N 2-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(=O)C=C VFZKVQVQOMDJEG-UHFFFAOYSA-N 0.000 claims 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims 1
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- 102100026735 Coagulation factor VIII Human genes 0.000 description 8
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 8
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- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 7
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
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- 238000002474 experimental method Methods 0.000 description 6
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- 238000000926 separation method Methods 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
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- 150000002148 esters Chemical group 0.000 description 4
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- 239000004698 Polyethylene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
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- 238000006243 chemical reaction Methods 0.000 description 3
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- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 3
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- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
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- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention provides potential hydrophilic resin, a composition containing the resin and the application thereof. The potential hydrophilic resin is composed of a monomer unit which is easy to saponify in alkali so as to generate carboxy groups, a monomer unit containing the carboxy groups and a monomer unit containing hydroxy groups. When processed with water containing soda, printed coating films of the composition containing the resin or flaky printed substances which are pasted on products are easy to fall off, and plastic products, etc. can be recovered for regeneration in a colorless state.
Description
The invention relates to the potential hydrophilic resin, contain the compoistion and method of use of this resin.
In recent years, plastics are used in many-side as goods such as container and packing bags, and these goods, great majority all impose printing on its surface, perhaps paste and go up the sheet print.These plastics are difficult to decompose at occurring in nature, and from economizing on resources and the consideration of economy aspect, a part of plastics must reclaim respectively and regeneration.Yet, when carrying out regeneration, the plastics that impose printing but are mingled in the recovery article, make again raw product whole go up color, perhaps part is painted, causes the commodity value of raw product significantly to reduce, perhaps again, most applications is to utilize again, also has the rerum natura of raw product is again caused fatal shortcoming.Therefore, this plastics that impose printing, when reclaiming, can only discard as refuse, perhaps carry out burning disposal, and bring social concern when burning again, generation De dioxine (dioxine) etc. has polluted environment, can help the method that recovery and reuse have the plastics of printing so strong request is a kind of.
According to above-mentioned requirements, certain methods has been proposed, when recycling has the plastics of printing, painted goods such as printing are decoloured.For example, put down in writing a kind of method that goods are decoloured in the special public clear 52-26549 communique, be about to printed matter and handle, made, made printing film break away from (peeling off) from goods by multiple printing film dissolving or expansion on these goods with organic solvent.The method of this use solvent, the problem of bringing is a lot, that is and, the Separation and Recovery of the organic solvent that exists in the waste liquid of decolouring processing usefulness, inflammableness etc. will be provided with explosion-proof equipment and security control etc.Have again, handle the method for printed matter with buck, be merely economical, but, when great majority formed printing by overlay film, having used polyurethane resin, acrylic resin, fiber was hydrophobic film forming compositions such as resin, rosin, ethylene-vinyl acetate copolymer, so, in above-mentioned alkaline purification, printing film can not easily break away from.
A kind of method that printing film is come off from product surface is disclosed in the public clear 58-152913 communique of spy, by in the printing-ink of article printing usefulness, add alkali soluble resins or hydrophilic resin, with the printed matter available bases water treatment of this printing-ink printing.Though this method has both the rerum natura that made up printing-ink and the alkali detachment to it, is a kind of good method, the problem that exists is that the scope of application of used printing-ink is very narrow.For example, consider with used printing-ink in the resin intermiscibility, and can not add alkali-soluble resin the time, cause printing-ink aggegation and tackified phenomenon, make the color and luster of print and the transparency reduce, very poor as the suitability of printing-ink.
Have again, when the resin in the printing-ink does not have elastic properties, owing to add alkali soluble resins or hydrophilic resin, even as breaking away from print.But also be not easy to come off, and then this cast forms fine dispersions in treatment solution, from treatment solution, reclaim this fine body that comes off and to use very expensive filtration unit.
Therefore, the objective of the invention is for solving an above-mentioned difficult problem of the prior art, and provide a kind of printing in plastics etc. by multiple film or stick on sheet print on these goods and can handle with buck and come off, with colourless state reclaiming plastics, simultaneously, can make the printing film that comes off and sheet print be easy to from treatment solution isolating potential hydrophilic resin, contain the compoistion and method of use of this resin.
The present invention according to the following stated can achieve the above object.That is, the invention provides a kind of potential hydrophilic resin (to call " resin of the present invention " in the following text), contain the potential hydrophilic resin oil/fat composition (to call " resin combination of the present invention " in the following text) (specifically being printing-ink, caking agent or substrate agent etc.) and the using method thereof of this resin.It is characterized in that at least by forming with lower unit, that is, in alkalescence, carry out easily saponification produce carboxyl monomeric unit, have the monomeric unit of carboxyl and have the monomeric unit of hydroxyl.
The printing-ink that contains resin of the present invention, itself, owing to do not contain water soluble resin, so the various rerum naturas of printing-ink are all fine.Utilize this printing-ink that article are implemented printing, thereafter, when printing is broken away from by overlay film, buck is easy to make the methacrylate unit in the print film to carry out saponification, improved the wetting ability of the printing film resin that forms, and expand, printing is easy to break away from from article surface by overlay film.Therefore, printing is dissolved in buck by overlay film and can not formed fine fragment, and as by overlay film, owing to can break away from, the printing film that breaks away from is easy to separate in the buck used from break away from.
The caking agent that contains resin of the present invention when utilizing this caking agent to be attached to the sheet print on the article, is said with regard to itself, owing to do not contain water soluble resin, has favorable durability for moistening and dewfall.When the sheet print broke away from, buck was easy to make caking agent to be carried out saponification by the methacrylate unit in the overlay film later on, improved to form caking agent by the wetting ability of film covered resin, and obtained expanding, and the sheet print is easy to separate from article surface.Therefore, caking agent is dissolved in buck by overlay film, can not form fine fragment, owing to the sheet print breaks away from simultaneously, so the caking agent that breaks away from is separated from break away from treatment solution with the sheet print at an easy rate by overlay film.
Use contains the substrate agent of resin of the present invention, the substrate agent is set by overlay film on article surface, prints on by the surface of overlay film in this substrate agent again, or when pasting the sheet print, itself say with regard to the substrate agent, owing to do not contain water soluble resin, so very good to the weather resistance of moist and dewfall.After, when printing film or sheet print are broken away from, buck is easy to make the substrate agent to be carried out saponification by the methacrylate unit in the overlay film, improve and form substrate by the wetting ability of film covered resin, and obtain expanding, printing is broken away from from article surface by overlay film with the substrate agent at an easy rate by overlay film or sheet print.Therefore, substrate is dissolved in the buck by overlay film, does not form fine fragment, is broken away from simultaneously by overlay film or sheet print owing to print, so the substrate agent that breaks away from is separated from break away from treatment solution by overlay film or sheet print at an easy rate by overlay film, printing.
In above-mentioned 3 kinds of using method, when making resin of the present invention, (a) monomer that use is big or (b) use linking agent or cross-linked resin use physics or chemistry, or (c) when forming printing and with linking agent, form by overlay film by overlay film, perhaps (a)～(c) made up, by composition form contacted with buck by overlay film the time, promote buck to the lining membrane permeability, further promote above-mentioned various by the disengaging of overlay film.
Below enumerate embodiment preferred to illustrate in greater detail the present invention.
The feature of resin of the present invention is at least by easily saponification produces the monomeric unit of carboxyl in alkalescence, the monomeric unit that has the monomeric unit of carboxyl and have a hydroxyl is formed.
As the monomer of easy saponification generation carboxyl in the alkalescence, the lower alkyl esters of the undersaturated carboxylic compound of known any polymerizability before can using, the fireballing methacrylic ester of the saponification that preferably in alkali, produces.Below with methacrylic ester as easily saponification and the monomer typical example that produces carboxyl describes in the alkalescence.
As monomer with carboxyl, the unsaturated carboxylic compound of known any polymerizability before can using, preferably good acrylic or methacrylic acid with the copolymerization of methacrylic ester.Below (methyl) vinylformic acid is described as the monomer typical example with carboxyl.
As monomer with hydroxyl, known any monomer before can using with hydroxyl, hydroxyalkyl (methyl) acrylate good with the methacrylic ester copolymerization, for example, as alkylidene group, hydroxyalkyl (methyl) acrylate of ethylidene, propylidene, butylidene etc. preferably.Below (methyl) hydroxyethyl acrylate is described as the monomer typical example with hydroxyl.
In a preferred embodiment of the invention, big monomer of adding and and usefulness in above-mentioned monomer.As big monomer; can use any known big monomer of the two keys that have polymerizability endways; as preferred big monomer; for example the molecular weight that has a polymerizability base at the hydrophobic resin end is 4000～30000 big monomer; for example have, have polystyrene resin, polymethacrylate resin (carbon number of ester residue is 1～17) of polymerizability bases such as methacryloyl etc. endways.
In above-mentioned, during as 100 weight %, the weight ratio of each monomeric unit is preferably as follows with the total monomer units of resin of the present invention.Promptly, methacrylic ester is 20～90 weight %, be preferably 30～80 weight %, (methyl) vinylformic acid is 0.5～35 weight %, preferred 1.0～20 weight %, hydroxyethyl (methyl) acrylate is 0.5～35 weight %, be preferably 1.0～20 weight %, big monomeric unit is 0～30 weight %, is preferably 1～20 weight %, other monomer components are 5～75 weight %, are preferably 5～50 weight %.
When the content of methacrylic ester is lower than 20 weight %, even the saponification of being undertaken by overlay film of gained resin formation of the present invention is handled, by resin formation of the present invention by the wetting ability deficiency of overlay film, resin-coated film is also insufficient from the detachment on the article.On the other hand, when surpassing 90 weight %, the resin formation of the present invention after the saponification by overlay film, water-soluble too high, buck is to slack-off by being soaked into by overlay film of resin formation of the present invention, owing to broken away from and need take long to by overlay film, so very undesirable.
When (methyl) acrylic acid content is lower than 0.5 weight %, by gained resin formation of the present invention by overlay film wetting ability deficiency, so the saponification treatment time of methacrylic ester is long, resin-coated film is also insufficient from the detachment on the article.On the other hand, when surpassing 35 weight %, water-soluble too high by overlay film is to being brought problem by the basic physical properties such as water tolerance of overlay film.
When the content of hydroxyethyl (methyl) acrylate is lower than 0.5 weight %, by gained resin formation of the present invention by the methacrylic ester in the overlay film, the saponification treatment time is long, resin-coated film is also insufficient from the detachment on the article.On the other hand, when surpassing 35 weight %, it is unstable, very impracticable that the manufacturing of resin of the present invention becomes.When making resin of the present invention with water system, hydroxyethyl (methyl) acrylate has played the effect of emulsifying agent when polymerization, obtain the finely divided liquid of stabilized resins.And when in non-water system, making resin of the present invention, this hydroxyethyl (methyl) acrylic ester unit, by this resin formation by overlay film in undertaken when crosslinked by linking agent, form and site that linking agent reacts.
The present invention, during in above-mentioned monomer component and with big monomer, its consumption is 0.5～35 weight %, when big monomer content surpassed 30 weight %, too high by the hydrophobicity of overlay film, water was to being become very slow by resin formation of the present invention by soaking into of overlay film, the saponification of methacrylic ester needs the long time, equally, breaking away from is also needed for a long time by overlay film, so very undesirable.Have, big monomer when making resin of the present invention with non-water system, is paid stabilization to polymerization system, can obtain the purpose resin with the high concentration liquid shape again.
Among the present invention, the methacrylic ester in the resin of the present invention and (methyl) acrylic acid gross weight are also very important.When the amount of each monomeric unit in above-mentioned scope, simultaneously, when being 100 weight % with resin of the present invention, this gross weight is 25～95 weight %, is preferably 30～80 weight %, when above-mentioned gross weight is lower than 25 weight %, resin of the present invention as a whole, wetting ability deficiency, also not enough after saponification is handled by the detachment of overlay film.On the other hand, when surpassing above-mentioned scope, resin of the present invention as a whole, wetting ability is too high, break away from processing speed and degenerate, simultaneously, being become by overlay film of disengaging is dispersed, disengaging is not had globality by overlay film, perhaps dissolves, and is difficult to separate from break away from treatment solution break away from by overlay film.
Among the present invention, the resin of the present invention that constitutes by above-mentioned monomer, and then can also and above-mentioned beyond monomer carry out copolymerization, can adjust the performance of gained resin of the present invention.As such monomer, methyl acrylate such as methylacrylic acid methyl ester, methylacrylic acid ethyl ester, (methyl) vinylformic acid n-propyl diester, (methyl) vinylformic acid isobutyl, (methyl) vinylformic acid tert-butyl ester (methyl) acrylic acid lower alkyl esters class is in addition for example arranged; Dialkyl group (the C of toxilic acid
1～C
5) monoalkyl (C of ester, toxilic acid
1～C
5) ester, N, N '-dimethyl (methyl) acrylic acid amides, N, (methyl) acrylic acid amides class of N '-diethyl (methyl) acrylic acid amides etc.; Molecular weight is styrenics such as list (methyl) acrylate, vinylbenzene, alpha-methyl styrene of 200～600 polyoxyethylene glycol; Vinyl acetate between to for plastic, ethylene chloride etc.These can use one or two or more kinds, when whole monomeric unit total amounts is taken as 100 weight %, can use its 0～50 weight %, are preferably 10～35 weight %.
Among the present invention, be purpose with the cross-linking density of adjusting gained resin of the present invention, further carry out copolymerization with polyfunctional vinyl monomer, it is crosslinked that resin at least a portion is formed.The content of multifunctional ethylene monomer unit adds with 0.1～10 weight % ratio of whole resin and to use, preferably with the ratio of 0.1～3.5 weight %.By using this multifunctional vinyl monomer, improved gained cross-linkage of resin of the present invention, the effect that above-mentioned in addition big monomer rises can produce better effect.
As multifunctional vinyl monomer, for example there are three or four (methyl) acrylate of divinylbenzene, ethylene glycol bisthioglycolate (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, polyvalent alcohol etc., divinylbenzene especially good.
The resin of the present invention that is made of above-mentioned monomer can carry out the copolymerization acquisition by former known polymerization, for example, and emulsion polymerization method, soap-free polymerization method (ソ-プ Off リ-) polymerization, dispersion copolymerization method etc.The weight-average molecular weight of the resin of the present invention of Huo Deing is preferably 10,000～100,000 like this, and acid number is preferably 8～250, and hydroxyl value is preferably 4～140.
As mentioned above, resin combination of the present invention is by resin of the present invention, caking agent composition or forms lining film component and dissolving or disperse their liquid medium to be formed, as its use-pattern caking agent, printing-ink and substrate agent etc. are arranged, but be not limited in these purposes.Resin combination of the present invention, when being 100 weight % with total composition, solids component is 5-75 weight %, when being 100 weight % with the solids component total amount, the potential hydrophilic resin is 10～90 weight %, is preferably 20～80 weight %, caking agent composition or formation lining film component are 1～85 weight %, be preferably 2～75 weight %, other compositions are 0.5～20 weight %, are preferably 1～15 weight %.
As caking agent composition or formation lining film component, protein is for example arranged, casein, starch, natural rubber, polyisoprene rubber, the chlorine piperylene rubber, isoprene-isobutylene rubber, the styrene butadiene copolymer rubber, the acrylonitrile-butadiene copolymer rubber, acrylic copolymer, the vinyl acetate between to for plastic based copolymer, vinyl chloride-based copolymerized thing, the ethene-vinyl acetate based copolymer, urethane, polymeric amide, polyester, polyethylene and polypropylene and their muriate, polyisobutene, polyvinyl butyral resin, silicone resin, coumarone resin, ketone resin, chlorine rubber, ring rubber etc.
Liquid medium as dissolving or dispersion the invention described above resin, caking agent or formation lining film component for example has water, methyl alcohol, ethanol, Virahol, methyl ethyl ketone, mibk, toluene, dimethylbenzene, hexalin or their mixture.
In the resin combination of the invention described above available before in the printing-ink used identical tinting material cooperate, make printing-ink.Or, make caking agent by cooperating the caking agent composition.When the substrate agent, preferably use as the substrate agent to form suitably by the composition of overlay film.And then can cooperate dicyclohexyl phthalic acid ester as softening agent, dioctyl phthalic acid ester, dibutyl phthalic acid ester, dibutyl adipic acid ester etc. as required, or other additives.
One of articles handling method of the present invention, be that the resin combination of the present invention (printing-ink) that will contain tinting material prints, is coated on the article surface, and carry out drying and form printing and formed article by overlay film, after this article use, handle with buck, make above-mentioned printing be formed saponification, improve the wetting ability of printing film by the methacrylic ester in the overlay film, make its expansion simultaneously, the expansible printing is broken away from from article by overlay film.
Another kind of articles handling method of the present invention, be that resin combination of the present invention is coated on the surface of article, make its dry formation by overlay film, this by the surface of overlay film on, utilizing arbitrarily, printing-ink is printed as desired literal and pattern, perhaps paste the article of going up other sheet prints, after this article use, handle with buck, make and above-mentionedly carried out saponification by the methacrylic ester in the overlay film, improve above-mentionedly by the wetting ability of overlay film, and make its expansion, expansible is broken away from from article by overlay film and lip-deep printing film thereof or sheet print.
In the aforesaid method, form printing by overlay film (during printing-ink) or caking agent by overlay film (during caking agent) or substrate during by overlay film (during the substrate agent), utilize the hydroxyl reaction in linking agent and the resin of the present invention and form crosslinked.By this crosslinked, in the normal state, can form good to humidity or dewfall weather resistance by overlay film.Have again, when breaking away from this, can promote that buck permeates in by overlay film by overlay film, and after keeping breaking away from by the integrity of overlay film, be easy to from disengaging liquid separation by overlay film.As this linking agent, polyisocyanate compounds, polyepoxides, aminoresin, glutaraldehyde etc. are for example arranged.
Specifically, as polyisocyanate compounds, tolylene diisocyanate (TDI) is for example arranged, 4,4 '-'-diphenylmethane diisocyanate (MDI), Xylene Diisocyanate (XDI), the biuret body of hexamethylene diisocyanate (HMDI) or isophorone diisocyanate vulcabond such as (IPDI), adducts with TriMethylolPropane(TMP) of above-mentioned vulcabond etc., polymeric polyisocyanate classes such as the tripolymer of vulcabond, and then with polymeric polyisocyanate, with alcohol (ethanol, Virahol, the n-butanols), derivative (the phenol of phenol, nitrophenol), lactan (hexanolactam), active methylene group based compound (diethyl malonate, methyl acetoacetate, ethyl 3-oxobutanoate, methyl ethyl diketone) carry out block polyisocyanate etc., and then to utilize the carbodiimide of above-mentioned isocyanic ester manufacturing is linking agent and derivative thereof etc.
As polyepoxides, three-glycidyl chlorinated isocyanurates, 3 is arranged, 4-epoxycyclohexyl methyl esters, 3,4-epoxycyclohexyl carboxylicesters etc.As aminoresin, dihydroxymethyl urea, methylol melamine, butylation methylol melamine etc. are arranged.In addition, also have glutaraldehyde, silane coupling agent, tetra isopropyl titanate, methyl ethyl diketone titanic acid ester or aluminum alcoholate, aluminum chelate class.
As the article that are applicable to resin combination of the present invention, various plastics such as container and packaging film, glasswork, woodwork and ferrous products etc. are for example arranged.The shape of these article does not have particular determination.Printing or glue spread preferably can form the amount that dry thickness is 0.01～20 μ m.The amount that is lower than 0.01 μ m is difficult to obtain uniform coating, and the amount that surpasses 20 μ m is uneconomical, also impracticable.
Can carry out with usual method in article surface printing or coating resin combination of the present invention, not have particular determination.For example, make photogravure, the coating of surface printing (flexographic printing), roller, oppositely roller coating (transfer printing mode), spraying method etc.The formation of resin-coated film and printing etc. are (pipeline system) in a continuous manner, also can carry out respectively.Among the present invention, can directly on article surface, carry out the printing of article or coating, also can stick on the article surface arbitrarily by overlay film on carry out, this is not had particular determination.
In the inventive method, for peel off by resin combination of the present invention form by overlay film, for example, according to the present invention, with printing or be pasted with the plastics film of literal and pattern etc. and plastic containers etc., be ground into small shreds with pulverizer etc. as required after, use the low concentration alkali water retting, handle carried out saponification by the methacrylate unit in the overlay film, expanded by buck by overlay film.For example, article are thrown in the buck, fully stir on one side and be heated to 70～80 ℃ on one side, making by overlay film or paste thereon print to break away from and remove, this is a kind of preferred method.As saponifying agent, can use bucks such as sodium hydroxide or yellow soda ash, expand by making resin-coated film, can both be broken away from well by the sheet print by overlay film or applying of overlay film or the printing on it.During saponification,, can in buck, add organic solvents such as methyl alcohol or ethanol for promoting saponification reaction.
Embodiment
Below enumerate embodiment and comparative example is described more specifically the present invention." part " in the literary composition or " % " if when not having specific qualification, are benchmark with weight.
Synthetic embodiment 1 (synthesis example of Resin A of the present invention)
The Diisopropyl azodicarboxylate that 60 parts methacrylic esters, 20 parts butyl methyl acrylate, 5 parts vinylformic acid, 5 parts hydroxyethyl meth acrylate, 10 parts end are had the polystyrene (molecular weight is about 6000) of polymerizability acryl, 210 parts vinyl acetic monomer, 90 parts Virahol and 1.2 parts is packed in the reaction vessel, is stirred down; in nitrogen atmosphere, 75 ℃ of following polymerizations 8 hours.Polymer fluid is the dispersion liquid of ultra-fine decentralized, and its solids component is 25%.The number-average molecular weight of the resin that obtains is 20,000, and acid number is 38.9, and hydroxyl value is 23.1.
With infrared absorption spectrum and gas chromatogram quality analysis apparatus, front and back are handled in the saponification of the invention described above resin analyze, by the result as can be known, methacrylic ester is to carry out saponification selectively, the butyl methyl acrylate decomposes hardly.With above-mentioned the same, synthesize the resin (I～J) of resin of the present invention (A～F, H) and comparative example with the monomer ratio of record in the table 1.
Synthetic embodiment 2 (synthesis example of resin G of the present invention)
The deionized water of 66.5 parts methacrylic esters, 22.1 parts ethyl-methyl acrylate, 6.7 parts vinylformic acid, 3.3 parts 2-hydroxyethyl meth acrylate, 1.3 parts divinylbenzene, 0.1 part Sodium dodecylbenzene sulfonate, 0.3 part Potassium Persulphate and 200 parts is packed in the reaction vessel, in the nitrogen atmosphere, 70 ℃ of following polymerizations 8 hours are adjusted into 8 with the polymer fluid pH after the polymerization.In 5% aqueous sodium hydroxide solution, under the normal temperature, dip treating is after 1 hour with the resin that obtains, and the water turgidity (deionized water) of resin is 200 times (volumetric ratios).With above-mentioned the same.The resin (K) that synthesizes comparative example with the monomer ratio of record in the table 1.
Table 1 monomer is formed
| Resin | Monomer is formed | Monomer is than (weight) | Solids component (%) | Solvent |
| A | MA/BMA/AA/HEMA/ MS | 60/20/5/5/10 | 25 | EtAc/iPA(7/3) |
| B | MA/St/AA/HEMA/MS | 50/20/10/15/5 | 50 | Tol/iPA(1/1) |
| C | MA/ST/MMA/AA/HE MA/MS | 35/15/15/15/5/15 | 45 | Tol/iPA(1/1) |
| D | MA/St/AA/HEMA/MS | 70/5/10/10/5 | 25 | MEK |
| E | MA/BMA/AA/HEMA/ MS/DVB | 45/10/20/10/15/1.5 | 45 | MEK |
| F | MA/iBA/AA/HEMA/ MS | 50/20/10/15/5 | 45 | Tol/iPA(1/1) |
| G | MA/EMA/AA/HEMA/ DVB | 66.5/22.1/6.7/3.3/1. 3 | 30 | Water |
| H | MA/BMA/AA/HEMA | 45/20/30/5 | 45 | Tol/iPA(1/1) |
| I | BA/nDA | 70/30 | 45 | Tol/iPA(1/1) |
| J | St/AA | 70/30 | 45 | Tol/iPA(1/1) |
| K | St/nDA/BA | 30/30/40 | 50 | Water |
(notes)
MA: methacrylic ester BMA: butyl methyl acrylate
AA: vinylformic acid HEMA: hydroxyethyl meth acrylate
MS: the molecular weight that end has an acryl is 6000 polystyrene
MMA: methyl methacrylate EMA: methacrylic acid ethyl ester
BMA: methacrylic acid butyl ester St: vinylbenzene
IBMA: methacrylic acid isobutyl BA: butyl acrylate cores
NDA: vinylformic acid dodecyl ester DVB: divinylbenzene
EtAc: ethyl acetate iPA: Virahol
TOl: toluene MEK: methyl ethyl ketone
The rerum natura of the resin of the present invention that table 2 obtains
| Resin | Weight-average molecular weight | Acid number mg (KOH)/g | Hydroxyl value mg (KOH)/g |
| A | 20,000 | 38.9 | 23.1 |
| B | 30,000 | 77.8 | 34.6 |
| C | 25,000 | 84.9 | 11.6 |
| D | 20,000 | 77.8 | 34.6 |
| E | Can not measure | 155.6 | 34.6 |
| F | 30,000 | 77.8 | 34.6 |
| G | Can not measure | 52.1 | 15.2 |
| H | 25,000 | 233.3 | 11.6 |
| I | 30,000 | 0 | 0 |
| J | 20,000 | 233.3 | 0 |
| K | 70,000 | 0 | 0 |
Embodiment 1, comparative example 1
The gravure printing that modulation is formed by the vinyl acetic monomer of 10 parts azoic dyestuff, 12 parts acrylic copolymer (based on the methacrylic acid butyl ester), 3 parts celluosic resin, 2 parts polyethylene-based wax, 27 parts Virahol, 27 parts propyl acetate and 6.5 parts is with printing ink (this printing ink is as comparative example 1).Replace 15 parts of resinous principles in the above-mentioned printing ink with following 15 parts resinous principle, modulate printing-ink of the present invention.
Embodiment 1-1
Aforesaid propylene acid based copolymer ... 6 parts
Cellulose-based resin ... 1.5 part
Resin A of the present invention ... 7.5 part
Embodiment 1-2
Aforesaid propylene acid based copolymer ... 6 parts
Cellulose-based resin ... 1.5 part
Resin B of the present invention ... 7.5 part
Embodiment 1-3
Aforesaid propylene acid based copolymer ... 6 parts
Cellulose-based resin ... 1.5 part
Resin C of the present invention ... 7.5 part
Embodiment 1-4
Aforesaid propylene acid based copolymer ... 6 parts
Cellulose-based resin ... 1.5 part
Resin D of the present invention ... 7.5 part
Block polyisocyanate resin (linking agent) ... 0.15 part
Embodiment 1-5
Aforesaid propylene acid based copolymer ... 6 parts
Cellulose-based resin ... 1.5 part
Resin E of the present invention ... 7.5 part
Embodiment 2, comparative example 2
The gravure printing that modulation is formed by the Virahol of 32 parts titanium oxide pigments, 23 parts urethane resin, 1 part cellulose-based resin, 0.4 part rosin, 0.5 part polyethylene-based wax, 26 parts toluene, 14.5 parts methylethylketone, 8.4 parts vinyl acetic monomer and 7 parts is with printing ink (this printing ink is as comparative example 2-1).Resinous principle with in 24.4 parts of above-mentioned printing ink of 24.4 parts of following resinous principles replacements is modulated into printing-ink of the present invention.
Embodiment 2-1
Above-mentioned urethane resin ... 11.5 part
Cellulose-based resin ... 0.5 part
Rosin ... 0.2 part
Resin A of the present invention ... 12.2 part
Embodiment 2-2
Above-mentioned urethane resin ... 11.5 part
Cellulose-based resin ... 0.5 part
Rosin ... 0.2 part
Resin B of the present invention ... 12.2 part
Embodiment 2-3
Above-mentioned urethane resin ... 11.5 part
Cellulose-based resin ... 0.5 part
Rosin ... 0.2 part
Resin C of the present invention ... 12.2 part
Embodiment 2-4
Above-mentioned urethane resin ... 11.5 part
Cellulose-based resin ... 0.5 part
Rosin ... 0.2 part
Resin D of the present invention ... 12.2 part
Butylated melamines ... 12.2 part
Embodiment 2-5
Above-mentioned urethane resin ... 11.5 part
Cellulose-based resin ... 0.5 part
Rosin ... 0.2 part
Resin E of the present invention ... 12.2 part
Comparative example 2-2
Above-mentioned urethane resin ... 11.5 part
Cellulose-based resin ... 0.5 part
Rosin ... 0.2 part
The resin J of comparative example ... 12.2 part
In order to last printing ink, by overlay film, test this printing by the detachment of overlay film, water tolerance and cementability according to following preparation printing.
Printing is by the preparation of overlay film
With 4# stripe shape spreader the PET film (Japan society system SC00 that twists flax fibers and weave: thickness 450 μ m) go up the dry back of coating thickness and be the various printing ink of 1～3 μ m after, 80 ℃ dry 10 minutes down (but embodiment 2-4 carries out the sintering processes in 30 seconds under 150 ℃).
Test method
(1) ablation experiment
The film of printing is flooded in 85 ℃ the 1.5%NaOH aqueous solution, take out through behind the specific time at every turn, the washing of gentle agitation limit, limit is observed printing by the disengaged position of overlay film.Test-results is shown in table 1.Judgement criteria in the table is as follows.
Zero: printing is broken away from fully by overlay film, and printing is identical by the preceding PET film of overlay film and printing.
*: printing is remained on the PET film fully by overlay film.
(2) water tolerance test
The film of printing in 85 ℃ deionized water, rather than in alkaline purification liquid, flood after 30 minutes, observe to print and whether broken away from by overlay film.
(3) adhesive test
Do not broken away from by overlay film to confirm printing with glass paper tape ablation experiment before the ablation experiment.
Table 3 (1) ablation experiment result
| Printing ink | Dipping time (branch) | ||
| 5 | 15 | 30 | |
| Embodiment 1-1 | ○ | ○ | ○ |
| Embodiment 1-2 | △ | ○ | ○ |
| Embodiment 1-3 | ○ | ○ | ○ |
| Embodiment 1-4 | ○ | ○ | ○ |
| Embodiment 1-5 | × | △ | ○ |
| Comparative example 1 | × | × | × |
| Printing ink | Dipping time (branch) | ||
| 5 | 15 | 30 | |
| Embodiment 2-1 | △ | ○ | ○ |
| Embodiment 2-2 | △ | ○ | ○ |
| Embodiment 2-3 | × | △ | ○ |
| Embodiment 2-4 | ○ | ○ | ○ |
| Embodiment 2-5 | ○ | ○ | ○ |
| Comparative example 2-1 | × | × | × |
| Comparative example 2-2 | × | × | × |
(2) water tolerance: the printing of any one example is not all had to break away from by overlay film.
(3) adhesive test: the printing of any one example is not broken away from by multiple all films.
Embodiment 3, comparative example 3
Caking agent X
The solids component weight ratio of above-mentioned resin K, three M-nitro benzoic acid glycerine and three M-nitro benzoic acid trimethyl propane is taken as 1.2/1.0/1.0 respectively, mixes the caking agent that the back forms thermal viscosity (ホ Star ト Star Network).
Caking agent Y
Use above-mentioned resin I.
Adhesive composite in the following table 4 is coated on the label made of paper of aluminium-vapour deposition, and dry, make dry thickness be about 10 μ m.Under 100 ℃, carry out hot pressing afterwards and be bonded on polyethylene terephthalate sheet (PET) and the sheet glass.For sheet glass, add 1% glutaraldehyde with respect to solids component, add 0.5% tosic acid equally as catalyzer, after the mixing, 150 ℃ of 30 seconds of following sintering.With the rerum natura of following these sticky objects of project testing, obtain result shown in the following table 4.
Cementability: zero (having) * (nothing)
Detachment: sticky object is flooded in 70 ℃ 5% aqueous sodium hydroxide solution, measure label from time (branch) that substrate material is peeled off.
Label breaks away from the back caking agent by the survivability of overlay film on substrate material:
Substrate material after caking agent broken away from by overlay film and label, water is estimated after washing for 10 seconds.
*: complete residual caking agent.△: residual half
Zero; Peel off fully.
Table 4
| Example | Caking agent is formed: Resin A/caking agent X (solids component weight ratio) | Cementability | Separation time (branch) | The survivability of caking agent | |||
| PET | Glass | PET | Glass | PET | Glass | ||
| Comparative example 3 | 0/100 | ○ | ○ | 60 | 60 | × | × |
| Embodiment 3-1 | 10/90 | ○ | ○ | 15 | 15 | ○ | ○ |
| Embodiment 3-2 | 15/85 | ○ | ○ | 3 | 5 | ○ | ○ |
| Embodiment 3-3 | 30/70 | ○ | ○ | 1 | 1 | ○ | ○ |
Embodiment 4, comparative example 4
Resin A, D～G, J/ caking agent X or Y are decided to be 40/60 (weight ratio), make up various resins and caking agent composition, form the adhesive composite of the present invention and comparative example, carry out the evaluation identical, obtain the result of table 5 with embodiment 3.
Table 5
| Resin/caking agent | Cementability | Separation time (branch) | The survivability of caking agent | ||||
| PET | Glass | PET | Glass | PET | Glass | ||
| Embodiment 4-1 | G/X | ○ | ○ | 12 | 10 | ○ | ○ |
| Embodiment 4-2 | A/Y | ○ | ○ | 5 | 3 | ○ | ○ |
| Embodiment 4-3 | D/Y | ○ | ○ | 5 | 3 | ○ | ○ |
| Embodiment 4-4 | E/Y | ○ | ○ | 5 | 2 | ○ | ○ |
| Embodiment 4-5 | F/Y | ○ | ○ | 15 | 10 | ○ | ○ |
| Comparative example 4 | J/Y | ○ | ○ | 60 | 60 | ×～△ | × |
In addition, in resin D, with respect to the polyisocyanate adduct (linking agent) of solids component interpolation 0.5%.
According to above-mentioned table 2, when using the low resin J of swelling property, do not obtain ideal results with regard to the survivability of separation time and caking agent.
Embodiment 5, comparative example 5
Use Resin A～E, the I～J of table 1 record, in table 6, form substrate on plastics film (the thick 25 μ m) surface of record by overlay film, and be coated with printing-ink described later in its surface.
(1) substrate is by the formation of overlay film
The ultra-fine decentralized solution coat of each Resin A～E, I～J on the plastics film of table 6 record, is formed the dry thickness of about 5 μ m, 80 ℃ dry 5 minutes down.Each plastics film of table 6 record is as follows.
HDPE: high density polyethylene(HDPE)
PET: handle PET (polyethylene terephthalate)
S-PET: shrink PET
S-PS: shrink PS (polystyrene)
OPP: the polypropylene that twin shaft is prolonged treatment
(2) modulation of printing ink
The printing ink that forms by 10 parts of cyanine orchids, 15 parts of polymeric amide, 3 parts of nitro-cottons, 10 parts of additives and 62 parts of solvents (toluene/isopropanol/vinyl acetic monomer) according to ordinary method preparation.
(3) print at substrate by overlay film
Substrate by overlay film on the above-mentioned printing ink of coating, form the thickness of about 5 μ m when making drying.When not having substrate by overlay film, printing ink is coated on the plastics film, form the thickness of about 5 μ m when dry.
To being coated with plastics film test detachment, water tolerance and the cementability of above printing ink.Test method is as follows.Test-results is shown in table 6 and table 7.
(1) detachment test
The film of printing is flooded in 85 ℃ the 1.5%NaOH aqueous solution, on one side simple agitation, printing observed on one side by the disengaging situation of overlay film.
Numeric representation printing is by overlay film, in 40 minutes spontaneously (film is taken out in the dipping back, be exposed in the flowing water, wiping, in the dipping in the raw) time (branch) of almost completely coming off.Not producing spontaneous disengaging is expressed as follows.
*: substrate is all remaining by overlay film by overlay film and printing, even wiping does not break away from yet.
(2) water tolerance test
The film of printing flood 30 minutes in 85 ℃ deionized water after, observation has or not and comes off.The result is expressed as follows.
Zero: even bath does not break away from yet.
*: spontaneously or water wash away down and break away from.
(3) adhesive test
Before ablation experiment, carry out ablation experiment with the glassine paper band, the printing of confirming is not broken away from by overlay film.Perhaps, after confirming to implement test, identical with normally used printing ink.
Table 6
| Embodiment 5 | |||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | |
| Abscission layer | A | A | A | B | B | B | D | D | D | C | E |
| Film | PET | OPP | HDPE | PET | OPP | HDPE | PET | OPP | HDPE | PET | PET |
| Detachment | 1 | 1 | 1 | 7 | 7 | 7 | 2 | 1 | 3 | 20 | 10 |
| Water tolerance | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Embodiment 5 | Comparative example 5 | ||||||||
| 12 | 13 | 14 | 1 | 2 | 3 | 4 | 5 | 6 | |
| Abscission layer | H | H | H | I | I | I | J | J | |
| Film | PET | OPP | HDPE | PET | OPP | HDPE | PET | OPP | PET |
| Detachment | 30 | 30 | 30 | × | × | × | 120 | 120 | × |
| Water tolerance | ○ | ○ | ○ | ○ | ○ | ○ | △ | △ | ○ |
In addition, in resin B and D, with respect to solids component interpolation polyisocyanate adduct (linking agent) O.5%.
A kind of potential hydrophilic resin can be provided according to the present invention, contain the compoistion and method of use of this resin.Will be in the printing of printing on the plastics by overlay film or stick on sheet print on these goods, handle and it is come off with buck, plastics of colourless state etc. are carried out reclaiming, and simultaneously, the printing that will come off is separated from treatment solution with the sheet print at an easy rate by overlay film.
Claims (15)
1. a potential hydrophilic resin is characterized in that, at least by being formed with lower unit, that is, and in alkalescence, carry out saponification easily and produce carboxyl monomeric unit, have the monomeric unit of carboxyl and have the monomeric unit of hydroxyl, wherein
The monomeric unit that carries out saponification easily and produce carboxyl in alkalescence is a methacrylic ester, and the monomeric unit with carboxyl is vinylformic acid and/or methacrylic acid, and the monomeric unit with hydroxyl is hydroxyalkyl acrylates and/or hydroxyalkyl methacrylates.
2. according to the potential hydrophilic resin of claim 1 record, it is characterized in that when being 100 weight % with the total amount of whole monomeric units, each unitary weight is as follows,
Methacrylic ester ... ... 20～90 weight %
Vinylformic acid and/or methacrylic acid ... ... 0.5～35 weight %
Hydroxyalkyl acrylates and/or hydroxyalkyl methacrylates ... ... 0.5～35 weight %
Other monomeric units ... ... ... ... 5～75 weight %
3. according to the potential hydrophilic resin of claim 1 record, it is characterized in that, also contain the big monomeric unit of the two keys that have polymerizability endways, the content of this big monomeric unit when being 100 weight % with the total amount of whole monomeric units, is 0.5～35 weight %.
4. according to the potential hydrophilic resin of claim 3 record, it is characterized in that, also contain multi-functional monomeric unit, this polyfunctional monomeric unit content, when being 100 weight % with the total amount of whole monomeric units, be 0.1～10 weight %, wherein polyfunctional monomer is at least a following monomer that is selected from: divinylbenzene, glycol diacrylate, ethylene glycol dimethacrylate, polyethyleneglycol diacrylate, polyethylene glycol dimethacrylate, propylene glycol diacrylate, the propylene glycol dimethacrylate, polypropyleneglycol diacrylate, polypropylene glycol dimethacrylate, three or tetramethyl-acrylate of three or tetraacrylate of polyvalent alcohol or polyvalent alcohol.
5. according to the potential hydrophilic resin of claim 4 record, it is characterized in that polyfunctional monomeric unit is a divinylbenzene.
6. a potential hydrophilic resin oil/fat composition is characterized in that, contains the potential hydrophilic resin and the caking agent composition of claim 1 record in the liquid solvent or forms by the composition of overlay film.
7. according to the potential hydrophilic resin oil/fat composition of claim 6 record, it is characterized in that when being 100 weight % with total composition, solids component is 5～75 weight %, when being 100 weight % with the solids component total amount, the weight ratio of each solids component is as follows,
The potential hydrophilic resin ... ... ... ... 10～90 weight %
Caking agent composition or formation lining film component ... 1～85 weight %
Other compositions ... ... ... ... ... ... 0.5～20 weight %
8. according to the potential hydrophilic resin oil/fat composition of record in claim 6 or 7, it is characterized in that, also contain linking agent.
9. according to the potential hydrophilic compositions of claim 6 record, it is characterized in that, also contain tinting material.
10. the recoverying and utilizing method of article, it is characterized in that, the potential hydrophilic compositions of record in printing or the coating claim 9 on the surface of article, its dry formation is printed by overlay film, after these article use, these article are handled with buck, made above-mentioned printing be carried out saponification by the methacrylic ester in the overlay film, above-mentioned printing is expanded by overlay film, and the expansible printing is broken away from from article by overlay film.
11. the article recoverying and utilizing method according to record in the claim 10 is characterized in that, printing is undertaken crosslinked by overlay film by linking agent.
12. the recoverying and utilizing method of article, it is characterized in that, the potential hydrophilic resin oil/fat composition of coating claim 6 record on the surface of article, make its dry formation by overlay film, this by the overlay film surface on printing or paste other sheet prints, after these article use, these article are handled with buck, so that above-mentionedly carried out saponification by the methacrylic ester in the overlay film, make and above-mentionedly expanded by overlay film, this expansible is broken away from from article by overlay film or sheet print by the printing on overlay film and surface thereof.
13. the article recoverying and utilizing method according to record in the claim 12 is characterized in that, is undertaken crosslinked by overlay film by linking agent.
14. the article recoverying and utilizing method according to record in claim 11 or 13 is characterized in that linking agent is aminoresin, polyisocyanate compounds or glutaraldehyde.
15. the article recoverying and utilizing method according to claim 10 record is characterized in that article are plastics or glasswork.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001043579A CN1161390C (en) | 2000-03-16 | 2000-03-16 | Potential hydrophilic resin and composition containing said resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001043579A CN1161390C (en) | 2000-03-16 | 2000-03-16 | Potential hydrophilic resin and composition containing said resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1314422A CN1314422A (en) | 2001-09-26 |
| CN1161390C true CN1161390C (en) | 2004-08-11 |
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|---|---|---|---|
| CNB001043579A Expired - Fee Related CN1161390C (en) | 2000-03-16 | 2000-03-16 | Potential hydrophilic resin and composition containing said resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5123539B2 (en) * | 2007-03-06 | 2013-01-23 | 大日精化工業株式会社 | Copolymer and use thereof |
| EP2431350B1 (en) | 2009-05-15 | 2017-10-04 | Nippon Shokubai Co., Ltd. | Method for producing (meth)acrylic acid and crystallization system |
| RU2523796C2 (en) * | 2009-05-15 | 2014-07-27 | Ниппон Сокубаи Ко., Лтд. | Method of producing (meth)acrylic acid |
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| CN1314422A (en) | 2001-09-26 |
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