CN102604567A - Emulsion type pressure sensitive adhesive composition having high adhesion and chopping-shape characteristics and use thereof - Google Patents
Emulsion type pressure sensitive adhesive composition having high adhesion and chopping-shape characteristics and use thereof Download PDFInfo
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- CN102604567A CN102604567A CN2011101569177A CN201110156917A CN102604567A CN 102604567 A CN102604567 A CN 102604567A CN 2011101569177 A CN2011101569177 A CN 2011101569177A CN 201110156917 A CN201110156917 A CN 201110156917A CN 102604567 A CN102604567 A CN 102604567A
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- type pressure
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- oil
- shape characteristic
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- 239000000203 mixture Substances 0.000 title abstract description 11
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title abstract description 4
- 239000000839 emulsion Substances 0.000 title abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000178 monomer Substances 0.000 claims abstract description 39
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 9
- 239000000872 buffer Substances 0.000 claims abstract description 6
- 239000003999 initiator Substances 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 36
- 239000000470 constituent Substances 0.000 claims description 26
- -1 polyoxy Polymers 0.000 claims description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 12
- 238000005520 cutting process Methods 0.000 claims description 9
- 230000001737 promoting effect Effects 0.000 claims description 8
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 5
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 239000001530 fumaric acid Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 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 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- XDSGMUJLZDSCPA-UHFFFAOYSA-N diazanium;phenoxybenzene;sulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=O.C=1C=CC=CC=1OC1=CC=CC=C1 XDSGMUJLZDSCPA-UHFFFAOYSA-N 0.000 claims description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 claims description 2
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 claims description 2
- WNMORWGTPVWAIB-UHFFFAOYSA-N ethenyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC=C WNMORWGTPVWAIB-UHFFFAOYSA-N 0.000 claims description 2
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019439 ethyl acetate Nutrition 0.000 claims description 2
- 238000009415 formwork Methods 0.000 claims description 2
- 235000019860 lauric fat Nutrition 0.000 claims description 2
- 229940065472 octyl acrylate Drugs 0.000 claims description 2
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims 2
- IONFSBQEDMUDQY-UHFFFAOYSA-M C(C=C)(=O)[O-].C[Ca+] Chemical compound C(C=C)(=O)[O-].C[Ca+] IONFSBQEDMUDQY-UHFFFAOYSA-M 0.000 claims 1
- 238000007334 copolymerization reaction Methods 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 4
- 238000010556 emulsion polymerization method Methods 0.000 abstract description 2
- 150000007934 α,β-unsaturated carboxylic acids Chemical group 0.000 abstract description 2
- 230000009477 glass transition Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 239000011265 semifinished product Substances 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 16
- 239000003292 glue Substances 0.000 description 11
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- 239000004816 latex Substances 0.000 description 7
- 229920000126 latex Polymers 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000004159 Potassium persulphate Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 238000004945 emulsification Methods 0.000 description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 5
- 235000019394 potassium persulphate Nutrition 0.000 description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 230000002045 lasting effect Effects 0.000 description 4
- 210000003739 neck Anatomy 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- STGNLGBPLOVYMA-MAZDBSFSSA-N (E)-but-2-enedioic acid Chemical compound OC(=O)\C=C\C(O)=O.OC(=O)\C=C\C(O)=O STGNLGBPLOVYMA-MAZDBSFSSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- GIEGKXINITVUOO-UHFFFAOYSA-N 2-methylidenebutanedioic acid Chemical compound OC(=O)CC(=C)C(O)=O.OC(=O)CC(=C)C(O)=O GIEGKXINITVUOO-UHFFFAOYSA-N 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention relates to an emulsion type pressure sensitive adhesive composition with high adhesion and chopping property, which can be applied to film label , and comprises: (a) having a structure of C4～12Alkyl acrylate monomer 70-90 phr (part per hondred); (b) vinyl ester (vinyl esters) containing monomers in an amount of 4 to 10 phr; (c) 5 to 15phr of a copolymerizable monomer having a glass transition temperature of 10 ℃ or higher; (d) 1 to 5phr of copolymerizable monomer containing alpha, beta unsaturated carboxylic acid group (carboxyl group); (a) + (b) + (c) + (d)) The total amount was 100 phr. Using (e) a reactive surfactant in an amount of 0.5 to 3.0phr, based on 100phr of (a) + (b) + (c) + (d); and adding an appropriate amount of deionized water, an initiator and a buffer, preparing a semi-finished product by an emulsion polymerization method, and adding (f) a tackifier resin (tackifier) in an amount of 15 to 35phr, based on 100phr of (a) + (b) + (c) + (d). Thus, an emulsion type pressure sensitive adhesive composition product of the present invention having high adhesion and chopping-like characteristics can be formed.
Description
Technical field
The present invention is the oil-in-water type pressure-sensitive sticking agent constituent that has high adhesion and cut the shape characteristic about a kind of, can be applicable to the preparation of film trade mark (film label).
Background technology
Common on the market film trade mark (film label) is used sticks together glue, and it is that (acrylic pressure sensitive adhesive PSA), is divided into solvent-borne type (solvent type) and oil-in-water type (emulsion type) to the acryl pressure-sensing glue usually.Yet along with environmental protection trend grows to even greater heights, the solvent-borne type pressure-sensing glue is receiving under the strict restriction, and oil-in-water type acryl pressure-sensing glue (hereinafter to be referred as latex) has become the main flow on the market.
The Production Flow Chart of general film trade mark comprises, the latex coating, dry, plane materiel is fitted and curl etc.It is divided into three-decker, be respectively lower floor from shape layer (release liner layer), the facestock layer on pressure sensing adhesive layer in middle layer (PSA layer) and upper strata (also being printed layers).And then, be printed on the printed layers of film trade mark according to needed pattern (pattern).Printing engineering simply is divided into printing, cut shape (die-cutting), divest (divesting part not) and curl etc.In film label printing process, one of modal quality complaint is exactly that to cut shape (die-cutting) bad, causes glutinous cutter and shuts down as overflow glue (adhesive bleeding) and collodion silk are oversize.Former because the facestock layer on die incision upper strata; Die retracted after the pressure sensing adhesive layer (PSA layer) in entering middle layer was chopped pressure-sensing glue off; But because of pressure-sensing glue too soft; So few pressure-sensitive gluing partly is brought to printing surface on die, cause printing surface to be polluted and viscose separated but still in each other's thoughts cause divesting bad.
A good film trade mark must be considered initial stage power (tack) and adhesion (peel strength) simultaneously.At this moment, the planner can be located at lower temperature with latex glass tansition temperatures (Tg), makes the molecule of latex have preferable flowability, when the film trade mark is affixed on affixed object, can produce the moment adhesion in the short period of time, is referred to as initial stage power (tack).Another side is when the film trade mark is affixed on low surface energy material (low surface energy substrates), like Vestolen PP 7052 (polypropylene; PP) or Vilaterm (polyethylene; PE), add usually and increase glutinous resin (tackifier), carry its high adhesion (peel strength).
In fact, reach good initial stage power and high adhesion and don't can to produce above-mentioned problem such as bad be not a nothing the matter.Its former because latex also is the reason that causes the glutinous cutter of die when cutting shape when low glass tansition temperatures (also being that glue is softer) increases initial stage power and interpolation and increases glutinous resin and improve adhesion, cause printing surface to be polluted and viscose separated but still in each other's thoughts divest bad.
For addressing the above problem, the present invention is the oil-in-water type pressure-sensitive sticking agent constituent that has high adhesion and cut the shape characteristic about a kind of, is applicable to the application of film trade mark (film label).
Summary of the invention
The present invention is the oil-in-water type pressure-sensitive sticking agent constituent that has high adhesion and cut the shape characteristic about a kind of, can be applicable on the film trade mark (film label), and its composition comprises: (a) have C
4～12Acrylate monomer 70～the 90phr of alkyl (part per hundred); (b) has the vinyl ester of containing (vinyl esters) monomer 4～10phr; (c) the glass tansition temperatures of polymer is the copolymerizable monomer 5～15phr more than 10 ℃ separately; (d) contain α, β unsaturated carboxylic acid base (carboxyl group) copolymerizable monomer 1～5phr; (a)+(b)+(c)+(d) total amount is 100phr.Use (e) reactive interfacial promoting agent with respect to (a)+(b)+(c)+(d)=100phr, its usage quantity is 0.5～3.0phr; And add an amount of deionized water, initiator and buffer reagent, and adopt emulsion polymerization method to process after the work in-process, add (f) tackifying resin (tackifier) 15～35phr again, be for (a)+(b)+(c)+(d)=100phr.Can form a kind of oil-in-water type pressure-sensitive sticking agent constituent product that has high adhesion and cut the shape characteristic of the present invention.
The present invention resultant a kind of have high adhesion and the oil-in-water type pressure-sensitive sticking agent constituent of cutting the shape characteristic when being used in film trade mark (film label), can obtaining high adhesion and cut shape characteristic effect.
A kind of oil-in-water type pressure-sensitive sticking agent constituent that has high adhesion and cut the shape characteristic of the present invention, its composition comprises:
(a) " C
4～12The acrylate monomer of alkyl ", mean Bing Xisuandingzhi, vinylformic acid-2 ethylhexyl, Octyl acrylate, decyl acrylate, isodecyl acrylate or vinylformic acid lauric fat, its perhaps use of the mixing more than 2 kinds separately.For obtaining low glass tansition temperatures and good tackyness, be preferably Bing Xisuandingzhi, vinylformic acid-2 ethylhexyl, its usage quantity scope is 70～90phr.
(b) " have the vinyl ester of containing (vinyl esters) monomer ", mean vinyl butyrate, propylene acetic ester, vinyl isobutyrate or vinyl acetate, its usage quantity scope is 4～10phr.
(c) " the glass tansition temperatures of polymer is the copolymerizable monomer more than 10 ℃ separately " means C
1～4Alkylmethacrylate (alkyl methacrylate), vinyl cyanide (acrylonitrile), vinylbenzene (styrene); It can be separately or the mixture more than 2 kinds; Be preferably TEB 3K, Jia Jibingxisuanyizhi, NSC 20956, its usage quantity scope is 5～15phr.
(d) " contain α; β unsaturated carboxylic acid base (carboxyl group) copolymerizable monomer ", mean vinylformic acid, methylacrylic acid, toxilic acid (maleic acid), fumaric acid (fumaric acid), methylene-succinic acid (itaconic acid), crotonol (crotonic acid), monoalkyl toxilic acid (mono alkyl maleic acid), monoalkyl fumaric acid (mono alkyl fumaric acid); It can be separately or the mixing more than 2 kinds use.The preferably is acrylic or methacrylic acid, and its usage quantity scope is 1～5phr.
(e) used in the present invention " reactive interfacial promoting agent ", it comprises phosphoric acid ester (phosphate ester functionalities), for example MAXEMUL
TM6112, MAXEMUL
TM5011 or MAXEMUL
TM5010, produce by U.S. Uniquema company; And polyoxy vinyl alkane phenyl ether ammonium sulfate salt (polyoxyethylene alkylphenyl ether ammonium sulfate), it can be HITENOL BC-10
TM, HITENOL BC-1025
TM, HITENOL BC-20
TM, HITENOL BC-2020
TMOr HITENOL BC-30
TM, produce by Japanese Dai-Ichi Kogyo Seiyaku company.
A kind of oil-in-water type pressure-sensitive sticking agent that has high adhesion and cut the shape characteristic; Can select for use dissimilar for making when emulsion polymerization carries out to reach the emulsification stability; Usage quantity is 0.2～3.0phr; (e) usage quantity of reactive interfacial promoting agent is for (a)+(b)+(c)+(d)=100phr total amount.
(f) used in the present invention " increases glutinous resin ", and it comprises that water-based rosin increases glutinous resin (dispersions rosin tackifier), and it can be Snowtack
TM765A, Snowtack
TM775A, Snowtack
TMSE780G is produced by U.S. Momentive Specialty Chemicals company, and SE-E720W, SE-E730-55, SE-E650, T-E 102A are produced by Japanese Arkawa Chemical company.
(f) used in the present invention " increases glutinous resin ", and usage quantity is 15～35phr, (f) increases the usage quantity of glutinous resin, is for (a)+(b)+(c)+(d)=100phr total amount.
A kind of oil-in-water type pressure-sensitive sticking agent constituent that has high adhesion and cut the shape characteristic can be participated in reaction by at least a initiator, buffer reagent and deionized water.Initiator can be the two bis-isobutyronitriles of Potassium Persulphate, Sodium Persulfate, ammonium persulphate, tributyl hydrogen peroxide (t-butyl hydroperoxide), azo (1,2-azobisisobutyronitrile) etc.Its usage quantity is 0.2～0.6phr, is for (a)+(b)+(c)+(d)=100phr total amount.
It can be sodium hydroxide, Pottasium Hydroxide, yellow soda ash or sodium hydrogencarbonate buffer reagent.Its usage quantity is 0.2-0.6phr, is for (a)+(b)+(c)+(d)=100phr total amount.
The present invention is the oil-in-water type pressure-sensitive sticking agent constituent that has high adhesion and cut the shape characteristic about a kind of, in reactive tank, carries out the emulsion polymerization reaction, and aforementioned (a) had C
4～12The acrylate monomer of alkyl, (b) have contain vinyl ester (vinyl esters) monomer, (c) separately the glass tansition temperatures of polymer be that copolymerizable monomer, (d) more than 10 ℃ contains α; β unsaturated carboxylic acid base (carboxyl group) copolymerizable monomer, (e) reactive interfacial promoting agent mix; And add down like the common existence of an amount of deionized water, initiator and buffer reagent; Heat and be heated and begin reaction, form latex particle.The emulsion polymerization temperature of reaction is 70～85 ℃; After reaction times is 5～10 hours; Be 7-8 through being cooled to room temperature adding ammoniacal liquor adjustment pH value; Form work in-process, add (f) again and increase glutinous resin, can form a kind of oil-in-water type pressure-sensitive sticking agent constituent product that has high adhesion and cut the shape characteristic of the present invention.
Embodiment
Following examples systems has high adhesion and illustrates with the preparation of cutting the oil-in-water type pressure-sensitive sticking agent constituent of shape characteristic to the present invention is a kind of, is not the protection domain that is used for limiting the present invention.
[embodiment 1]
At first vinylformic acid-2 ethylhexyl monomer [forming (a)], the Butyl Acrylate Monomer [composition (a)] of 150.4g, 12.8g vinyl acetate [forming (b)], 41.6g methyl acrylate [forming (c)], 3.2g Acrylic Acid Monomer [forming (d)], 3.2g methacrylic acid monomer [forming (d)], the even stirring with 108.8g is prepared into A solution.
Other gets the deionized water of 95.4g and the 20%MAXEMUL of 26.0g
TMEvenly stir and be prepared into B solution 6112 [forming (e)].
Pour A solution into B solution lasting the stirring and be prepared into preparatory emulsification C solution.
The deionized water that other gets 30.0g is prepared into D solution.
The even stirring of Potassium Persulphate that other gets deionized water, 1.6g sodium hydrogencarbonate and the 1.6g of 147.6g is prepared into E solution.
Pour D solution into emulsion polymerization equipment, it comprises: in whisking appliance, TM, well heater, reflux condensing tube, five necks and the one liter of round-bottomed bottle.When being heated to 80 ℃, E solution and C solution were fed emulsion polymerization equipment respectively at 240 minutes.Then temperature is risen to 85 ℃, keep 90 minutes postcooling to room temperature, adding 10% ammoniacal liquor 3g adjustment pH value is 7.5, forms work in-process; Add 120g Snowtack again
TM775A increases glutinous resin [forming (f)], can form a kind of oil-in-water type pressure-sensitive sticking agent constituent product that has high adhesion and cut the shape characteristic of the present invention, and its physical properties is following, and solid content is 53%, and viscosity is 400cps, and latex particle size is 250nm.
[embodiment 2]
At first vinylformic acid-2 ethylhexyl monomer [forming (a)], the Butyl Acrylate Monomer [composition (a)] of 90.72g, 16.0g vinyl acetate [forming (b)], 38.4g methyl acrylate [forming (c)], 3.2g Acrylic Acid Monomer [forming (d)], 3.2g methacrylic acid monomer [forming (d)], the even stirring with 168.4g is prepared into A solution.
Other gets the deionized water of 95.4g and the 25%HITENOL BC-1025 of 26.0g
TM[forming (e)] evenly stirs and is prepared into B solution.
Pour A solution into B solution lasting the stirring and be prepared into preparatory emulsification C solution.
The deionized water that other gets 30.0g is prepared into D solution.
The even stirring of Potassium Persulphate that other gets deionized water, 1.6g sodium hydrogencarbonate and the 1.6g of 140.6g is prepared into E solution.
Pour D solution into emulsion polymerization equipment, it comprises: in whisking appliance, TM, well heater, reflux condensing tube, five necks and the one liter of round-bottomed bottle.When being heated to 80 ℃, E solution and C solution were fed emulsion polymerization equipment respectively at 240 minutes.Then temperature is risen to 85 ℃, keep 90 minutes postcooling to room temperature, adding 10% ammoniacal liquor 3g adjustment pH value is 7.5, forms work in-process; Add 120g T-E-102A again and increase glutinous resin [forming (f)], can form a kind of oil-in-water type pressure-sensitive sticking agent constituent product that has high adhesion and cut the shape characteristic of the present invention.
[comparing embodiment 1]
At first vinylformic acid-2 ethylhexyl monomer [forming (a)], the Butyl Acrylate Monomer [composition (a)] of 150.4g, 12.8g vinyl acetate [forming (b)], 41.6g methyl acrylate [forming (c)], 3.2g Acrylic Acid Monomer [forming (d)], 3.2g methacrylic acid monomer [forming (d)], the even stirring with 108.8g is prepared into A solution.
Other gets the deionized water of 95.4g and polyalkylene glycol alkyl phenolic ether and even stirring of 6.0g sulfonic group-dodecyl phenyl ether disodium of 1.8g is prepared into B solution.
Pour A solution into B solution lasting the stirring and be prepared into preparatory emulsification C solution.
The deionized water that other gets 30.0g is prepared into D solution.
The even stirring of Potassium Persulphate that other gets deionized water, 1.6g sodium hydrogencarbonate and the 1.6g of 135.2g is prepared into E solution.
Pour D solution into emulsion polymerization equipment, it comprises: in whisking appliance, TM, well heater, reflux condensing tube, five necks and the one liter of round-bottomed bottle.When being heated to 80 ℃, E solution and C solution were fed emulsion polymerization equipment respectively at 240 minutes.Then temperature is risen to 85 ℃, keep 90 minutes postcooling to room temperature, adding 10% ammoniacal liquor 3g adjustment pH value is 7.5.Add 120g Snowtack again
TM775A increases glutinous resin, can form oil-in-water type pressure-sensitive sticking agent constituent.
[comparing embodiment 2]
At first vinylformic acid-2 ethylhexyl monomer [forming (a)], the Butyl Acrylate Monomer [composition (a)] of 150.4g, 12.8g vinyl acetate [forming (b)], 41.6g methyl acrylate [forming (c)], 3.2g Acrylic Acid Monomer [forming (d)], 3.2g methacrylic acid monomer [forming (d)], the even stirring with 108.8g is prepared into A solution.
Other gets the deionized water of 95.4g and polyalkylene glycol alkyl phenolic ether and even stirring of 6.0g sulfonic group-dodecyl phenyl ether disodium of 1.8g is prepared into B solution.
Pour A solution into B solution lasting the stirring and be prepared into preparatory emulsification C solution.
The deionized water that other gets 30.0g is prepared into D solution.
The even stirring of Potassium Persulphate that other gets deionized water, 1.6g sodium hydrogencarbonate and the 1.6g of 135.2g is prepared into E solution.
Pour D solution into emulsion polymerization equipment, it comprises: in whisking appliance, TM, well heater, reflux condensing tube, five necks and the one liter of round-bottomed bottle.When being heated to 80 ℃, E solution and C solution were fed emulsion polymerization equipment respectively at 240 minutes.Then temperature is risen to 85 ℃, keep 90 minutes postcooling to room temperature, adding 10% ammoniacal liquor 3g adjustment pH value is 7.5, adds 120g SE-E720W again and increases glutinous resin, can form oil-in-water type pressure-sensitive sticking agent constituent.
The monomer of the embodiment of the invention 1,2 and comparing embodiment 1,2 uses is formed (a)～(d), and reactive emulsifier (e) and tackifying resin (f) compare, shown in following table one.
Table one,
Zero: have interpolation *: add
[making of specimen]
The oil-in-water type pressure-sensitive sticking agent of the embodiment of the invention 1,2 and comparing embodiment 1,2 gained; Be applied to 38 μ m polyester (PET) fractal films (release liner) respectively; Its coating layer thickness is 20 μ m; Put into baking oven (80 ℃ * 5 minutes), fit in 50 μ m polyester (PET) films then, can form film trade mark (film label) product.
Following testing method is carried out steel plate adhesion (performance numbering 1), PE plate adhesion respectively: (performance numbering 2), ring-type initial stage power (performance numbering 3), cut shape characteristic (performance numbering 4), The performance test results is with reference to following
Table two.
[testing method]
1. steel plate adhesion: (performance numbering 1)
According to ASTM D-1000 standard.
2.PE plate adhesion: (performance numbering 2)
According to ASTM D-1000 standard.
3. ring-type initial stage power: (performance numbering 3)
Sample size is 25mm * 200mm, and glue faces down, and two ends 25mm overlaps and forms ring-type end to end, stops after making the adhesive tape below and steel plate contacting just, and the speed with 300mm/min rises the maximum adhesion power (kg/in) when asking adhesive tape to leave steel plate again.
4. cut the shape characteristic: (performance numbering 4)
Sample size is 15cm * 2.54cm, and glue faces up, and is positioned over the puller system platform.Get die 8cm * 0.9cm * 0.42mm and be installed on the puller system, the adjustment level.The parameter of setting puller system reaches mucigel with the speed incision of 0.1mm/sec, during the about 18 μ m of the degree of depth, and with the speed of 0.02mm/sec toward being back to the die original position.When collodion silk is brought up by die, have a reactive force, leave the distance that the glue face is walked by measuring die when the most capable strength makes zero, promptly can be considered collodion silk length.As collodion silk length shorter (μ m), expression is cut the shape characteristic better.
[test result]
The embodiment of the invention 1,2 and comparing embodiment 1,2 rerum naturas are carried out gained result such as table two according to aforementioned testing method respectively:
Table two, the embodiment of the invention 1,2 and the rerum natura comparison sheet of embodiment 1,2 quite.
This shows that the present invention a kind of has high adhesion and the made film trade mark of oil-in-water type pressure-sensitive sticking agent constituent of cutting the shape characteristic and have and can obtain high steel plate adhesion and cut effect such as shape characteristic.Above embodiment only is used for illustrating the object of the invention, technology contents, characteristics and effect, is not to be used for limiting protection scope of the present invention.
Claims (10)
1. one kind has high adhesion and the oil-in-water type pressure-sensitive sticking agent constituent of cutting the shape characteristic, comprising:
(a) has C
4～12Acrylate monomer 70～the 90phr of alkyl;
(b) has the vinyl ester monomers of containing 4～10phr;
(c) but separately the glass tansition temperatures of polymer be the copolymerization more than 10 ℃
5～15phr；
Close monomer
(d) has the α of containing, β unsaturated carboxylic acid base copolymerizable monomer 1～5phr;
(e) reactive interfacial promoting agent 0.5～3.0phr;
(f) increase glutinous resin 15～35phr;
(a)+(b)+(c)+(d)=100phr wherein; (e) usage quantity system is for (a)+(b)+(c)+(d)=100phr; And add an amount of deionized water, initiator and buffer reagent, and form work in-process through the emulsion polymerization reaction, add (f) then and increase glutinous resin and form; (f) usage quantity system is for (a)+(b)+(c)+(d)=100phr, and wherein the reactive interfacial promoting agent can be phosphoric acid ester or polyoxy vinyl alkane phenyl ether ammonium sulfate salt again.
2. like 1 said a kind of oil-in-water type pressure-sensitive sticking agent constituent that has high adhesion and cut the shape characteristic of claim the, wherein (a) comprises having C
4～12The acrylate monomer of alkyl, it can be Bing Xisuandingzhi, vinylformic acid-2 ethylhexyl, Octyl acrylate, decyl acrylate, isodecyl acrylate or vinylformic acid lauric fat.
As said a kind of of 1 of claim the have height stick together with and cut the oil-in-water type pressure-sensitive sticking agent constituent of shape characteristic, wherein (b) comprises vinyl butyrate, propylene acetic ester, vinyl isobutyrate or vinyl acetate.
4. like 1 said a kind of oil-in-water type pressure-sensitive sticking agent constituent that has high adhesion and cut the shape characteristic of claim the, wherein (c) comprises having C
1～4Alkyl methyl CALCIUM ACRYLATE, vinyl cyanide or vinylbenzene.
5. like 1 said a kind of oil-in-water type pressure-sensitive sticking agent constituent that has high adhesion and cut the shape characteristic of claim the; Wherein (d) comprises having the α of containing; β unsaturated carboxylic acid base copolymerizable monomer, it can be vinylformic acid, methylacrylic acid, toxilic acid, fumaric acid, methylene-succinic acid, crotonol, monoalkyl toxilic acid or monoalkyl fumaric acid.
6. like 1 said a kind of oil-in-water type pressure-sensitive sticking agent constituent that has high adhesion and cut the shape characteristic of claim the, wherein, (e) comprise phosphoric acid ester reactive interfacial promoting agent, it can be MAXEMUL
TM6112, MAXEMUL
TM5011 or MAXEMUL
TM5010.
7. like 1 said a kind of oil-in-water type pressure-sensitive sticking agent constituent that has high adhesion and cut the shape characteristic of claim the, wherein, (e) comprise polyoxy vinyl alkane phenyl ether ammonium sulfate salt reactive interfacial promoting agent, it can be HITENOL BC-10
TM, HITENOL BC-1025
TM, HITENOL BC-20
TM, HITENOL BC-2020
TMOr HITENOL BC-30
TM
8. have high adhesion and the oil-in-water type pressure-sensitive sticking agent constituent of cutting the shape characteristic like said a kind of of 1 of claim the, wherein (f) comprises and increases glutinous resin, can be water-based rosin and increases glutinous resin.
9. like 1 said a kind of oil-in-water type pressure-sensitive sticking agent constituent that has high adhesion and cut the shape characteristic of claim the, wherein (f) comprises that water-based rosin increases glutinous resin and can be Snowtack
TM765A, Snowtack
TM775A, Snowtack
TMSE780G, SE-E720W, SE-E-730-55, SE-E-650 or T-E-102A.
10. each said a kind ofly have high adhesion and cuts the purposes of the oil-in-water type pressure-sensitive sticking agent constituent of shape characteristic as the film trade mark in 1 to 9 of the claim the.
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| TW100101771 | 2011-01-18 | ||
| TW100101771A TWI507495B (en) | 2011-01-18 | 2011-01-18 | Emulsion pressure sensitive adhesive composition having high peel strength and good die-cutting property, and adhesive film |
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| CN102604567A true CN102604567A (en) | 2012-07-25 |
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| US6013722A (en) * | 1998-01-27 | 2000-01-11 | 3M Innovative Properties Company | Non-whitening emulsion pressure sensitive adhesives |
| KR20050067158A (en) * | 2002-09-26 | 2005-06-30 | 설패이스 스페셜티즈, 에스.에이. | Removable, water-whitening resistant pressure sensitive adhesives |
| JP4204838B2 (en) * | 2002-10-04 | 2009-01-07 | リンテック株式会社 | Overlamination adhesive film |
| TWI255289B (en) * | 2004-05-05 | 2006-05-21 | Four Pillars Entpr Co Ltd | Emulsion type acrylic pressure sensitive adhesives |
| US20060235131A1 (en) * | 2005-04-15 | 2006-10-19 | Hughes Kathleen A | Process for preparing aqueous dispersions of multistage emulsion polymers |
| JP4938256B2 (en) * | 2005-07-14 | 2012-05-23 | リンテック株式会社 | (Meth) acrylic emulsion-type pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
| US20090004394A1 (en) * | 2007-06-29 | 2009-01-01 | Anne Denise Koller | Aqueous polymeric composition |
| EP2342245B1 (en) * | 2008-10-09 | 2019-03-06 | Allnex Netherlands B.V. | Aqueous hybrid dispersions |
| TWI414575B (en) * | 2009-02-25 | 2013-11-11 | Symbio Inc | Water-whitening resistant, removable emulsion pressure sensitive adhesives |
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| JP3358437B2 (en) * | 1996-04-15 | 2002-12-16 | 東洋インキ製造株式会社 | Water-based pressure-sensitive adhesive |
| US20040127121A1 (en) * | 2002-12-31 | 2004-07-01 | Schwab Jeffrey J. | Adhesive tape |
| CN101062850A (en) * | 2007-04-20 | 2007-10-31 | 王鑫平 | Flexible acrylic ester emulsion for sand pulp |
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| TWI507495B (en) | 2015-11-11 |
| TW201231583A (en) | 2012-08-01 |
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