CN103614109A - Polyurethane adhesive for package materials - Google Patents
Polyurethane adhesive for package materials Download PDFInfo
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- CN103614109A CN103614109A CN201310534701.9A CN201310534701A CN103614109A CN 103614109 A CN103614109 A CN 103614109A CN 201310534701 A CN201310534701 A CN 201310534701A CN 103614109 A CN103614109 A CN 103614109A
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- isocyanate
- isocyanic ester
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Abstract
The invention discloses a polyurethane adhesive for package materials. The polyurethane composite adhesive is prepared from the following materials in percentage by weight: 65% to 75% of polyester type polyurethane adhesive, 10% to 16% of isocyanate, 2% to 3% of catalyst, and 13% to 16% of reinforcing agent; wherein the isocyanate is taken as the bridging agent, the catalyst is selected from a compound represented by a formula, which is represented in the description, or an organic tin catalyst; in the formula, the R1 represents a residue which is obtained by removing a hydrogen atom from a carbon chain of methyl acetoacetate, the R2 represents a residue which is obtained by removing a hydrogen atom from a carbon chain of methyl-n-amyl ketone, the R3 represents a residue which is obtained by removing a hydrogen atom from a carbon chain of 6-methyl-5-heptenyl-2-one, and the M represents aluminum; the isocyanate is obtained by evenly mixing m-methyl-phenyl isocyanate and p-bromophenyl isocyanate according to a mass ratio of 1:2. The invention aims to solve the problems that: in the prior art, during the polyurethane production process, the reaction time is too long, the product does not have a satisfactory adhesive strength, the adhesive strength of the product is not easy to control, and the adjustment period is too long when the adhesive strength is abnormal.
Description
Technical field
The present invention relates to a kind of polyurethane adhesive for wrapping material, belong to adhesive material technical field.
Background technology
Along with the raising of people's living standard, the requirement of the quality-guarantee of commodity packaging and health assurance is also improved constantly.
Conventional compound package material is mainly that to take the flexible packages such as paper, glassine paper, plastics film, tinsel be base mateiral, through the resulting flexibility compound package material with over-all properties of various combined machining methods.In the quality of compound package material and health influence factor, composite adhesive also plays vital effect.
The composite adhesive of using on market is now that polyurethane adhesive is subsequent reactions type, polyurethane adhesive is after adding a certain proportion of bridging agent, coating is fallen solvent evaporates through high temperature, enclose rolling after matrix material, be work in-process, in room temperature, place 7 days or at the temperature of 50 degree, place 3 days, allowing the active group of bridging agent and the active group of tackiness agent fully react, will obtain the matrix material of required adhesion strength.Its reaction times is long, affects production efficiency, and required adhesion strength is not easy to control.
Summary of the invention
The invention provides a kind of polyurethane adhesive for wrapping material, object is to solve existing polyurethane adhesive in process of production, and the required reaction times is long, and adhesion strength is inadequate, required adhesion strength is wayward, and occurs the long problem of adjustment cycle when abnormal in adhesion strength.
For achieving the above object, the technical solution used in the present invention is: a kind of polyurethane adhesive for wrapping material, and described polyurethane composite gel stick is made after reaction by the material of following quality percentage composition:
Described bridging agent is isocyanic ester;
Described catalyzer is selected from compound or the organotin catalysts of general formula (I);
In formula, R
1in carbochain for batanone acid methyl esters, remove residue, a R after hydrogen atom
2in carbochain for methyl-n-amyl ketone, remove residue, a R after hydrogen atom
3in carbochain for 6-methyl-methyl heptenone, remove a residue after hydrogen atom, M represents aluminium;
Described isocyanic ester be between aminomethyl phenyl isocyanic ester and bromophenyl isocyanic ester is mixed according to the mass ratio of 1:2;
Described toughener is vinylformic acid, methacrylic acid, methyl acrylate, butyl polyacrylate, polymethylmethacrylate, Isooctyl methacrylate, Hydroxyethyl acrylate, methyl methacrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, methacrylic acid-beta-hydroxy ethyl ester, Propylene glycol monoacrylate, Rocryl 410, vinylformic acid glyceryl ester, glyceral methacrylate, vinylformic acid ring pentyl ester, methacrylic acid ring pentyl ester, at least one in cyclohexyl acrylate and methacrylic acid cyclohexyl ester.
Related content in technique scheme is explained as follows:
1, in such scheme, urethane full name is polyurethane(s), and it is the general designation that contains the macromolecular cpd of repetition carbamate groups (NHCOO) on main chain.Urethane is with polyvalent alcohol (comprising glycol) condensation (or transesterify) or by lactone and polyvalent alcohol polymerization by Dicarboxylic Acids (acid anhydrides or ether), make the polyester of hydroxyl as hydroxy component, then react the family macromolecule compound obtaining with vulcabond or polyisocyanates.The urethane making with aliphatic isocyanates is called aliphatic polyurethane, and the urethane making with aromatic isocyanate is called aromatic urethane.The composition of one or more arbitrary proportions of aliphatic polyurethane and aromatic urethane and Kapton have good binding property.Straight or branched, saturated or unsaturated, replace or there is no the isocyanic ester of replacement and polyol reaction and the urethane that generates can be used.Wherein aliphatic isocyanates comprises alkyl monoisocyanate class: methyl isocyanate, n-butyl isocyanate, tertiary butyl isocyanic ester, octadecylisocyanate, cyclohexyl isocyanate.Aromatic isocyanate comprises phenyl monoisocyanates class: parachlorobenzyl isocyanic ester, 3-chloro-phenyl-isocyanic ester, 3, 4-dichlorophenyl isocyanate, 3, 5-dichlorophenyl isocyanate, p-methylphenyl isocyanic ester, between aminomethyl phenyl isocyanic ester, the chloro-4-aminomethyl phenyl of 3-isocyanic ester, p-trifluoromethyl phenyl isocyanic ester, 3-trifluoromethylbenzene based isocyanate), 3-chloro-4-methoxy phenyl isocyanate, p-isopropyl phenyl isocyanate, to bromophenyl isocyanic ester, p-nitrophenyl based isocyanate, 4-(is to chlorophenoxy)-phenyl isocyanate, 4-(is to methoxyphenoxy)-phenyl isocyanate, 4-(is to methylbenzene oxyethyl group)-phenyl isocyanate, (2) alpha-substitution benzyl isocyanate ester class a: tetramethylxylene diisocyanate, to tetramethylxylene diisocyanate, isopropyl alkene-α, α-dimethylbenzyl isocyanic ester (mTMI), due to the isocyanate group of these 3 kinds of compounds not with aromatic ring key conjugation, and α hydrogen is entirely by methyl substituted, so there is the light fastness the same with aliphatics or aromatic isocyanate, thereby become the good raw material of manufacturing light color or white polyurethane coating.Its toxicity is identical with famous light urethane raw isophorone diisocyanate (IPDI).Especially it is to be noted: m TMI, owing to containing ethylene linkage group and isocyanate groups simultaneously, has double activity, thereby expanded its range of application, simultaneously also for the urethane that adopts this raw material to prepare has increased synthetic route.Polyisocyanates: isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI).In addition, also have several important polyisocyanic acid compounds for tackiness agent: triphenylmethane triisocyanate, 4,4 ', 4 "-tri-isocyanic acid phenyl phosphate ester, 4,4 ', 4 "-tri-isocyanic acid phenyl thiophosphatephosphorothioates.Reasonable is IPDI and HDI.
Wherein polyvalent alcohol has: polyether glycol, such as: polyoxypropyleneglycol claims again polypropylene glycol (polyoxypropylene glycol, abbreviation PPG), polytetrahydrofuran diol (polytetrahydrofuran glycol, be called for short PTHF) or polyoxy tetramethylene glycol (polyoxytetramethylene glycol, be called for short PIG, PTMEG, PTMG, PTMO), tetrahydrofuran (THF)-propylene oxide copolymerization glycol (tetrahydrofuran, oxide propylene copolymer glycol).Special polyether polyvalent alcohol, such as, active polyether polyvalent alcohol, flame-retardant polyether glycol, graft type polyether glycol, unsaturated link(age) polyether glycol, polytetrahydrofuran polyvalent alcohol, heterocyclic modified polyether glycol etc.Polyester polyol is normally by Dicarboxylic Acids (acid anhydrides or ester) and polyvalent alcohol (comprising glycol) condensation (or transesterify) or be polymerized by lactone and polyvalent alcohol.
2,, in such scheme, described organotin catalysts is dibutyl tin laurate, stannous octoate, two (dodecyl sulphur) dibutyl tin, dibutyltin diacetate.
Because technique scheme is used, the present invention compared with prior art has following advantages and effect:
The present invention utilizes acrylate (or vinylformic acid) modified polyurethane adhesive for the polyurethane adhesive of wrapping material, can effectively shorten the reaction times of urethane and bridging agent, strengthen the cohesive strength between tackiness agent and matrix material, enhance productivity, reduce production costs; The present invention is simple to operate, and production cost is low, and the cohesive strength of matrix material is good, thereby shortens follow-up set time, and production efficiency is provided.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Embodiment: a kind of polyurethane adhesive for wrapping material, described polyurethane composite gel stick is made after reaction by the material of following quality percentage composition:
Described bridging agent is isocyanic ester;
Described catalyzer is selected from compound or the organotin catalysts of general formula (I);
In formula, R
1in carbochain for batanone acid methyl esters, remove residue, a R after hydrogen atom
2in carbochain for methyl-n-amyl ketone, remove residue, a R after hydrogen atom
3in carbochain for 6-methyl-methyl heptenone, remove a residue after hydrogen atom, M represents aluminium;
Described isocyanic ester be between aminomethyl phenyl isocyanic ester and bromophenyl isocyanic ester is mixed according to the mass ratio of 1:2;
Described toughener is vinylformic acid, methacrylic acid, methyl acrylate, butyl polyacrylate, polymethylmethacrylate, Isooctyl methacrylate, Hydroxyethyl acrylate, methyl methacrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, methacrylic acid-beta-hydroxy ethyl ester, Propylene glycol monoacrylate, Rocryl 410, vinylformic acid glyceryl ester, glyceral methacrylate, vinylformic acid ring pentyl ester, methacrylic acid ring pentyl ester, at least one in cyclohexyl acrylate and methacrylic acid cyclohexyl ester.
In vinylformic acid, exist carboxyl (
), carboxyl can react with the isocyano of complete reaction (-N=C=O) not, produces acid amides, the binding strength between can reinforced composite, the intensity of reinforced composite.
In the polyurethane composite gel of this scheme modification, contain on urethane (polyurethane) macromolecular main chain, contain many carbamate groups (
), ester group (
), amide group (
), between macromole, be easy to generate hydrogen bond, strengthened the force of cohesion of composite gum, strengthen the cohesive strength of composite gum.
Above-described embodiment is only explanation technical conceive of the present invention and feature, and its object is to allow person skilled in the art can understand content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences that spirit is done according to the present invention change or modify, within all should being encompassed in protection scope of the present invention.
Claims (2)
1. for a polyurethane adhesive for wrapping material, it is characterized in that: described polyurethane composite gel stick is made after reaction by the material of following quality percentage composition:
Polyester-type polyurethane adhesive 65% ~ 75%;
Isocyanic ester 10% ~ 16%;
Catalyzer 2% ~ 3%;
Toughener 13% ~ 16%;
Described bridging agent is isocyanic ester;
Described catalyzer be selected from general formula (
) compound or organotin catalysts;
In formula, R
1in carbochain for batanone acid methyl esters, remove residue, a R after hydrogen atom
2in carbochain for methyl-n-amyl ketone, remove residue, a R after hydrogen atom
3in carbochain for 6-methyl-methyl heptenone, remove a residue after hydrogen atom, M represents aluminium;
Described isocyanic ester be between aminomethyl phenyl isocyanic ester and bromophenyl isocyanic ester is mixed according to the mass ratio of 1:2;
Described toughener is vinylformic acid, methacrylic acid, methyl acrylate, butyl polyacrylate, polymethylmethacrylate, Isooctyl methacrylate, Hydroxyethyl acrylate, methyl methacrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, methacrylic acid-beta-hydroxy ethyl ester, Propylene glycol monoacrylate, Rocryl 410, vinylformic acid glyceryl ester, glyceral methacrylate, vinylformic acid ring pentyl ester, methacrylic acid ring pentyl ester, at least one in cyclohexyl acrylate and methacrylic acid cyclohexyl ester.
2. polyurethane adhesive according to claim 1, is characterized in that: described isocyanic ester is methyl isocyanate, n-butyl isocyanate, tertiary butyl isocyanic ester, octadecylisocyanate, cyclohexyl isocyanate, parachlorobenzyl isocyanic ester, 3-chloro-phenyl-isocyanic ester, 3,4-dichlorophenyl isocyanate, 3,5-dichlorophenyl isocyanate, p-methylphenyl isocyanic ester, between aminomethyl phenyl isocyanic ester, the chloro-4-aminomethyl phenyl of 3-isocyanic ester, p-trifluoromethyl phenyl isocyanic ester, 3-chloro-4-methoxy phenyl isocyanate, p-isopropyl phenyl isocyanate, to bromophenyl isocyanic ester, p-nitrophenyl based isocyanate, 4-(is to chlorophenoxy)-phenyl isocyanate, 4-(is to methoxyphenoxy)-phenyl isocyanate, 4-(is to methylbenzene oxyethyl group)-phenyl isocyanate, between tetramethylxylene diisocyanate, to tetramethylxylene diisocyanate, between isopropyl alkene-alpha, alpha-dimethylbenzyl isocyanic ester, isophorone diisocyanate, hexamethylene diisocyanate, triphenylmethane triisocyanate, 4,4 ', 4 " isocyanic acid phenyl phosphate ester or 4-tri-, 4 ', 4 "-tri-isocyanic acid phenyl thiophosphatephosphorothioates.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210107756 CN102618205B (en) | 2012-04-13 | 2012-04-13 | Polyurethane composite adhesive |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210107756 Division CN102618205B (en) | 2012-04-13 | 2012-04-13 | Polyurethane composite adhesive |
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| Publication Number | Publication Date |
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| CN103614109A true CN103614109A (en) | 2014-03-05 |
| CN103614109B CN103614109B (en) | 2015-11-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210107756 Active CN102618205B (en) | 2012-04-13 | 2012-04-13 | Polyurethane composite adhesive |
| CN201310534701.9A Active CN103614109B (en) | 2012-04-13 | 2012-04-13 | For the polyurethane adhesive of wrapping material |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210107756 Active CN102618205B (en) | 2012-04-13 | 2012-04-13 | Polyurethane composite adhesive |
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| CN (2) | CN102618205B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104087048A (en) * | 2014-07-29 | 2014-10-08 | 广西梧州龙鱼漆业有限公司 | Moisture-resistant paint |
| CN110240794A (en) * | 2019-05-06 | 2019-09-17 | 阜阳大可新材料股份有限公司 | A kind of mould proof fiber board adhesive |
| CN110330932A (en) * | 2019-07-23 | 2019-10-15 | 苏州市合谦纺织整理有限公司 | A kind of fabric glue and preparation method thereof |
| CN113234398A (en) * | 2021-04-30 | 2021-08-10 | 广东裕田霸力科技股份有限公司 | Environment-friendly cold-bonding polyurethane adhesive and preparation method thereof |
| CN113963842A (en) * | 2021-10-13 | 2022-01-21 | 瑞安复合材料(深圳)有限公司 | High partial discharge insulating material for oil-cooled motor and preparation method thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709975B (en) * | 2013-11-29 | 2016-07-06 | 中国科学院长春应用化学研究所 | Polyurethane adhesive for compound fluorine plastic film and preparation method thereof |
| CN104497945A (en) * | 2014-12-11 | 2015-04-08 | 昆山东羽纺织品有限公司 | Adhesive oil glue for cloth bonding |
| CN105131865A (en) * | 2015-08-31 | 2015-12-09 | 北京正元天瑞建筑墙体保温技术有限责任公司 | High-strength polyurethane construction glue and preparing method thereof |
| CN107081686A (en) * | 2017-05-27 | 2017-08-22 | 江苏省江南新型复合研磨材料及制品工程技术研究中心有限公司 | A kind of high-strength polyester gauze cloth base handling process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2000014138A1 (en) * | 1998-09-04 | 2000-03-16 | Bayer Aktiengesellschaft | Reactive binding agent with an extended pot life |
| CN101547985A (en) * | 2006-10-26 | 2009-09-30 | 亚什兰许可和知识产权有限公司 | Method of producing flexible laminates |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6309507B1 (en) * | 1999-03-01 | 2001-10-30 | Nippon Polyurethane Industry Co., Ltd. | Polyisocyanate curing agent for laminate adhesive laminate adhesive comprising the same and its use |
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2012
- 2012-04-13 CN CN 201210107756 patent/CN102618205B/en active Active
- 2012-04-13 CN CN201310534701.9A patent/CN103614109B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000014138A1 (en) * | 1998-09-04 | 2000-03-16 | Bayer Aktiengesellschaft | Reactive binding agent with an extended pot life |
| CN101547985A (en) * | 2006-10-26 | 2009-09-30 | 亚什兰许可和知识产权有限公司 | Method of producing flexible laminates |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104087048A (en) * | 2014-07-29 | 2014-10-08 | 广西梧州龙鱼漆业有限公司 | Moisture-resistant paint |
| CN110240794A (en) * | 2019-05-06 | 2019-09-17 | 阜阳大可新材料股份有限公司 | A kind of mould proof fiber board adhesive |
| CN110330932A (en) * | 2019-07-23 | 2019-10-15 | 苏州市合谦纺织整理有限公司 | A kind of fabric glue and preparation method thereof |
| CN113234398A (en) * | 2021-04-30 | 2021-08-10 | 广东裕田霸力科技股份有限公司 | Environment-friendly cold-bonding polyurethane adhesive and preparation method thereof |
| CN113963842A (en) * | 2021-10-13 | 2022-01-21 | 瑞安复合材料(深圳)有限公司 | High partial discharge insulating material for oil-cooled motor and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102618205A (en) | 2012-08-01 |
| CN102618205B (en) | 2013-10-30 |
| CN103614109B (en) | 2015-11-18 |
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Address after: 223900 Sihong Province Economic Development Zone, Suqian, West Ocean West Road, No. 6 Patentee after: Jiangsu Stick new materials Polytron Technologies Inc Address before: 215400 Taicang, Suzhou, Taicang Economic Development Zone, Qingdao West Road, No. 11, No. Patentee before: Suzhou Sidike New Material Science & Technology Co., Ltd. |
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Effective date of registration: 20170705 Address after: 215400 Taicang, Suzhou, Taicang Economic Development Zone, Qingdao West Road, No. 11, No. Patentee after: Taicang Stick new Mstar Technology Ltd Address before: 223900 Sihong Province Economic Development Zone, Suqian, West Ocean West Road, No. 6 Patentee before: Jiangsu Stick new materials Polytron Technologies Inc |