CN1394891A - Polyisocyanate curing agent for laminated adhensive and laminated adhensive using the same - Google Patents
Polyisocyanate curing agent for laminated adhensive and laminated adhensive using the same Download PDFInfo
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- CN1394891A CN1394891A CN 01122449 CN01122449A CN1394891A CN 1394891 A CN1394891 A CN 1394891A CN 01122449 CN01122449 CN 01122449 CN 01122449 A CN01122449 A CN 01122449A CN 1394891 A CN1394891 A CN 1394891A
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Abstract
The present invention provides a polyisocyanate solidifying agent for laminating adhesive containing isocyanate terminal prepolymer and silane coupling agent and laminating adhesive containing said polyisocyanate solidifying agent and resin containing active hydrogen radical.
Description
Technical field
The present invention relates to the laminated bonding agent of laminated bonding agent with polyisocyanate curing agent and this solidifying agent of use.Particularly, the laminated bonding agent that the present invention relates to have specific nonionic hydrophilic group is with polyisocyanate curing agent with contain this solidifying agent and contain the laminated bonding agent of the resin of active hydrogen base.
Background technology
Recently as Packaging Method; thereby owing to the operation adaptability during from the intensity, commodity protectiveness of packing, packing, utilize the effect of publicity of packing, supply with film in a large number and at an easy rate and reduce aspect such as packing cost and consider that the composite and flexible packing significantly grows up.As the laminated bonding agent that is used for this kind film, consider from aspect such as sticking and performance, weather resistance, excellent heat resistance and to the aspect such as applied widely of various films, by host with have the 2 fluid polyurethane class bonding agents that the solidifying agent of isocyanate group forms and become main flow with active hydrogen base.
As this laminated bonding agent, for example there is the spy to open the disclosed urethanes that imported the wetting ability base and the solvent based 2 liquid type bonding agents of polyisocyanate compounds of containing in the flat 5-112766 communique.Open the spy in addition and disclose self-emulsifying type polyisocyanate composition that has imported the wetting ability base and the water-based bonding agent composition that uses said composition in the flat 7-48429 communique.
But open the polyisocyanate compounds of putting down in writing in the flat 5-112766 communique the spy, using the urethanes that has imported the wetting ability base during as host, insufficient with the sticking and property of tinsel, metal evaporation film and polyolefin film.Open in the water-based bonding agent composition of putting down in writing in the flat 7-48429 communique the spy,, must expend lot of energy for the water of use disperses.
On the other hand, open the spy and proposed in the clear 63-110272 communique to improving sticking and property use silane coupling agent.In this communique, also proposed by polyvalent alcohols such as polyether glycol, polyester polyol, polyether urethane polyvalent alcohol, polyester urethane ester polyols and contained the silane coupling agent of isocyanate group and composite laminated bonding agent composition that polyisocyanate compounds is formed.
Along with the variation of dietetic life in this year, more and more higher for the performance requriements of the laminate film that uses in the various food product pack, for example require high temperature resistant distillation to handle.The spy opens the laminate film that the technology put down in writing in the clear 63-110272 communique is difficult to be met this requirement.
Summary of the invention
The purpose of this invention is to provide a kind of exhibiting excellent stability with time, thermotolerance, weather resistance, particularly to the sticking and good laminated bonding agent polyisocyanate curing agent of property of metal species film and polyolefin film, and the laminated bonding agent that uses this solidifying agent.
The present invention includes following (1)-(a 4) invention.
(1) laminated bonding agent polyisocyanate curing agent, it is characterized in that containing the prepolymer (A) of isocyanate group end and the silane coupling agent (B) of general formula (2) expression, wherein (A) obtained by block type polyethers monohydroxy-alcohol (a) reaction that the general formula (1) that organic polymeric polyisocyanate that contains aliphatic polymeric isocyanate and/or alicyclic polymeric isocyanate (c) at least and oxypropylene group content are Duoed than oxyethylene group content is represented
In the formula, R represents the alkyl of carbonatoms 1-5, and m, n represent the integer more than 1,
In the formula, R ' expression methyl or ethyl, r represents the integer of 1-5.
(2) laminated bonding agent polyisocyanate curing agent, it is characterized in that containing the prepolymer of isocyanate group end, (A ') and general formula, (2) Biao Shi silane coupling agent, (B), wherein, (A ') be by containing aliphatic polymeric isocyanate and/or alicyclic polymeric isocyanate at least, (c) general formula that organic polymeric polyisocyanate and oxypropylene group content are Duoed than oxyethylene group content, (1) Biao Shi block type polyethers monohydroxy-alcohol, (a) and, (a) the aliphatic category compound that contains active hydrogen in addition, (b) reaction obtains
In the formula, R represents the alkyl of carbonatoms 1-5, and m, n represent the integer more than 1 respectively,
In the formula, R ' expression methyl or ethyl, r represents the integer of 1-5.
(3) laminated bonding agent, the resin that it is characterized in that containing the polyisocyanate curing agent of (1) record and contain the active hydrogen base.
(4) laminated bonding agent, the resin that it is characterized in that containing the polyisocyanate curing agent of (2) record and contain the active hydrogen base.
The invention example
The terminal prepolymer (A) of isocyanate group among the present invention or (A ') are than the block type polyethers monohydroxy-alcohol (a) of general formula (1) expression of oxyethylene group content many (by weight proportion) or according to circumstances react with (a) aliphatic category compound (b) that contains active hydrogen in addition again and obtain by the organic polymeric polyisocyanate that contains aliphatic polymeric isocyanate and/or alicyclic polymeric isocyanate (c) at least and oxypropylene group content.
In the formula, R represents the alkyl of carbonatoms 1-5, and m, n represent the integer more than 1 respectively,
The carbonatoms of R is the block type polyethers monohydroxy-alcohol (a) of the group more than 6 in the general formula (1), and the polyisocyanate curing agent and the sticking of base material of using it to obtain reduce easily with property.When oxyethylene group content was more than oxypropylene group content (by weight proportion) in the block type polyethers monohydroxy-alcohol (a), the water tolerance of laminate film reduced easily.
The number-average molecular weight of block type polyethers monohydroxy-alcohol (a) is more than 800, preferred 800-5000, more preferably 1000-3000.Number-average molecular weight is lower than down in limited time, and the sticking of bonding agent that contains the polyisocyanate curing agent that uses (a) obtain reduces easily with property.Surpass last prescribing a time limit, the viscosity increased of the polyisocyanate curing agent that use (a) obtains, operability reduces.
Block type polyethers monohydroxy-alcohol (a) can be obtained by known method.With the monohydroxy-alcohol is starting raw material, makes itself and oxyethane carry out opening, and poly-(oxygen ethene) monohydroxy-alcohol of preparation carries out opening with itself and propylene oxide again and makes.
As the monohydroxy-alcohol of starting raw material, aliphatic monobasic alcohol classes such as particular methanol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol.Wherein more preferably methyl alcohol and ethanol.
Among the present invention, consider and the raising of the intermiscibility of host and foreign material between sticking and etc., as required, can be with block type polyethers monohydroxy-alcohol (a) and with (a) aliphatic category compound (b) that contains the active hydrogen base in addition.
Contain the fatty compounds (b) of active hydrogen base as this, methyl alcohol is for example arranged, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, amylalcohol, hexanol, enanthol, octanol, 2-Ethylhexyl Alcohol, phenylcarbinol, low molecule unary alcohol such as alkylene glycol monoalkyl ethers, ethamine, low molecule uncle such as butylamine monoamine, diethylamine, low molecule secondary monoamine such as dibutylamine class, the polyester that contains the active hydrogen base, with the oxyalkylene of carbonatoms more than 3 is to repeat the unitary polyethers that contains the active hydrogen base, the polycarbonate that contains the active hydrogen base, the polyolefine that contains the active hydrogen base, carbonatoms hydroxyl higher fatty acid or its ester etc. more than 6.The aliphatic category compound (b) that preferably contains the active hydrogen base among the present invention is (a) aliphatic category monohydroxy-alcohol in addition.
Aliphatic polymeric isocyanate that uses among the present invention and/or alicyclic polymeric isocyanate (c), the modification body of preferred fat (cyclo) aliphatic diisocyanates and/or alicyclic diisocyanate, more preferably intramolecularly has any the above material that is selected from isocyanuric acid ester group, uretdion (uretdione), biuret groups and the allophanate group.The modification body that intramolecularly has in urethano, urea groups, carbodiimide and the semicarbazono (uretimine) any above aliphatic diisocyanate and/or alicyclic diisocyanate also is fit to use.Aliphatic diisocyanate for example has tetramethylene diisocyanate, hexamethylene diisocyanate, 2-methyl isophthalic acid, 5-pentane vulcabond, 3-methyl isophthalic acid, 5-pentane vulcabond, lysinediisocyanate etc.Alicyclic diisocyanate for example has different Buddhist ketone vulcabond, hydrogenation diphenylmethanediisocyanate, hydrogenation cresylene vulcabond etc., hydrogenation xylylene vulcabond, hydrogenation tetramethyl-benzene dimethyl vulcabond, cyclohexyl diisocyanate etc.Can separately or mix more than 2 kinds and use.Preferred aliphatic polymeric isocyanate and/or alicyclic polymeric isocyanate (c) among the present invention are hexamethylene diisocyanate or the modified polyisocyanurate that obtains with hexamethylene diisocyanate.
Among the present invention, can (c) organic polymeric polyisocyanate in addition in aliphatic polymeric isocyanate and/or alicyclic polymeric isocyanate (c).Concrete example is if any 2,4-cresylene vulcabond, 2,6-cresylene vulcabond, xylylene-1, the 4-vulcabond, xylylene-1, the 3-vulcabond, xylylene-1, the 2-vulcabond, 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate, 4,4 '-diphenyl ether vulcabond, 2-nitro phenylbenzene-4,4 '-vulcabond, 3,3 '-dimethyl diphenylmethane-4,4 '-vulcabond, 4,4 '-diphenyl propane vulcabond, the metaphenylene vulcabond, to phenylene vulcabond, naphthylidene-1, the 4-vulcabond, naphthylidene-1, the 5-vulcabond, 3,3 '-dimethoxy phenylbenzene-4,4 '-vulcabond, or its urethane modified polyisocyanate, biuret modified polymeric polyisocyanate, the carbodiimide modified polymeric polyisocyanate, the imine modified polymeric polyisocyanate of urea, urea diketone modified polyisocyanate, isocyanurate-modified polymeric polyisocyanate.Can separately or mix more than 2 kinds and use.
Temperature of reaction in the preparation of the prepolymer (A) of the isocyanate group end among the present invention or (A ') is 30-120 ℃, preferred 40-100 ℃.The aliphatic category compound (b) that contains the active hydrogen base of Shi Yonging can react together with organic polymeric polyisocyanate with block type polyethers monohydroxy-alcohol (a) as required, also can react with organic polymeric polyisocyanate respectively.Can use urethane catalyzer such as dibutyl tin laurate, triethylenediamine as required during reaction.
In the prepolymer (A) of isocyanate group end or (A '), the import volume of block type polyethers monohydroxy-alcohol (a), by weight (a): (c)=1: 100-80: 100, more preferably (a): (c)=1.5: 100-70: 100.In (a) and with under the situation of (b), import volume (b) is (b) by weight: (c)=1: 100-80: 100, more preferably (b): (c)=1: 100-70: 100.The import volume of block type polyethers monohydroxy-alcohol (a) is lower than down in limited time, and the sticking and property of bonding agent reduces easily.And be higher than in limited time, isocyanate group content reduces as a result, and sticking and intensity reduces easily.
The average sense radix of the terminal prepolymer (A) of isocyanate group or (A ') is 2-5, preferred 2.1-4.9.Average sense radix is crossed when hanging down, and the intensity of cured article or weather resistance become too high, and cured article becomes fragile easily.
The isocyanate group content of the terminal prepolymer (A) of isocyanate group or (A ') is 7-20 weight %, preferred 8-18 weight %.When isocyanate group content is too small, the cross-linking density step-down of bonding agent, the intensity or the weather resistance of cured article reduce easily.When isocyanate group content was too much, the import volume of the block type polyethers monohydroxy-alcohol (a) among the terminal prepolymer (A) of isocyanate group or (A ') tailed off as a result, and the sticking and property of bonding agent reduces easily.
The content of the free organic polymeric polyisocyanate among the terminal prepolymer (A) of isocyanate group or (A ') is below the 1 weight %, more preferably below the 0.9 weight %.When the content of the organic polymeric polyisocyanate of free was too much, shortened the working life of bonding agent, causes the foul smell problem easily.
Silane coupling agent among the present invention (B) is the compound of general formula (2) expression.
In the formula, R ' expression methyl or ethyl, r represents the integer of 1-5.
Also use silane coupling agent in bonding agent, known can the raising glued and property, thermotolerance, resistance to chemical reagents etc.But, in host, particularly having in advance in functional groups' such as amino or epoxy group(ing) the host and cooperate silane coupling agent, time dependent ground causes painted or viscosity increases sometimes.This is considered to organoalkoxysilane owing to functional group in the host and silane coupling agent and partly waits to react and cause.In addition, silane coupling agent is usually owing to have functional groups such as amino, epoxy group(ing), when cooperating silane coupling agent in polyisocyanate curing agent, isocyanate group in the same polyisocyanate curing agent and the reaction of the functional group in the silane coupling agent cause that sometimes viscosity increases by the time.
For the ageing stability of laminated bonding agent, each composition should separately be taken care of, and mixes each composition before use.But, therefore require the laminated bonding agent of exploitation 2 compositions system because the cooperation of the place of keeping or each composition is pretty troublesome.If do not use silane coupling agent, yes 2 compositions system, but when obtaining laminate film that high temperature resistant distillation handles, sticking and property is insufficient.Therefore, in the laminated bonding agent that high temperature resistant distillation is handled, be necessary and use silane coupling agent.
The functional group of the silane coupling agent that uses among the present invention (B) is for-NCO and Si-OR ' (R ' be methyl or ethyl), under common maintaining requirement, do not react with isocyanate group end prepolymer (A) or (A ').Therefore, the ageing stability of polyisocyanate curing agent of the present invention is good.
Host in the laminating adhesive of the present invention, then do not have special restriction if contain the resin of active hydrogen base, for example have polyurethanes resin, polyester resin, polyamide-based resin, acrylic resin, coumarone resinoid, melamine resinoid, urea resinoid, rosin based resin, redix, natural resin, petroleum resinoids such as cellulosic resin, starch or glue such as resol, polyvinyl alcohol, vinyl acetate between to for plastic base ester resin, polyvinyl chloride (PVC) RESINS, ethene-vinyl acetate base ester resin, nitrile resin, Nitrocellulose.Wherein, the binding property of consideration and base material, weather resistance etc., optimization polyurethane resinoid.
The number-average molecular weight of the resin that contains the active hydrogen base that uses as host is 500-100000, more preferably 1000-80000.
Except the urethane resin that only has urethane bond, also contain urethane urea resin with urethane bond and urea bond etc. in this polyurethanes resin.
The polyurethanes resin has preferred hydroxyl isoreactivity hydrogen base more than 2 more than 1.Among the present invention, in urethane resin, add polyisocyanate curing agent, use as 2 solution curing type laminating adhesives with specific wetting ability base.
The polyurethanes resin can obtain by containing the reaction of compound bearing active hydrogen and organic polymeric polyisocyanate.
Contain in the compound of active hydrogen base and contain long-chain polyhydric alcohol and chain extension agent, wherein, preferably contain long-chain polyhydric alcohol 50-90 weight %.
Long-chain polyhydric alcohol for example has polyester polyol, polyesteramide polyvalent alcohol, polycarbonate polyol, polyether glycol, polyolefin polyhydric alcohol, animals and plants oils polyvalent alcohol, and their polyol etc.Among the present invention, consider binding property, weather resistance etc., the preferred polyester polyvalent alcohol.Use these long-chain polyhydric alcohols separately or also can mix use more than 2 kinds.
The preferred 500-10000 of the number-average molecular weight of long-chain polyhydric alcohol.
As the pure and mild polyesteramide polyvalent alcohol of polyester polyols, Succinic Acid is for example arranged, hexanodioic acid, sebacic acid, terephthalic acid, m-phthalic acid, phthalic acid, six hydrogen terephthalic acids, six hydrogen m-phthalic acids, hexahydrophthalic acid, naphthalic acid, polycarboxylic acids such as trimellitic acid, acid esters, or acid anhydrides etc. more than a kind and ethylene glycol, 1, the 1-propylene glycol, 1, ammediol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, the 3-methyl isophthalic acid, the 5-pentanediol, neopentyl glycol, 1, the 8-ethohexadiol, 1, the 9-nonanediol, Diethylene Glycol, dipropylene glycol, 1,4 cyclohexane dimethanol, or the first of the oxyethane of dihydroxyphenyl propane or propylene oxide becomes thing, glycerine, TriMethylolPropane(TMP), low molecular polylol classes such as tetramethylolmethane, hexamethylene-diamine, the xylylene diamines, low molecule alkamine such as isophorone diamine etc. carry out the material that dehydration condensation obtains more than a kind." low molecule " in low molecular polylol class among the present invention, low molecule polyamines class and the low molecule alkamine is meant that number-average molecular weight is lower than 500.
As starting raw material, make cyclic ester (lactone) monomers such as itself and 6-caprolactone, γ-Wu Neizhi carry out the lactone polyester polyol that ring-opening polymerization obtains with above-mentioned low molecular polylol class.
As polycarbonate polyol, for example there are above-mentioned low molecular polylol class and carbonic acid diethylidene ester, methylcarbonate, diethyl carbonate, diphenyl carbonate etc. to carry out the material that dealcoholization, dephenolize reaction obtains.
As polyether glycol, polyoxyethylene glycol that ring-opening polymerizations such as oxyethane, propylene oxide, tetrahydrofuran (THF) obtain, polypropylene glycol, polytetramethylene ether diol etc. are for example arranged, and the polyether glycol that its copolymerization is obtained, can also enumerate with above-mentioned polyester polyol, polyesteramide polyvalent alcohol or polycarbonate polyol in addition is the polyester ether polyvalent alcohol that starting raw material obtains.
As polyolefin polyhydric alcohol, the polyhutadiene that contains hydroxyl, hydrogenation hydroxyl polyhutadiene, hydroxyl polyisoprene, hydrogenation hydroxyl polyisoprene, hydroxyl Chlorinated Polypropylene III, hydroxyl chlorinatedpolyethylene etc. are for example arranged.
As animals and plants oils polyvalent alcohol, dehydrated castor oils polyvalent alcohol, castor-oil plant oils polyvalent alcohol, the fine albumen of spun silk etc. are for example arranged.
If number-average molecular weight 500-10000, contain the material of 2 above active hydrogen bases, as long-chain polyhydric alcohol also be fit to use dipolymer acids polyvalent alcohol, hydrogenation dipolymer acids polyvalent alcohol, polyester resin, polyamide-based resin, acrylic resin, coumarone resinoid, melamine resinoid, urea resinoid, rosin based resin, redix, resenes such as natural resins such as cellulosic resin, starch or glue, polyvinyl alcohol such as resol, Mierocrystalline cellulose.
The chain extension agent is that the number-average molecular weight that intramolecularly contains the active hydrogen base more than 2 is lower than 500 compound, and above-mentioned low molecular polylol class, low molecule polyamines class, low molecule alkamine etc. are for example arranged.Can separately or mix more than 2 kinds and use.
The resinoid synthetic middle organic polymeric polyisocyanate that uses of urethane for example has the organic diisocyanate or its modification body that use in the manufacturing of above-mentioned laminating adhesive with polyisocyanate curing agent.
Urethane is resinoid when synthetic, and the isocyanate group/active hydrogen base (mol ratio) that contains compound and organic polymeric polyisocyanate of active hydrogen base is preferably 0.6/1-1/0.6.Urethane is resinoid when synthetic, average sense radix according to the average sense radix of the isocyanate group of organic polymeric polyisocyanate and the active hydrogen base of the compound that contains the active hydrogen base decides the condition of not carrying out gelation, and cooperating each raw material is very important to satisfy this condition.Its cooperation ratio is according to J.P.Flory, the Theoretical Calculation of Khun etc., in fact, by the reactivity of considering the reactive group that contains in the above-mentioned compound that contains the active hydrogen base and each molecule of organic polymeric polyisocyanate than and the proportioning that adopts, can be without gelation and the synthesis of polyurethane resinoid.
Synthetic polyurethanes resin contains active hydrogen base or isocyanate group, and its number-average molecular weight is 800-100000, preferred especially 1000-80000.When number-average molecular weight was excessive, the viscosity of resin became too high, and operability is poor.When number-average molecular weight is too small, the bond strength deficiency.
During preparation polyurethanes resin,, be about to the solution reaction method that material dissolution reacts in organic solvent, in solvent-free solvent-free reaction method of down each raw material thorough mixing being reacted etc. by known method.
The compound and the one-shot method of organic polymeric polyisocyanate primary first-order equation, the compound that contains the active hydrogen base and the organic polymeric polyisocyanate that contain the active hydrogen base react under the condition of isocyanate group surplus, the prepolymer of synthesizing isocyanate base end, and then make it with the prepolymer method of the compound reaction that contains the active hydrogen base etc.
Under the situation of One-shot method, the mol ratio of isocyanate group/active hydrogen base is 0.5-2, more preferably 0.8-1.5.Be lower than at 0.5 o'clock, the resinoid molecular weight of urethane is too small, the shortcoming weather resistance.2 when above, and during synthetic resins, the organic isocyanate irrelevant with reaction too much exists.
Under the situation of prepolymer method, the mol ratio of the isocyanate group/active hydrogen base when prepolymer is synthetic is 1.1-5.0, more preferably 1.5-4.0.Be lower than at 1.1 o'clock, the molecular weight of prepolymer becomes excessive, and reaction afterwards is difficult to carry out.Be higher than at 5.0 o'clock, tackiness agent lacks binding property.
In the prepolymer method, as with the compound bearing active hydrogen that contains of the prepolymer of isocyanate group end reaction, above-mentioned low molecular polylol class, low molecule polyamines class, low molecule alkamine etc. are for example arranged.In addition, as required, also can use monoamines such as a part of ethamine, diethylamine, aniline, end-capping reagents such as unary alcohol such as methyl alcohol, ethanol.
When terminal prepolymer of synthesizing isocyanate base or polyurethanes resin, can use urethane resinoid normally used catalyzer or stablizer etc. when synthetic.As this catalyzer, tertiary amines such as triethylamine, Triethylene Diamine are for example arranged, metal-salts such as Potassium ethanoate, Zinic stearas, organometallic compounds such as dibutyl tin dilaurate, dibutyl tin oxide.As stablizer, thermal oxidation stabilizers such as ultra-violet stabilizer, phenol derivatives such as the benzotriazole category of replacement are for example arranged.
The temperature of reaction of urethaneization is 10-120 ℃, preferred 30-100 ℃.
Laminating adhesive of the present invention is with cooperating additive or auxiliary agent commonly used in the tackiness agent in polyisocyanate curing agent and the laminating adhesive as required.For example dyestuff, pigment, coupler, dispersion stabilizer, viscosity modifier, flow agent, gelation prevent agent, photostabilizer, antioxidant, UV light absorber, thermotolerance rising agent, plasticizer, charged preventor, strengthening agent, catalyzer, shake change agent, antiseptic-germicide, mould inhibitor, lubricant, inorganic and organic filler.
Fitting method has known method such as stirring, dispersion.
Laminating adhesive of the present invention with polyisocyanate curing agent and laminating adhesive in, also can and with the adjustment of viscosity with improve the organic solvent of wettability.Organic solvent for example has toluene, dimethylbenzene, suwazol (aromatic hydrocarbon solvents of cosmo oil Co., Ltd. system), solvesso aromatic series kind solvents such as (the fragrant same clan hydrocarbon solvents of Exxon KCC system), acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ketones solvents such as pimelinketone, ethyl acetate, butylacetate, esters solvents such as isobutyl acetate, ethyl cellosolve acetate, methyl proxitol acetate, 3-methyl-3-methoxyl group butylacetic acid ester, ethyl-polyol ethers esters solvents such as 3-ethoxy-c acid esters, tetrahydrofuran (THF); ether solvents such as diox.These solvents can separately or mix more than 2 kinds and use.
The proportioning that contains the resin and the polyisocyanate curing agent of active hydrogen base by weight, contains the resin/polyisocyanate curing agent=100/1-100/200 of active hydrogen base, preferred especially 100/5-100/180.When the usage quantity of polyisocyanate curing agent was very few, the weather resistance of cured article was insufficient, the flexibility of cured article shortcoming in the time of too much.
Laminating adhesive of the present invention and metal or polyolefinic binding property are good, so particularly useful when the manufacturing of the laminate film that uses tinsel, metal evaporation film, polyolefin film.In addition also very good, so can be used for each field of adherent of laminated wood, furniture, automobile, railway, electrochemistry goods, non-woven fabrics, footwear, bag etc. with aspects such as the binding property of various base materials, weather resistance.
Suitable membrane when being suitable for laminating adhesive of the present invention, extended polypropylene is for example arranged, extended polypropylene not, polyethylene terephthalate, polybutylene terephthalate, PEN, PBN, nylon, new LDPE (film grade), medium-density polyethylene, high density polyethylene(HDPE), ethene-vinyl acetate base ester copolymer, the vinyl-vinyl alcohol copolymer, vinylchlorid, polyvinyl alcohol, polystyrene, polycarbonate, polyvinylidene chloride, the film of polymer classes such as glassine paper, aluminium, the tinsel of copper etc., or the film that on high score subclass film, forms of these metal evaporations, paper, and the film after coat polymers on these materials.
After surface treatments such as high score subclass film enforcement Corona discharge Treatment, can improve bounding force, so preferred.For polymer-coated film, consider kind, amount and the surface property of the polymkeric substance that applies.
Use the laminating method of laminating adhesive of the present invention, wet laminate process is arranged, do laminated method, known method such as the laminated method of thermosol, extruded layer are legal, the laminated method of non-solvent.
The coating amount of laminating adhesive on film is divided into 0.5-10g/m by resin portion
2, preferred 1-8g/m
2Glue spread is outside this scope the time, and the bond strength of film is insufficient.
Use laminating adhesive of the present invention to make laminate film, for example can carry out by the following method.
That is, at first, coating laminating adhesive of the present invention afterwards, carries out drying as required on film, and film is fitted.Afterwards, as required to laminated film pressurization, heating, the curing reaction of promotion tackiness agent.This moment, preferred pressure was 0.01-2Mpa, and preferred temperature is 40-150 ℃.
Utilize this method, just 2 retes are not closed, also can prepare the goods that 3 above retes close.
As above explanation, polyisocyanate curing agent of the present invention, ageing stability are good especially.Laminating adhesive of the present invention, particularly binding property and the weather resistance with the metal species base material is good.
Embodiment
Embodiment
Below illustrate in greater detail the present invention with embodiment.But the present invention is not limited to embodiment.In addition, " % " in synthesis example, embodiment and the comparative example be not as having special explanation, expression " weight % ".
[preparation of polyisocyanate curing agent]
Embodiment 1
In the reaction unit of 2 liters of the capacity that has stirrer, thermometer, Allihn cooling tube and nitrogen ingress pipe, add colonate (registered trademark) the HX601 gram of Nippon Polyurethane Industry Co., Ltd.'s system, monohydroxy-alcohol (1) 399 gram reacted 3 hours down at 70 ℃.Then to wherein adding coupler (1) 1 gram, preparation polyisocyanate curing agent A.
Viscosity under 25 ℃ of polyisocyanate curing agent A is 2720mPas, and isocyanate group content is 11.1%.Polyisocyanate curing agent A is 25 ℃ of down keepings 1 month in the dark, observe ageing stability, and unconfirmed have special variation in appearance.
Embodiment 2-6, comparative example 1,2
Use the raw material in the table 1, reaction similarly to Example 1, preparation polyisocyanate curing agent B-H.The polyisocyanate curing agent that obtains was in the dark taken care of visual judgement ageing stability 1 month down for 25 ℃.
Result such as table 1 are summed up.
Table 1
Notes 1) in the mensuration of the bond strength of the PET film/aluminium foil of embodiment 7-12 and comparative example 3 and 4, the PET film destroy.
| Embodiment | Comparative example | |||||||
| ?7 | ?8 | ?9 | ????10 | ?11 | ????12 | ????3 | ????4 | |
| Polyisocyanate curing agent (is scaled the solid composition, g) A B C D E F G H | ?5 | ?5 | ?5 | ????5 | ?5 | ????5 | ????5 | ????5 |
| Polyurethane resin solution (is scaled solid formation branch, g) PU-1 | ?100 | ?100 | ?100 | ????100 | ?100 | ????100 | ????100 | ????100 |
| Laminating adhesive bond strength (N/cm) PET/AL 1)Bond strength (N/cm) PET/AL AL/CPP after the AL/CPP pyrogenic distillation is handled | ?AD-1 ?2.9 ?6.9 | ?AD-2 ?3.0 ?6.8 | ?AD-3 ?3.1 ?6.7 | ????AD-4 ????2.9 ????6.8 | ?AD-5 ?3.4 ?7.2 | ????AD-6 ????3.3 ????6.8 | ????AD-7 ????3.3 ????6.8 | ????AD-8 ????3.1 ????6.7 |
| Can not peel off | ????1.3 | Can not peel off | ||||||
| ?6.5 | ?6.4 | ?6.3 | ????7.0 | ????6.9 | ????6.7 | ????3.4 | ????6.6 | |
In embodiment 1-6, comparative example 1,2 and the table 1
ColonateHX: the isocyanate-modified polymeric polyisocyanate that obtains by hexamethylene diisocyanate
Isocyanate group content=21.3%
Viscosity=1500mPas/25 ℃
Monohydroxy-alcohol (1): the number-average molecular weight of the monohydroxy-alcohol that the addition oxypropylene obtains in the methoxy poly (ethylene glycol) of number-average molecular weight 400=1100
Monohydroxy-alcohol (2): the number-average molecular weight of the monohydroxy-alcohol that the addition oxypropylene obtains in the methoxy poly (ethylene glycol) of number-average molecular weight 400=1400
Monohydroxy-alcohol (3): the number-average molecular weight of the monohydroxy-alcohol that the addition oxypropylene obtains in the methoxy poly (ethylene glycol) of number-average molecular weight 700=1700
Monohydroxy-alcohol (4): methoxy poly (ethylene glycol) number-average molecular weight=400
Monohydroxy-alcohol (5) ricinoleic acid methyl ester
Coupler (1): γ-isocyanic ester propyl trimethoxy silicane
Coupler (2): γ-isocyanic ester propyl-triethoxysilicane
Coupler (3): gamma-amino propyl trimethoxy silicane
The determinating reference of ageing stability
Zero: outward appearance no change (not having the generation of curing or throw out or seston)
*: irrelevant change (generation of curing or throw out, seston is arranged)
As shown in Table 1, polyisocyanate curing agent of the present invention has good storage stability.On the other hand, it is bad to have added the ageing stability of the polyisocyanate curing agent H that contains amino coupler.
[synthesizing of urethane resin]
Synthesis example 1
In device similarly to Example 1, add polyvalent alcohol A 246 grams, NPG 13 grams, ethyl acetate 200 grams, 30 ℃ of dissolvings down.Add TDI 41 grams, DOTDL 0.03 gram then therein, reacted 4 hours down at 80 ℃.Along with the carrying out of urethane reaction, viscosity increases, and appends for several times so ethyl acetate is divided into.When the peak of the isocyanate group of infrared absorptiometric analysis disappears, add ethyl acetate 350 grams again, dilution obtains solid formation branch and accounts for 50% polyurethane resin solution PU-1.
In synthesis example 1
Polyvalent alcohol A: the polyester glycol that obtains by ethylene glycol/neopentyl glycol=1/1 (mol ratio) and hexanodioic acid/phthalic acid=1/1 (mol ratio)
Number-average molecular weight=2000
NPG: neopentyl glycol
TDI:2,4-toluene support vulcabond
DOTDL: dilaurate dioctyl tin
[modulation of laminating adhesive]
Embodiment 7-12, comparative example 3,4
Polyurethane resin solution PU-1 and polyisocyanate curing agent A-H are converted into solid formation branch respectively, by weight, fit in urethane resin/polyisocyanate curing agent=100/5, modulate laminated adhesive A D-1-8.
[mensuration of bond strength]
PET film (thickness: 12 microns), aluminium foil (thickness: 7 microns) and the corona treatment CPP film (thickness: 70 microns) of each laminating adhesive AD-1-8, corona treatment are placed the dry type laminator.Respectively with gravure roll dry method coating on the corona treatment face of corona treatment PET film, glue spread is 3.5g/m with AD-1-8
2Behind the coating adhesive, by being set at 80 ℃ drying oven, with the doubling roller applying aluminium foil of 100 ℃ * 0.3Mpa.Be coated with laminated adhesive A D-1-8 with gravure roll respectively again on aluminium foil surface, glue spread is 3.5g/m
2Behind the coating adhesive, by being set at 80 ℃ drying oven, with the corona treatment face of the CPP film of the doubling roller applying corona treatment of 100 ℃ * 0.3Mpa.Film speed is 50 meters/minute.After laminated,, obtain laminate film 40 ℃ of following maintenances 3 days.
Laminate film directly is cut into 15 mm wides respectively, under the condition of 300 millimeters/minute of draw speeds, 25 ℃ * 50%RH of mensuration atmosphere gas, carries out the stripping test of T type.
With laminate film is the inboard with the CPP face respectively, under the condition of 180 ℃ * 0.3Mpa * 1 second, with 3 sides heat-sealing, make bag after, in this bag, add the mixed solution of tomato-sauce/salad oil/vinegar=1/1/1 (weight ratio), seal under these conditions, airtight.135 ℃ of following pyrogenic distillations 20 minutes, carry out T type stripping test (sample is wide 15 millimeters, 300 millimeters/minute of draw speeds) afterwards, measure 25 ℃ * 50%RH of atmosphere gas.
The results are shown in table 2.
Table 2
| Embodiment | Comparative example | |||||||
| ????1 | ????2 | ????3 | ??4 | ????5 | ????6 | ????1 | ????2 | |
| Aliphatic polymeric isocyanate (g) colonate HX | ????601 | ????493 | ????648 | ??567 | ????685 | ????781 | ????860 | ????720 |
| Polyethers monohydroxy-alcohol (g) monohydroxy-alcohol (1) monohydroxy-alcohol (2) monohydroxy-alcohol (3) monohydroxy-alcohol (4) | ????399 | ????507 | ????352 | ??376 | ????315 | ????219 | ????140 | ????140 |
| Aliphatic category compound (g) monohydroxy-alcohol (5) that contains the active hydrogen base | ??57 | ????140 | ||||||
| Silane coupling agent (g) coupler (1) coupler (2) coupler (3) | ????1 | ????5 | ????3 | ??0.5 | ????0.5 | ????1 | ????1 | |
| Polyisocyanate curing agent isocyanate group content (%) viscosity (mPas/25 ℃) storage stability | ????A ????11.1 ????2720 ????○ | ????B ????8.4 ????2800 ????○ | ????C ????12.5 ????2420 ????○ | ??D ??9.9 ??2600 ??○ | ????E ????13.6 ????2300 ????○ | ????F ????16.1 ????2200 ????○ | ????G ????16.9 ????2380 ????○ | ????H ????12.0 ????2720 ????× |
In embodiment 7-12, comparative example 3,4 and table 2
PET: polyethyleneterephthalate
Al: aluminium
CPP: extended polypropylene not
Use the laminating adhesive of polyisocyanate curing agent of the present invention all to show good binding property, but do not use the bond strength of adhesive A D-7 after pyrogenic distillation is handled of coupler to reduce.
Claims (14)
1. laminated bonding agent polyisocyanate curing agent, it is characterized in that containing the prepolymer (A) of isocyanate group end and the silane coupling agent (B) of general formula (2) expression, wherein (A) obtained by block type polyethers monohydroxy-alcohol (a) reaction that the general formula (1) that organic polymeric polyisocyanate that contains aliphatic polymeric isocyanate and/or alicyclic polymeric isocyanate (c) at least and oxypropylene group content are Duoed than oxyethylene group content is represented
In the formula, R represents the alkyl of carbonatoms 1-5, and m, n represent the integer more than 1,
In the formula, R ' expression methyl or ethyl, r represents the integer of 1-5.
2. the laminated bonding agent polyisocyanate curing agent of claim 1 record, the number-average molecular weight of wherein said block type polyethers monohydroxy-alcohol (a) is more than 800.
3. the laminated bonding agent polyisocyanate curing agent of claim 1 record, wherein said organic polymeric polyisocyanate is aliphatic polymeric isocyanate and/or alicyclic polymeric isocyanate (c).
4. the laminated bonding agent polyisocyanate curing agent of claim 1 record, wherein said organic polymeric polyisocyanate is the modified polyisocyanate that is obtained by aliphatic diisocyanate and/or alicyclic diisocyanate.
5. the laminated bonding agent polyisocyanate curing agent of claim 1 record, wherein said organic polymeric polyisocyanate is the isocyanurate-modified polymeric polyisocyanate that is obtained by aliphatic diisocyanate.
6. laminated bonding agent polyisocyanate curing agent, it is characterized in that containing the prepolymer of isocyanate group end, (A ') and general formula, (2) Biao Shi silane coupling agent, (B), wherein, (A ') be by containing aliphatic polymeric isocyanate and/or alicyclic polymeric isocyanate at least, (c) general formula that organic polymeric polyisocyanate and oxypropylene group content are Duoed than oxyethylene group content, (1) Biao Shi block type polyethers monohydroxy-alcohol, (a) and, (a) the aliphatic category compound that contains active hydrogen in addition, (b) reaction obtains
In the formula, R represents the alkyl of carbonatoms 1-5, and m, n represent the integer more than 1 respectively,
In the formula, R ' expression methyl or ethyl, r represents the integer of 1-5.
7. the laminated bonding agent polyisocyanate curing agent of claim 6 record, the number-average molecular weight of wherein said block type polyethers monohydroxy-alcohol (a) is more than 800.
8. the laminated bonding agent polyisocyanate curing agent of claim 6 record, wherein said organic polymeric polyisocyanate is aliphatic polymeric isocyanate and/or alicyclic polymeric isocyanate (c).
9. the laminated bonding agent polyisocyanate curing agent of claim 6 record, wherein said organic polymeric polyisocyanate is the modified polyisocyanate that is obtained by aliphatic diisocyanate and/or alicyclic diisocyanate.
10. the laminated bonding agent polyisocyanate curing agent of claim 6 record, wherein said organic polymeric polyisocyanate is the isocyanurate-modified polymeric polyisocyanate that is obtained by aliphatic diisocyanate.
11. laminated bonding agent, the resin that it is characterized in that containing the polyisocyanate curing agent of claim 1 record and contain the active hydrogen base.
12. the laminated bonding agent of claim 11 record, the wherein said resin that contains the active hydrogen base is the polyurethane resinoid.
13. laminated bonding agent, the resin that it is characterized in that containing the polyisocyanate curing agent of claim 6 record and contain the active hydrogen base.
14. the laminated bonding agent of claim 13 record, the wherein said resin that contains the active hydrogen base is the polyurethane resinoid.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01122449 CN1241966C (en) | 2001-07-09 | 2001-07-09 | Polyisocyanate curing agent for laminated adhensive and laminated adhensive using the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01122449 CN1241966C (en) | 2001-07-09 | 2001-07-09 | Polyisocyanate curing agent for laminated adhensive and laminated adhensive using the same |
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| Publication Number | Publication Date |
|---|---|
| CN1394891A true CN1394891A (en) | 2003-02-05 |
| CN1241966C CN1241966C (en) | 2006-02-15 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101218273B (en) * | 2005-07-08 | 2011-01-05 | 日本聚氨酯工业株式会社 | Composition for forming water-expanded rigid polyisocyanurate foam, process for producing water-expanded rigid polyisocyanurate foam from the composition, and water-expanded rigid polyisocyanurate foa |
| CN101370842B (en) * | 2006-01-19 | 2011-11-09 | 巴斯夫欧洲公司 | Polyurethane adhesive comprising silane groups and carbodiimide groups |
| CN102712732A (en) * | 2010-01-14 | 2012-10-03 | 汉高股份有限及两合公司 | One-component laminating adhesive having silane cross-linking |
| CN102137755B (en) * | 2008-07-22 | 2014-08-06 | 东洋制罐株式会社 | Multilayer film using solvent-free adhesive, method for producing same and packaging container using same |
| WO2023216153A1 (en) * | 2022-05-11 | 2023-11-16 | Rohm and Haas Electronic Materials (Shanghai) Ltd. | Two-component polyurethane adhesive composition |
-
2001
- 2001-07-09 CN CN 01122449 patent/CN1241966C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101218273B (en) * | 2005-07-08 | 2011-01-05 | 日本聚氨酯工业株式会社 | Composition for forming water-expanded rigid polyisocyanurate foam, process for producing water-expanded rigid polyisocyanurate foam from the composition, and water-expanded rigid polyisocyanurate foa |
| CN101370842B (en) * | 2006-01-19 | 2011-11-09 | 巴斯夫欧洲公司 | Polyurethane adhesive comprising silane groups and carbodiimide groups |
| CN102137755B (en) * | 2008-07-22 | 2014-08-06 | 东洋制罐株式会社 | Multilayer film using solvent-free adhesive, method for producing same and packaging container using same |
| CN102712732A (en) * | 2010-01-14 | 2012-10-03 | 汉高股份有限及两合公司 | One-component laminating adhesive having silane cross-linking |
| CN102712732B (en) * | 2010-01-14 | 2015-11-25 | 汉高股份有限及两合公司 | The single-component laminating adhesive of crosslinked with silicane |
| WO2023216153A1 (en) * | 2022-05-11 | 2023-11-16 | Rohm and Haas Electronic Materials (Shanghai) Ltd. | Two-component polyurethane adhesive composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1241966C (en) | 2006-02-15 |
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