CN107987713A - A kind of lacquer painting silane coupling agent and its application - Google Patents
A kind of lacquer painting silane coupling agent and its application Download PDFInfo
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- CN107987713A CN107987713A CN201711403454.3A CN201711403454A CN107987713A CN 107987713 A CN107987713 A CN 107987713A CN 201711403454 A CN201711403454 A CN 201711403454A CN 107987713 A CN107987713 A CN 107987713A
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- Prior art keywords
- silane coupling
- coupling agent
- lacquer painting
- isocyanate
- terminated polymer
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-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
Abstract
This application provides a kind of lacquer painting silane coupling agent, in terms of parts by weight, including following components：5~20 parts of isocyanate-terminated polymer；5~15 parts of polyisocyanates；10~30 parts of mill base；0.5~3 part of latent curing agent；50~125 parts of solvent；0.1~1 part of catalyst；The isocyanate-terminated polymer is made by isocyanates and polyol reaction；One or more of the polyisocyanates in polymethylene multi-phenenyl isocyanate, polymethylene diisocyanate oligomer, three-functionality-degree isocyanates and tetra functional isocyanates.Present invention also offers application of the lacquer painting silane coupling agent as the pretreating agent of polyurethane sealant.The silane coupling agent can improve adhesive effect of the polyurethane glass glue on 1k and 2k lacquer paintings；The silane coupling agent provided using the application, can not only improve the caking property between vehicle body lacquer painting and polyurethane adhesive, additionally it is possible to shorten the construction time, improve construction efficiency.
Description
Technical field
The present invention relates to adhering and sealing field, more particularly, to a kind of lacquer painting silane coupling agent and its application.
Background technology
As requirement of the transportation and communications such as automobile, rail vehicle, car to comfort and security is higher and higher, its
The glass in driver's cabin and compartment is generally connected using the method for elastic adhesive with car body, is sealed instead of traditional rubber strip.It is several at present
100% passenger car uses polyurethane glass glue sticking glass for vehicle window, and commercial car, rail vehicle are also progressively gathered using one pack system
Urethane adhesive technology substitutes rubber strip and is sealed.Compared with common rubber weather strip, single component polyurethane adhesive technique tool
There is the advantages of easy, reliability is high.Using the method for bonding, windshield can not only be made to be firmly attached with vehicle body and be attached to one
Rise, overall sealing performance is obviously improved, and improves the vehicle body integral rigidity of automobile, adds holding during glass breaking
Rate, increases substantially the security of automobile.
During using polyurethane glass glue, generally require to match silane coupling agent, so as to improve glass cement and vehicle body and glass
Cementability.Body of a motor car paint has 1k paint (one-component paint) and 2k paint two kinds of (two-component paint), wherein 1k paint
Surface usually requires to brush one layer of varnish again, and the main component of varnish is generally acrylate, polyester resin, phenolic resin etc. thoroughly
Ming tree fat, it is stronger with the active force of polyurethane glass glue, often can also be realized without using silane coupling agent polyurethane glass glue with
The bonding of vehicle body lacquer painting.And 2k paint carries brightness, without reusing varnish increase gloss.2k lacquer paintings due to no varnish, its
Surface composition is mainly the filler and resin in painting, relatively weak with the effect of polyurethane glass glue, when polyurethane glass glue
Interface peel often occurs during applied to 2k lacquer paintings, it is therefore desirable to the use of vehicle body lacquer painting silane coupling agent is equipped with, it is close to reach bonding
The purpose of envelope.
Prior art discloses the method that some prepare lacquer painting silane coupling agent, for example, application publication number is CN102604527A
Chinese patent literature report a kind of preparation method of polyurethane paint primer agent.This method is by the film forming matter of 8~12wt%
Matter, the pigment of 3~6wt% are added in the organic solvent of 70~76wt%, are stirred with the rotating speed of 25~35r/min in ball mill
Mix 2~4h to be uniformly mixed, obtain primary mix, curing agent, the auxiliary agent of 8~13wt% are added, with the rotating speed of 25~35r/min
2~4h is stirred in ball mill to be uniformly mixed, and obtains lacquer painting silane coupling agent.
The diluted polyester resin of above-mentioned prior art generally use solvent, curing agent, pigment etc. are the primary coat of key component
Agent, but when these silane coupling agents and polyurethane glass glue match, the cohesional failure rate ＜ 80% on 2k lacquer paintings, it is seen that poly-
Cementability of the urethane glass cement on 2k lacquer paintings has much room for improvement.
The content of the invention
In view of this, the application, which provides a kind of lacquer painting silane coupling agent and its application, the lacquer painting silane coupling agent, can improve polyurethane glass
Adhesive effect of the glass glue on 2k lacquer paintings, so as to improve the adhesive strength of glass and vehicle body, ensures vehicle safety.
The present invention provides a kind of lacquer painting silane coupling agent, in terms of parts by weight, including following components：5~20 parts of isocyanates
Terminated polymer；5~15 parts of polyisocyanates；10~30 parts of mill base；0.5~3 part of latent curing agent；50~125 parts
Solvent；0.1~1 part of catalyst；The isocyanate-terminated polymer is made by isocyanates and polyol reaction；It is described more
Isocyanates is selected from polymethylene multi-phenenyl isocyanate, polymethylene diisocyanate oligomer, three-functionality-degree isocyanates
With the one or more in tetra functional isocyanates.
Preferably, the isocyanate-terminated polymer is prepared in accordance with the following methods：By isocyanates and polyalcohol in 60
2~5h is reacted at~80 DEG C, obtains isocyanate-terminated polymer.
Preferably, the amount ratio of the isocyanate group of the isocyanate-terminated polymer and the material of polyol hydroxyls group
For 2.0~3.0.
Preferably, the isocyanates is selected from toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, 1,6- oneself is two different
One or more in cyanate, dicyclohexyl methyl hydride diisocyanate and isophorone diisocyanate.
Preferably, one kind in polyether polyol, modified polyether polylol and polyester polyol of the polyalcohol or
It is a variety of.
Preferably, one kind in three-functionality-degree isocyanates and tetra functional isocyanates of the polyisocyanates or
It is a variety of.
Preferably, one or more of the latent curing agent in ketimide He oxazolidine.
Preferably, the mill base is oiliness black color paste, generally comprises the components such as carbon black and water；It is further preferred that institute
State carbon black mass content in oiliness black color paste and be more than 10% and less than or equal to 30%, the mass content of water is less than 0.4%.
Preferably, one or more of the solvent in ethyl acetate, methyl acetate, acetone and butanone.
Preferably, the catalyst is selected from organic bismuth catalyst, titanate ester catalyst, organotin catalysts and amine catalysis
One or more in agent；It is further preferred that the organic bismuth catalyst is selected from bismuth neodecanoate, laurate bismuth, isooctyl acid bismuth
With the one or more in bismuth naphthenate；The titanate catalyst is selected from positive isopropyl titanate, positive butyl titanate, four fourth of metatitanic acid
Ester, poly(tributoxy titanium), four different monooctyl ester of metatitanic acid, purity titanium tetraethoxide, four (2-Ethylhexyl Alcohol) titaniums, n-propyl titanate, the oil of propyl group two
Sour acyloxy (dioctyl phosphoric acid acyloxy) titanate esters, isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters, the oil of isopropyl three
Sour acyloxy titanate esters, isopropyl three (dodecyl benzene sulfonic acid) titanate esters, isopropyl three (dioctylphyrophosphoric acid acyloxy) titanium
Acid esters, (dioctylphyrophosphoric acid acyloxy) the ethylene titanate esters of isopropyl three and tetra isopropyl two (dioctyl phosphito acyloxy) titanium
One or more in acid esters；The amine catalyst is selected from N, N- dimethyl cyclohexyl amines, double (2- dimethylaminoethyls) ethers, N, N,
One or more in N', N'- tetramethyl Alkylenediamine, triethylamine and N, N- dimethyl benzylamine；Described is organotin catalyzed
Agent is selected from dibutyltin dilaurate, stannous octoate, two (dodecyl sulphur) dibutyl tins and dibutyltin diacetate
It is one or more kinds of.
In addition, the answering as the pretreating agent of polyurethane sealant the present invention also provides lacquer painting silane coupling agent described above
With.
Compared with prior art, lacquer painting silane coupling agent provided by the invention is mainly by isocyanate-terminated polymer, more isocyanides
The components such as acid esters, mill base, latent curing agent and catalyst form.In the present invention, each component collective effect under certain proportioning, makes
Obtain the silane coupling agent to be not only able to improve adhesive effect of the polyurethane glass glue on 2k lacquer paintings, moreover it is possible to ensure that polyurethane glass glue exists
Adhesive effect on 1k lacquer paintings.The silane coupling agent provided using the application, can not only improve vehicle body lacquer painting and polyurethane adhesive it
Between caking property, additionally it is possible to shorten the construction time, improve construction efficiency.Experiment shows, lacquer painting silane coupling agent provided by the invention without
More than 90% is attained by by the cohesional failure on 1k lacquer paintings or 2k lacquer paintings, so that the adhesive strength of glass and vehicle body is improved,
Ensure vehicle safety.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is attached drawing needed in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
The embodiment of invention, for those of ordinary skill in the art, without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the adhesive effect figure of the embodiment of the present application 1,1~2 lacquer painting primary coat of comparative example on BASF white 2k lacquer paintings；
Fig. 2 is the adhesive effect figure of the embodiment of the present application 1,1~2 lacquer painting primary coat of comparative example on PPG red 1k lacquer paintings.
Embodiment
The technical solution in the embodiment of the present invention is clearly and completely described below, it is clear that described embodiment
Only part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this area
Art personnel all other embodiments obtained without making creative work, belong to the model that the present invention protects
Enclose.
The present invention provides a kind of lacquer painting silane coupling agent, in terms of parts by weight, including following components：5~20 parts of isocyanic acid
Ester terminated polymer；5~15 parts of polyisocyanates；10~30 parts of mill base；0.5~3 part of latent curing agent；50~125 parts
Solvent；0.1~1 part of catalyst；The isocyanate-terminated polymer is made by isocyanates and polyol reaction；It is described
Polyisocyanates is selected from polymethylene multi-phenenyl isocyanate, polymethylene diisocyanate oligomer, three-functionality-degree isocyanic acid
One or more in ester and tetra functional isocyanates.
Silane coupling agent provided by the invention can not only improve adhesive effect of the polyurethane glass glue on 2K lacquer paintings, additionally it is possible to protect
Demonstrate,prove adhesive effect of the polyurethane glass glue on 1k lacquer paintings.
In terms of parts by weight, lacquer painting silane coupling agent provided by the invention includes 5~20 parts of isocyanate-terminated polymer, excellent
Elect 7~20 parts as.The isocyanate-terminated polymer is isocyanates and polyol reaction, isocyanate-terminated obtained poly-
Compound, it primarily serves filming function.The isocyanate group of the isocyanate-terminated polymer and polyol hydroxyls group
The ratio between amount of material, is denoted as the R values of isocyanate-terminated polymer, is preferably selected from 2.0~3.0.
In the present invention, the isocyanate-terminated polymer is preferably prepared in accordance with the following methods：By isocyanates and more
First alcohol mixing, reacts 2h~5h under conditions of being 60~80 DEG C in temperature, obtains isocyanate-terminated polymer.The isocyanic acid
Isocyanates in ester terminated polymer is usually diisocyanate, is preferably selected from toluene di-isocyanate(TDI), diphenyl methane two
One kind in isocyanates, hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate and isophorone diisocyanate
Or it is a variety of, it is more preferably methyl diphenylene diisocyanate, toluene di-isocyanate(TDI), 1, hexamethylene-diisocyanate or isophorone
Diisocyanate (IPDI).The one kind of the polyalcohol in polyether polyol, modified polyether polylol and polyester polyol
Or it is a variety of, it is preferably polypropylene oxide trihydroxylic alcohol, polyester diol or polyether Glycols；Average molecular weight can be 2000~
4800g/mol。
In an embodiment of the present invention, isocyanate-terminated polymer is prepared in protective gas, such as nitrogen (N2) existing
Under the conditions of carry out.Polyalcohol is preferably dehydrated by the present invention, such as 90 DEG C of stirrings, vacuum dehydration 3h；Then 60~80 are cooled to
DEG C, isocyanates is added, in N2Stirring reaction 2h~5h, that is, obtain isocyanate-terminated polymer under atmosphere.
The embodiment of the present invention by the isocyanate-terminated polymer and solvent, mill base, polyisocyanates, latent curing agent and
Catalyst mixes, and lacquer painting silane coupling agent is prepared.The raw materials such as the solvent, mill base and polyisocyanates use commercial product；
The present invention is also not particularly limited the preparation method, can stirring at normal temperature disperse, be eventually adding catalyst and continue stirring at normal temperature point
Dissipate.
In lacquer painting silane coupling agent of the present invention, the parts by weight of the polyisocyanates are 5~15 parts.More isocyanides
Typically contain two or more active sites in acid ester molecules to be reacted, the present invention is different selected from polymethylene polyphenyl
Cyanate, polymethylene diisocyanate oligomer, three-functionality-degree isocyanates and one kind in tetra functional isocyanates or
It is a variety of, it is different for example with tri o cresyl thiophosphate phenyl isocyanate, dimethyl triphenyl methane tetraisocyanate or hexa-methylene two
Cyanate tripolymer (HDI trimer) etc..
Lacquer painting silane coupling agent of the present invention includes the mill base of 10~30 parts by weight, is preferably 15~30 parts；The mill base one
As include pigment and organic solvent.In the present invention, the mill base can be oiliness, be preferably selected from oiliness black color paste.The present invention
The oiliness black color paste of some embodiments includes the components such as carbon black and water；Preferably, charcoal black substance in the oiliness black color paste
Measure content and be more than 10% and less than or equal to 30%, the mass content of water is less than 0.4%.
In the present invention, the lacquer painting silane coupling agent includes 0.5~3 part of latent curing agent.Described latent (property) curing agent is one
Kind of curing agent, at room temperature can stored longer, heating can play curing reaction；Latent curing agent of the present invention is preferably selected from ketone
One or more in imines He oxazolidine.The lacquer painting silane coupling agent includes 50~125 parts of solvent, preferably includes 90~125
The solvent of part.The solvent is preferably selected from the one or more in ethyl acetate, methyl acetate, acetone and butanone, more preferably
Ethyl acetate or butanone.
In the present invention, the lacquer painting silane coupling agent includes 0.1~1 part of catalyst.The catalyst is preferably selected from organic
One or more in bismuth catalyst, titanate catalyst, organotin catalysts and amine catalyst, more preferably wherein two classes are catalyzed
Agent is used with any quality than mixture.Wherein：
The organic bismuth catalyst may be selected from bismuth neodecanoate, laurate bismuth, isooctyl acid bismuth and one kind in bismuth naphthenate or
It is a variety of, it is preferably bismuth neodecanoate, laurate bismuth or isooctyl acid bismuth；
The titanate catalyst may be selected from positive isopropyl titanate, positive butyl titanate, butyl titanate and its mixture, gather
Butyl titanate, four different monooctyl ester of metatitanic acid, purity titanium tetraethoxide, four (2-Ethylhexyl Alcohol) titaniums, n-propyl titanate, two oleic acid acyl-oxygen of propyl group
Base (dioctyl phosphoric acid acyloxy) titanate esters, isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters, three oleic acid acyl-oxygen of isopropyl
It is base titanate esters, isopropyl three (dodecyl benzene sulfonic acid) titanate esters, isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, different
In (dioctylphyrophosphoric acid acyloxy) the ethylene titanate esters of propyl group three and tetra isopropyl two (dioctyl phosphito acyloxy) titanate esters
One or more, be preferably isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters；
The amine catalyst may be selected from N, N- dimethyl cyclohexyl amines, double (2- dimethylaminoethyls) ethers,
One or more in N, N, N', N'- tetramethyl Alkylenediamine, triethylamine and N, N- dimethyl benzylamine, preferably
For triethylamine, N, N- dimethyl cyclohexyl amines, N, N- dimethyl benzylamines, N, N, N', N'- tetramethyl Alkylenediamines；
The organotin catalysts may be selected from dibutyltin dilaurate, stannous octoate, two (dodecyl sulphur) two fourths
One or more in Ji Xi and dibutyltin diacetate, are preferably stannous octoate, dibutyltin dilaurate or two vinegar
Sour dibutyl tin.
In some embodiments of the invention, the catalyst is bismuth neodecanoate and double (2- dimethylaminoethyls) ethers.
In some embodiments of the present invention, the catalyst is dibutyltin dilaurate and N, N- dimethyl cyclohexyl amine.In this hair
In other bright embodiments, the catalyst is (the dioctyl phosphoric acid acyloxy) titanate esters of isopropyl three and N, N- dimethylbenzyl
Amine.
The embodiment of the present invention is mixed with to obtain above-mentioned lacquer painting silane coupling agent according to a certain ratio；The surface drying of the lacquer painting silane coupling agent
Time ＜ 10min, viscosity ＜ 15mPa.s, density~0.98g/mL.The silane coupling agent with mono-component polyurethane bonding agent is supporting makes
With being used for polyurethane glass glue vehicle body lacquer painting bonding and whens other elastic adhesives, polyurethane glass glue and vehicle body can be improved
Adhesive strength.
In addition, the answering as the pretreating agent of polyurethane sealant present invention also offers lacquer painting silane coupling agent described above
With.Specifically include：Above-mentioned lacquer painting silane coupling agent is brushed on lacquer painting base material, after dry tack free, it is close to break polyurethane in its surface
Sealing.Wherein, the lacquer painting can be conventional 1k lacquer painting or 2k lacquer paintings (alternatively referred to as painting plate)；The dosage of the silane coupling agent is 10
~20g/m2。
In embodiments of the present invention, the bond effect of silane coupling agent is tested using the above method：In primary coat (agent) table
After polyurethane sealant 48h is beaten in face, the bond effect of method test polyurethane sealant and glass surface is cut with knife.Experiment shows,
No matter the cohesional failure on 1k lacquer paintings or 2k lacquer paintings is attained by more than 90% even to lacquer painting silane coupling agent provided by the invention
100%, beneficial to its application on the pretreating agent as polyurethane sealant.
For a further understanding of the application, the lacquer painting silane coupling agent provided with reference to embodiment the application and its application into
The specific description of row.
In following embodiments and comparative example, 2k paint plates derive from BASF AG, are 2k pearl white paint plates, and 1k paint plates derive from
PPG companies, be red paint plate.The polyurethane sealant of primed surface is purchased from Zhijiang Organosilicon Chemical Co., Ltd., Hangzhou, is JS-
311 polyurethane glass fluid sealants, for oiliness black color paste, (wherein carbon black mass content is more than 10% and is less than or equal to mill base
30%, 0.4%) mass content of water is less than.
Embodiment 1
120g polypropylene oxide trihydroxylic alcohols (average molecular weight 4800g/mol) are added to mechanical agitation, vacuum, nitrogen
In the reactor of gas shielded and heating unit, 90 DEG C of stirrings, vacuum dehydration 3h；Then 70 DEG C are cooled to, adds 23.44g bis-
Methylenebis phenyl isocyanate, N22h is reacted under atmosphere, that is, obtains isocyanate-terminated polymer, it is described isocyanate-terminated poly-
The R values of compound are 2.5；
In N2Under atmosphere, progressively by the above-mentioned isocyanate-terminated polymer of 10g, 125g ethyl acetate, 25g mill bases, 1.5g
Oxazolidine latent curing agent (Britain's incorez limited companies IncozolEH oxazolidines latent curing agent) and 15g tri o cresyl thiophosphates
Phenyl isocyanate mixes, and stirring at normal temperature disperses 30min；Add 0.1g bismuth neodecanoates and 0.2g is double (2- dimethylaminoethyls)
Ether, continues stirring at normal temperature and disperses 30min, that is, obtain lacquer painting silane coupling agent, surface drying time~1.5min of the lacquer painting primary coat, and viscosity~
7.0mPa.s, density are about 0.98g/mL.
Adhesive effect test method as described above, the present invention carry out cementability to silane coupling agent prepared by embodiment 1
Test, the dosage of silane coupling agent is 15g/m2, test data the results are shown in Table 1；Adhesive effect such as Fig. 1 on BASF white 2k lacquer paintings
Shown, the adhesive effect on PPG red 1k lacquer paintings is as shown in Figure 2.
Table 1 is the performance test results of the silane coupling agent of the embodiment of the present invention 1~5 and the preparation of comparative example 1~5, can by table 1
Know, no matter the cohesional failure on 1k lacquer paintings or 2k lacquer paintings is attained by more than 90% even to lacquer painting silane coupling agent provided by the invention
100%.From Fig. 1 and Fig. 2 as it can be seen that using lacquer painting silane coupling agent of the present invention, bonding of the polyurethane glass glue on 1k, 2k lacquer painting
Effect is preferable.
The performance test results of silane coupling agent prepared by 1 embodiment of the present invention 1~5 of table and comparative example 1~5
Comparative example 1
120g polypropylene oxide trihydroxylic alcohols (average molecular weight 4800g/mol) are added to mechanical agitation, vacuum, nitrogen
In the reactor of gas shielded and heating unit, 90 DEG C of stirrings, vacuum dehydration 3h；Then 70 DEG C are cooled to, adds 23.44g bis-
Methylenebis phenyl isocyanate, N22h is reacted under atmosphere, that is, obtains isocyanate-terminated polymer, it is described isocyanate-terminated poly-
The R values of compound are 2.5；
In N2Under atmosphere, progressively by the above-mentioned isocyanate-terminated polymer of 10g, 137g ethyl acetate, 25g mill bases, 1.5g
Oxazolidine latent curing agent (Britain's incorez limited companies IncozolEH oxazolidines latent curing agent) and 10g tri o cresyl thiophosphates
Phenyl isocyanate mixes, and stirring at normal temperature disperses 30min；Then 3g N- (normal-butyl)-γ-aminopropyl trimethoxy silicon is added
Alkane and 3g pairs-(γ-trimethoxy silicon propyl group) amine, stirring at normal temperature 20min；Add 0.1g bismuth neodecanoates and the double (2- bis- of 0.2g
Methylaminoethyl) ether, continue stirring at normal temperature and disperse 30min, that is, obtain lacquer painting silane coupling agent, the surface drying time of the lacquer painting primary coat~
1.5min, viscosity~9.0mPa.s, density are about 1.0g/mL.
Adhesive effect test method as described above, the present invention carry out cementability to silane coupling agent prepared by comparative example 1
Test, test data the results are shown in Table 1；Adhesive effect on BASF white 2k lacquer paintings is as shown in Figure 1, in PPG red 1k lacquer paintings
On adhesive effect it is as shown in Figure 2.
Comparative example 2
130g polypropylene oxide trihydroxylic alcohols (average molecular weight 500g/mol) are added to mechanical agitation, vacuum, nitrogen
In the reactor of gas shielded and heating unit, 90 DEG C of stirrings, vacuum dehydration 3h；Then 70 DEG C are cooled to, adds 234.4g bis-
Methylenebis phenyl isocyanate, N22h is reacted under atmosphere, adds 400g ethyl acetate, that is, obtains isocyanate-terminated polymerization
Thing, the R values of the isocyanate-terminated polymer are 2.4；
In N2It is under atmosphere, 5g isophorone diisocyanate (IPDI) and 5g 3-mercaptopropyi trimethoxy silanes is normal
Temperature is uniformly mixed, and is to slowly warm up to 80 DEG C while stirring, reacts 2h, then cools to 65 DEG C, adds the catalysis of 0.01g stannous octoates
Agent, the reaction was continued 0.5 it is small when, obtain isophorone diisocyanate modification silane.
In N2Under atmosphere, progressively the above-mentioned isocyanate-terminated polymer of 84g, the above-mentioned isophorone diisocyanates of 10g are changed
Property silane, 56g ethyl acetate, 25g mill bases and 1g γ-glycidyl ether oxygen propyl trimethoxy silicane mixing, stirring at normal temperature
Scattered 30min；Double (2- dimethylaminoethyls) ethers of 0.2g are added, continues stirring at normal temperature and disperses 30min, should up to silane coupling agent is arrived
Surface drying time~6min of lacquer painting primary coat, viscosity~11.6mPa.s, density are about 0.98g/mL.
Adhesive effect test method as described above, the present invention carry out cementability to silane coupling agent prepared by comparative example 2
Test, test data the results are shown in Table 1；Adhesive effect on BASF white 2k lacquer paintings is as shown in Figure 1, in PPG red 1k lacquer paintings
On adhesive effect it is as shown in Figure 2.
Comparative example 3
130g polyester diols (average molecular weight 600g/mol) are added to mechanical agitation, vacuum, nitrogen protection
And in the reactor of heating unit, 90 DEG C of stirrings, vacuum dehydration 3h；Then 70 DEG C are cooled to, adds 140g diphenyl methanes
Diisocyanate, N22h is reacted under atmosphere, adds 270g ethyl acetate；Isocyanate-terminated polymer is obtained, it is described different
The R values of cyanate terminated polymer are 2.6；
In N2Under atmosphere, 70g hexamethylene diisocyanates are mixed with 30g mercaptopropyi trimethoxy silane room temperature
It is even, 80 DEG C are to slowly warm up to while stirring, reacts 2h, then cools to 65 DEG C, add 0.1g Triethylamine catalysts, the reaction was continued
0.5 it is small when, obtain silane-modified isocyanates.
In N2Under atmosphere, progressively by the above-mentioned isocyanate-terminated polymer of 60g, the above-mentioned silane-modified isocyanates of 20g,
56g ethyl acetate and the mixing of 25g mill bases, stirring at normal temperature disperse 30min；0.2g stannous octoate catalysts are added, continues room temperature and stirs
Scattered 30min is mixed, up to silane coupling agent is arrived, surface drying time~5min of the lacquer painting primary coat, viscosity~8.8mPa.s, density is about
0.98g/mL。
Adhesive effect test method as described above, the present invention carry out cementability to silane coupling agent prepared by comparative example 3
Test, test result are shown in Table 1.
Embodiment 2
120g polyester diols (average molecular weight 2000g/mol) are added to mechanical agitation, vacuum, nitrogen protection
And in the reactor of heating unit, 90 DEG C of stirrings, vacuum dehydration 2h；Then 70 DEG C are cooled to, adds 50g diphenyl methanes two
Isocyanates, N22h is reacted under atmosphere, that is, obtains isocyanate-terminated polymer, the R values of the isocyanate-terminated polymer
For 3.0；
In N2Under atmosphere, progressively by the above-mentioned isocyanate-terminated polymer of 20g, 95g butanone, 25g mill bases, 0.5g hexichol first
Base ketimide latent curing agent and the mixing of 12g hexamethylene diisocyanate trimers, stirring at normal temperature disperse 30min；Add
0.1g dibutyltin dilaurates and 0.2g N, N- dimethyl cyclohexyl amines, continue stirring at normal temperature and disperse 30min, that is, painted
Face silane coupling agent, surface drying time~3min of the lacquer painting primary coat, viscosity~8.3mPa.s, density is about 0.98g/mL.
Adhesive effect test method as described above, the present invention carry out cementability to silane coupling agent prepared by embodiment 2
Test, test result are shown in Table 1.
Comparative example 4
120g polyester diols (average molecular weight 2000g/mol) are added to mechanical agitation, vacuum, nitrogen protection
And in the reactor of heating unit, 90 DEG C of stirrings, vacuum dehydration 4h；Then 70 DEG C are cooled to, adds 20g diphenyl methanes two
Isocyanates, N22h is reacted under atmosphere, that is, obtains isocyanate-terminated polymer, the R values of the isocyanate-terminated polymer
For 1.2；
In N2Under atmosphere, progressively by the above-mentioned isocyanate-terminated polymer of 20g, 75g acetone, 30g mill bases, 1.0g oxazolidines
Latent curing agent (incorez limited companies of Britain Incozol BH oxazolidines latent curing agent) and 15g toluene di-isocyanate(TDI)s
Mixing, stirring at normal temperature disperse 30min；0.1g dibutyltin dilaurates and 0.2g isooctyl acid bismuths are added, continues stirring at normal temperature
Scattered 30min, up to silane coupling agent is arrived, surface drying time~4.5min of the lacquer painting primary coat, viscosity~13.2mPa.s, density is about
0.98g/mL。
Adhesive effect test method as described above, the present invention carry out cementability to silane coupling agent prepared by comparative example 4
Test, test result are shown in Table 1.
Embodiment 3
120g polyether Glycols (average molecular weight 2000g/mol) are added to mechanical agitation, vacuum, nitrogen protection
And in the reactor of heating unit, 100 DEG C of stirrings, vacuum dehydration 1h；Then 70 DEG C are cooled to, adds 30g toluene diisocyanates
Acid esters, N22h is reacted under atmosphere, that is, obtains isocyanate-terminated polymer, the R values of the isocyanate-terminated polymer are
2.65；
In N2Under atmosphere, progressively by the above-mentioned isocyanate-terminated polymer of 15g, 92g ethyl acetate, 25g mill bases, 2.0g Evil
Oxazolidine latent curing agent (incorez limited companies of Britain Incozol BH oxazolidines latent curing agent) and 14g dimethyl triphens
Methylmethane tetraisocyanate mixes, and stirring at normal temperature disperses 30min；Add three (dioctyl phosphoric acid acyloxy) metatitanic acid of 0.5g isopropyls
Ester and 0.3g N, N- dimethyl benzylamines, continue stirring at normal temperature and disperse 30min, that is, obtain lacquer painting silane coupling agent, the table of the lacquer painting primary coat
Dry time~3.5min, viscosity~6.8mPa.s, density is about 0.98g/mL.
Adhesive effect test method as described above, the present invention carry out cementability to silane coupling agent prepared by embodiment 3
Test, test result are shown in Table 1.
Comparative example 5
120g polyether Glycols (average molecular weight 2000g/mol) are added to mechanical agitation, vacuum, nitrogen protection
And in the reactor of heating unit, 90 DEG C of stirrings, vacuum dehydration 3h；Then 70 DEG C are cooled to, adds 30g toluene diisocynates
Ester, N22h is reacted under atmosphere, the stirring of 150g methyl acetates is added, that is, obtains isocyanate-terminated polymer, the isocyanates
The R values of terminated polymer are 2.65；
In N2Under atmosphere, progressively by the above-mentioned isocyanate-terminated polymer of 30g, 70g ethyl acetate, 25g mill bases, 2.0g Evil
Oxazolidine latent curing agent (incorez limited companies of Britain Incozol EH oxazolidines latent curing agent) and 2g dimethyl triphenyls
Methane tetraisocyanate mixes, and stirring at normal temperature disperses 30min；Add three (dioctyl phosphoric acid acyloxy) titanate esters of 0.5g isopropyls
With 0.3g N, N- dimethyl benzylamines, continue stirring at normal temperature and disperse 30min, that is, obtain lacquer painting silane coupling agent, the surface drying of the lacquer painting primary coat
Time~2.0min, viscosity~11.5mPa.s, density are about 0.98g/mL.
Adhesive effect test method as described above, the present invention carry out cementability to silane coupling agent prepared by comparative example 5
Test, test result are shown in Table 1.
Embodiment 4
120g polyester diols (average molecular weight 2000g/mol) are added to mechanical agitation, vacuum, nitrogen protection
And in the reactor of heating unit, 90 DEG C of stirrings, vacuum dehydration 3h；Then it is cooled to 70 DEG C, adds 22g 1, oneself is two different by 6-
Cyanate, N25h is reacted under atmosphere, that is, obtains isocyanate-terminated polymer, the R values of the isocyanate-terminated polymer are
2.0；
In N2Under atmosphere, progressively by the above-mentioned isocyanate-terminated polymer of 15g, 90g butanone, 20g mill bases, 1.0g hexichol first
Base ketimide latent curing agent and the mixing of 8g dimethyl triphenyl methanes tetraisocyanate, stirring at normal temperature disperse 30min；Add 0.5g
Laurate bismuth and 0.1g N, N, N', N'- tetramethyl Alkylenediamines, continue stirring at normal temperature and disperse 30min, that is, obtain lacquer painting bottom
Paint, surface drying time~1.5min of the lacquer painting primary coat, viscosity~5.8mPa.s, density is about 0.98g/mL.
Adhesive effect test method as described above, the present invention carry out cementability to silane coupling agent prepared by embodiment 4
Test, test result are shown in Table 1.
Embodiment 5
120g polyether Glycols (average molecular weight 2000g/mol) are added to mechanical agitation, vacuum, nitrogen protection
And in the reactor of heating unit, 90 DEG C of stirrings, vacuum dehydration 3h；Then 70 DEG C are cooled to, it is different to add 32g isophorones two
Cyanate, N24h is reacted under atmosphere, that is, obtains isocyanate-terminated polymer, the R values of the isocyanate-terminated polymer are
2.2；
In N2Under atmosphere, progressively by the above-mentioned isocyanate-terminated polymer of 7g, 90g ethyl acetate, 30g mill bases, 2.0g bis-
Benzyl ketimide latent curing agent, 6g hexamethylene diisocyanate trimers and 7g tri o cresyl thiophosphate phenyl isocyanates are mixed
Close, stirring at normal temperature disperses 30min；0.5g dibutyltin diacetates and 0.3g N, N- dimethyl benzylamines are added, continues stirring at normal temperature
Scattered 30min, that is, obtain lacquer painting silane coupling agent, surface drying time~3.5min of the lacquer painting primary coat, viscosity~5.0mPa.s, density is about
For 0.98g/mL.
Adhesive effect test method as described above, the present invention carry out cementability to silane coupling agent prepared by embodiment 5
Test, test result are shown in Table 1.
As seen from the above embodiment, lacquer painting silane coupling agent provided by the invention is mainly by isocyanate-terminated polymer, polyisocyanate
The components such as cyanate, mill base, latent curing agent and catalyst form.In the present invention, which is not only able to improve polyurethane
Adhesive effect of the glass cement on 2k lacquer paintings, moreover it is possible to ensure adhesive effect of the polyurethane glass glue on 1k lacquer paintings.Experiment shows,
No matter the cohesional failure on 1k lacquer paintings or 2k lacquer paintings is attained by more than 90% to lacquer painting silane coupling agent provided by the invention, so as to carry
The adhesive strength of high glass and vehicle body, ensures vehicle safety.
The above is only the preferred embodiment of the present invention, it is noted that the professional technique for making the art
Personnel, without departing from the technical principles of the invention, are that by a variety of modifications to these embodiments, and these
Modification also should be regarded as the scope that the present invention should protect.
Claims (10)
1. a kind of lacquer painting silane coupling agent, in terms of parts by weight, including following components：
5~20 parts of isocyanate-terminated polymer；
5~15 parts of polyisocyanates；
10~30 parts of mill base；
0.5~3 part of latent curing agent；
50~125 parts of solvent；
0.1~1 part of catalyst；
The isocyanate-terminated polymer is made by isocyanates and polyol reaction；
The polyisocyanates is selected from polymethylene multi-phenenyl isocyanate, polymethylene diisocyanate oligomer, trifunctional
Spend the one or more in isocyanates and tetra functional isocyanates.
2. lacquer painting silane coupling agent according to claim 1, it is characterised in that the isocyanic acid of the isocyanate-terminated polymer
The amount ratio of group and the material of polyol hydroxyls group is 2.0~3.0.
3. lacquer painting silane coupling agent according to claim 1, it is characterised in that the isocyanate-terminated polymer is according to following
It is prepared by method：Isocyanates and polyalcohol are reacted into 2~5h at 60~80 DEG C, obtain isocyanate-terminated polymer.
4. according to claims 1 to 3 any one of them lacquer painting silane coupling agent, it is characterised in that the isocyanates is selected from toluene
Diisocyanate, methyl diphenylene diisocyanate, hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate and different Buddhist
One or more in your ketone diisocyanate.
5. according to claims 1 to 3 any one of them lacquer painting silane coupling agent, it is characterised in that it is more that the polyalcohol is selected from polyethers
One or more in first alcohol and polyester polyol.
6. according to claims 1 to 3 any one of them lacquer painting silane coupling agent, it is characterised in that it is sub- that the latent curing agent is selected from ketone
One or more in An He oxazolidine.
7. according to claims 1 to 3 any one of them lacquer painting silane coupling agent, it is characterised in that the mill base is oiliness black color
Slurry.
8. according to claims 1 to 3 any one of them lacquer painting silane coupling agent, it is characterised in that the solvent be selected from ethyl acetate,
One or more in methyl acetate, acetone and butanone.
9. according to claims 1 to 3 any one of them lacquer painting silane coupling agent, it is characterised in that the catalyst is selected from organo-bismuth
One or more in catalyst, titanate ester catalyst, organotin catalysts and amine catalyst；
One or more of the organic bismuth catalyst in bismuth neodecanoate, laurate bismuth, isooctyl acid bismuth and bismuth naphthenate；
The titanate ester catalyst is selected from positive isopropyl titanate, positive butyl titanate, butyl titanate, poly(tributoxy titanium), titanium
Sour four different monooctyl esters, purity titanium tetraethoxide, four (2-Ethylhexyl Alcohol) titaniums, n-propyl titanate, two oleic acid acyloxy (dioctyl phosphorus of propyl group
Sour acyloxy) it is titanate esters, isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters, three oleic acid acyloxy titanate esters of isopropyl, different
Propyl group three (dodecyl benzene sulfonic acid) titanate esters, isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, (two is pungent for isopropyl three
Base pyrophosphoric acid acyloxy) one kind or more in ethylene titanate esters and tetra isopropyl two (dioctyl phosphito acyloxy) titanate esters
Kind；
The organotin catalysts are selected from dibutyltin dilaurate, stannous octoate, two (dodecyl sulphur) dibutyl tins
With the one or more in dibutyltin diacetate；
The amine catalyst is selected from N, N- dimethyl cyclohexyl amines, double (2- dimethylaminoethyls) ethers, N, N, N', N'- tetramethyls Asia
One or more in alkyl diamine, triethylamine and N, N- dimethyl benzylamine.
10. lacquer painting silane coupling agent as claimed in any one of claims 1 to 9 wherein should as the pretreating agent of polyurethane sealant
With.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112375484A (en) * | 2020-11-13 | 2021-02-19 | 杭州之江新材料有限公司 | Long-acting prime coat on glass surface, preparation method and application thereof, glass sealant and glass product |
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| CN106634534A (en) * | 2016-12-27 | 2017-05-10 | 苏州中材非金属矿工业设计研究院有限公司 | Anti-sagging single-ingredient polyurethane waterproof paint and preparation method thereof |
| CN106675373A (en) * | 2016-12-26 | 2017-05-17 | 徐州卧牛山新型防水材料有限公司 | Non-cured polyurethane waterproof paint and preparation method thereof |
| CN107418419A (en) * | 2017-06-13 | 2017-12-01 | 杭州之江新材料有限公司 | A kind of quick-dry type silane coupling agent, its preparation method and its application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106675373A (en) * | 2016-12-26 | 2017-05-17 | 徐州卧牛山新型防水材料有限公司 | Non-cured polyurethane waterproof paint and preparation method thereof |
| CN106634534A (en) * | 2016-12-27 | 2017-05-10 | 苏州中材非金属矿工业设计研究院有限公司 | Anti-sagging single-ingredient polyurethane waterproof paint and preparation method thereof |
| CN107418419A (en) * | 2017-06-13 | 2017-12-01 | 杭州之江新材料有限公司 | A kind of quick-dry type silane coupling agent, its preparation method and its application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112375484A (en) * | 2020-11-13 | 2021-02-19 | 杭州之江新材料有限公司 | Long-acting prime coat on glass surface, preparation method and application thereof, glass sealant and glass product |
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