CN107556941B - A kind of bonding agent and application and composite article and its preparation method and application - Google Patents
A kind of bonding agent and application and composite article and its preparation method and application Download PDFInfo
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- CN107556941B CN107556941B CN201610503140.XA CN201610503140A CN107556941B CN 107556941 B CN107556941 B CN 107556941B CN 201610503140 A CN201610503140 A CN 201610503140A CN 107556941 B CN107556941 B CN 107556941B
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Abstract
The present invention relates to binder field, a kind of bonding agent and application and composite article and its preparation method and application are disclosed.The bonding agent contains double triazine thiol compounds with structure shown in formula (1): R C1‑C16Linear chain or branched chain alkylidene, C6‑C16At least one of segment containing arlydene.Organic film is formed using the binder of double triazine thiol compounds containing structure shown in formula (1) between metal layer and plastic layer, contain the thiol functionalities of more conjugation in double triazine thiol compounds containing structure shown in formula (1), fine and close organic film can be bound to each other to form, extra thiol functionalities can between metal, plastics by chemical bond mode in conjunction with, to achieve the effect that bonding.
Description
Technical field
The present invention relates to electronics fields, and in particular, to a kind of bonding agent, the bonding agent are as metal and modeling
The application on binder, a kind of composite article, a kind of preparation method of composite article between material are prepared by this method
The application of composite article and the composite article as electronic product casing.
Background technique
Currently, the quadric injection mould technology of metal and plastics has become mainstream in IT industry.Wherein, metal and plastics it
Between adhesive property become the core of technology.Currently, applicant uses self-developed PMH (Polymer Metal Hybrid)
Technology carries out the bonding between metal and plastics, and batch has used well.PMH technology is a kind of emerging molding skill
Art, metallic stamping pieces are put into injection mold by it, and injection moldable polymers on the surface thereof, by certain bonding mechanism and at
Type technique is by plastics and metallic combination at single structural member.With the increasingly application of the technology, to plastics and metal
Between bonding interface intensity requirement it is higher and higher.
The method for now improving adhesion strength is to form nanoscale micropore, molding in metal surface by microcosmic method of roughening
When plastics fill up nano-pore, insertion forms rivet effect, to improve the adhesion strength between plastics and metal, realize metal with
The combination of plastics.However, above method is physical methods, opposite and chemical bonds still deposit certain caking property and closed
The difference of property.
Summary of the invention
The object of the present invention is to provide a kind of new bonding agent, the bonding agents as the bonding between metal and plastics
Application, a kind of composite article, a kind of preparation method of composite article in agent, the composite article being prepared by this method and
Application of the composite article as electronic product casing.
Specifically, the present invention provides a kind of bonding agents, wherein the bonding agent contains with structure shown in formula (1)
Double triazine thiol compounds:
R is C1-C16Linear chain or branched chain alkylidene, C6-C16At least one of segment containing arlydene.
The present invention also provides the bonding agents as the application on the binder between metal and plastics.
The present invention also provides a kind of composite articles, wherein the composite article includes the metal layer stacked gradually, organic film
Layer and plastic layer, the organic film are formed by above-mentioned bonding agent.
The present invention also provides a kind of preparation method of composite article, this method includes the shape on a side surface of metal layer
At organic film, then injection-moulded plastic is on the organic film to form plastic layer, and the organic film is by above-mentioned bonding agent
It is formed.
The present invention also provides composite articles prepared by the above method.
In addition, the application the present invention also provides the composite article as electronic product casing.
The present inventor uses between metal layer and plastic layer by finding after further investigation and contains formula (1) institute
Show that the bonding agent of double triazine thiol compounds of structure forms organic film, double triazine thiols containing structure shown in formula (1)
It closes and contains more conjugation thiol functionalities in object, fine and close organic film, extra thiol functionalities can be bound to each other to form
Can between metal, plastics by chemical bond mode in conjunction with, to achieve the effect that bonding.In addition, knot provided by the invention
Mixture also has good anticorrosive property, waterproofness and airtightness.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
Bonding agent provided by the invention contains double triazine thiol compounds with structure shown in formula (1):
R is C1-C16Linear chain or branched chain alkylidene, C6-C16At least one of segment containing arlydene, preferably C1-
C10Linear chain or branched chain alkylidene, more preferably C1-C6Linear chain or branched chain alkylidene.
A preferred embodiment of the invention, double triazine thiol compounds are prepared into accordance with the following methods
It arrives:
It (1) is NH by Cyanuric Chloride and general formula2-R-NH2Diamino compound carried out at 0-15 DEG C first reaction；
(2) the first reaction product is successively reacted and is being returned in 0-10 DEG C of progress second later with vulcanized sodium and mixed in hydrochloric acid
Third reaction is carried out under the conditions of stream.
Specific reaction process is as follows:
The present invention does not limit the reaction time in each stage in the preparation process of double triazine thiol compounds particularly
It is fixed.The time of first reaction is preferably 1-5 hours, more preferably 2-4 hours.The time of second reaction is preferably 1-
3 hours, more preferably 1-2 hours.The time of the third reaction is preferably 2-6 hours, more preferably 3-5 hours.
The time of a preferred embodiment of the invention, first reaction is 1-5 hours, second reaction
Time be 1-3 hour, and the third reaction time be 2-6 hours.
According to another preferred method of implementation of the present invention, the time of first reaction is 2-4 hours, and described second is anti-
The time answered is 1-2 hours, and the time of third reaction is 3-5 hours.
The present invention is not particularly limited the dosage of each substance of preparation process of double triazine thiol compounds.It is described
The molar ratio of Cyanuric Chloride and diamino compound is preferably 1-5:1, more preferably 2-3:1.The vulcanized sodium and Cyanuric Chloride
Molar ratio be preferably 1-5:1, more preferably 2-4:1.The molar ratio of HCl and vulcanized sodium in the hydrochloric acid are preferably 0.5-2:
1, more preferably 0.8-1.5:1.
The molar ratio of a preferred embodiment of the invention, the Cyanuric Chloride and diamino compound is 1-5:
1, the molar ratio of the vulcanized sodium and Cyanuric Chloride is 1-5:1, and the molar ratio of the HCl and vulcanized sodium in the hydrochloric acid are 0.5-
2:1。
According to another preferred method of implementation of the present invention, the molar ratio of the Cyanuric Chloride and diamino compound is 2-
The molar ratio of 3:1, the vulcanized sodium and Cyanuric Chloride is 2-4:1, and the molar ratio of the HCl and vulcanized sodium in the hydrochloric acid are
0.8-1.5:1。
A kind of specific embodiment according to the present invention, double triazine thiol compounds are prepared into accordance with the following methods
It arrives:
(1) in dry round-bottomed flask, Cyanuric Chloride organic solvent is dissolved into (the matter of organic solvent and Cyanuric Chloride
Amount is than being 8-12:1, preferably 9-11:1), it is cooled to 0-5 DEG C later, is preferably cooled to 0-3 DEG C, obtains Cyanuric Chloride solution.
By diamino compound, (molar ratio of Cyanuric Chloride and diamino compound is 1-5:1, preferably 2-3:1, more preferably 2.2-
2.8:1) be slowly added into above-mentioned Cyanuric Chloride solution, then under low temperature (0-15 DEG C, preferably 5-13 DEG C) react 1-5h,
It is preferred that reaction 2-4h, forms intermediate, by-product is HCl；
(2) by vulcanized sodium (Na2The molar ratio of S and Cyanuric Chloride is 1-5:1, preferably 2-4:1, more preferably 2.2-3:
1) soluble in water, aqueous hydrochloric acid solution (HCl and Na in the aqueous hydrochloric acid solution are slowly added under stirring condition2The molar ratio of S is
0.5-2:1, preferably 0.8-1.5:1, more preferably 0.8-1.3:1), intermediate is then added, low temperature (0-10 DEG C, preferably
Be 0-8 DEG C) under react 1-3h, preferably react 1-2h, then temperature rising reflux reaction 2-6h, preferably react 3-5h.Final reaction produces
Object is repeatedly washed with water to pH value close to 7 or so, and rotary evaporation forms solid product.
According to the present invention, on the basis of the total weight of the bonding agent, with structure shown in formula (1) in the bonding agent
The content of double triazine thiol compounds is preferably 80 weight % or more, more preferably 90-100 weight %, most preferably 100 weights
Measure %.
The present invention also provides above-mentioned bonding agents as the application on the binder between metal and plastics.
Composite article provided by the invention includes the metal layer, organic film and plastic layer stacked gradually, the organic film
Layer is formed by above-mentioned bonding agent.
The metal layer is preferably at least one in magnesium layer, aluminium layer, layers of copper, aluminium alloy layer, magnesium alloy layer and stainless steel layer
Kind, more preferably aluminium alloy layer and/or magnesium alloy layer.Wherein, the aluminium alloy layer is the alloy shape of aluminium and copper, zinc, silicon and manganese
At layer, the magnesium alloy layer is the layer that the alloy of magnesium and aluminium, zinc, manganese, iron, copper and silicon is formed.
The present invention is not particularly limited the thickness of the organic film, for example, its average thickness can be 100-
8000nm, preferably 100-6000nm, more preferably 200-5000nm.In addition, the thickness of the metal layer and plastic layer can be with
For the conventional selection of this field, this those skilled in the art can be known, therefore not to repeat here.
The plastic layer is preferably polyphenylene sulfide (PPS) layer, polycarbonate (PC) layer, acrylonitrile-butadiene-styrene (ABS)
The layer that at least one of copolymer (ABS) layer, polyethylene terephthalate (PET) layer and polypropylene (PP) layer are formed,
The layer that at least one of preferably PPS layers, PC layers and abs layer are formed.
The preparation method of composite article provided by the invention includes being formed on the surface for needing casting resin of metal layer
Organic film, then injection-moulded plastic is on the organic film to form plastic layer, and the organic film is by above-mentioned combination dosage form
At.
The present invention is not particularly limited the method for forming the organic film, for example, can be spray coating method, three electrodes
Electrolysis method etc..Preferably, the method for the organic film is formed for three electrolysis methods, used by the three electrolysis method
Electrolyte is the aqueous solution of the bonding agent.At this point, in addition to double triazine thiol chemical combination of structure shown in formula (1) in the electrolyte
Except object, preferably also contain sodium nitrite, to provide electrolyte needed for electrolyte.Wherein, double triazines in the electrolyte
The content of mercaptan compound can be 0.5-10mmol/L, preferably 1-8mmol/L；The content of the sodium nitrite can be
0.005-0.5mol/L, preferably 0.1-0.4mol/L.
A kind of specific embodiment according to the present invention, with 50mm × 30mm × 0.3mm aluminium alloy plate (such as AA505) work
For working electrode, using saturated calomel electrode as reference electrode, using stainless steel plate (such as SUS304) as auxiliary electrode, by metal
Layer carries out electrochemical filming by cyclic voltammetry in the aqueous solution of above-mentioned bonding agent to form organic film, wherein voltage
Scanning range is 0.7-3.8V, sweep speed 5-15mV/s.
The present invention is not particularly limited the thickness of the organic film, for example, its average thickness can be 100-
8000nm, preferably 100-6000nm, more preferably 200-5000nm.In addition, the thickness of the metal layer and plastic layer can be with
For the conventional selection of this field, this those skilled in the art can be known, therefore not to repeat here.
The metal layer is preferably at least one in magnesium layer, aluminium layer, layers of copper, aluminium alloy layer, magnesium alloy layer and stainless steel layer
Kind, more preferably aluminium alloy layer and/or magnesium alloy layer.Wherein, the aluminium alloy layer is the alloy shape of aluminium and copper, zinc, silicon and manganese
At layer, the magnesium alloy layer is the layer that the alloy of magnesium and aluminium, zinc, manganese, iron, copper and silicon is formed.The plastic layer is preferably PPS
Layer, PC layer, abs layer, the formation of at least one of pet layer and PP layers layer, in preferably PPS layers, PC layers and abs layer at least
A kind of layer of formation.
The present invention also provides composite articles prepared by the above method.
Application the present invention also provides the composite article as electronic product casing.
The present invention does not limit the type of the electronic product, for example, can be mobile phone, notebook etc..
The present invention will be described in detail by way of examples below.
In following embodiment and comparative example, the thickness of organic film is carried out by coating film thickness tester (German PHRNIX)
Measurement.
Preparation example 1
The preparation example is used to illustrate the preparation of double triazine thiol compounds provided by the invention with structure shown in formula (1)
Method.
(1) in dry round-bottomed flask, by 55.35g (0.3mol) Cyanuric Chloride 498.15g acetone solution (acetone
Mass ratio with Cyanuric Chloride is 9:1), it is cooled to 0 DEG C, obtains Cyanuric Chloride solution.By 8.18g (0.136mol) ethylenediamine
(molar ratio of Cyanuric Chloride and ethylenediamine is 2.2:1) is slowly added into above-mentioned Cyanuric Chloride solution, reacts 4h at 5 DEG C,
Intermediate A 1 is formed, by-product is HCl.
(2) by the Na of 51.48g (0.66mol)2S(Na2The molar ratio of S and Cyanuric Chloride is 2.2:1) soluble in water, stirring
Under the conditions of be slowly added to aqueous hydrochloric acid solution 264ml (HCl and the Na of 2mol/L2The molar ratio of S is 0.8:1), it is then added intermediate
Body A1 reacts 2h, then temperature rising reflux 3h at 0 DEG C.Reaction product is repeatedly washed with water to pH value close to 7 or so, and rotation is steamed
Hair obtains double triazine thiol compounds, is denoted as B1.It is detected through nuclear-magnetism, which has ties shown in formula (1)
Structure, wherein R is ethylidene.
Preparation example 2
The preparation example is used to illustrate the preparation of double triazine thiol compounds provided by the invention with structure shown in formula (1)
Method.
(1) in dry round-bottomed flask, by 55.35g (0.3mol) Cyanuric Chloride 608.85g acetone solution (acetone
Mass ratio with Cyanuric Chloride is 11:1), 3 DEG C are cooled to, Cyanuric Chloride solution is obtained.By 12.41g (0.107mol) hexamethylene diamine
(molar ratio of Cyanuric Chloride and hexamethylene diamine is 2.8:1) is slowly added into above-mentioned Cyanuric Chloride solution, reacts 2h at 13 DEG C,
Intermediate A 2 is formed, by-product is HCl.
(2) by the Na of 70.2g (0.9mol)2S(Na2The molar ratio of S and Cyanuric Chloride is 3:1) soluble in water, stirring condition
Under be slowly added to aqueous hydrochloric acid solution 585ml (HCl and the Na of 2mol/L2The molar ratio of S is 0.8:1), intermediate A 2 is then added,
1h is reacted at 8 DEG C, then temperature rising reflux 5h.Reaction product is repeatedly washed with water to pH value close to 7 or so, and rotary evaporation obtains
To double triazine thiol compounds, it is denoted as B2.It is detected through nuclear-magnetism, which has structure shown in formula (1),
In, R is hexylidene.
Embodiment 1
The embodiment is for illustrating composite article provided by the invention and preparation method thereof.
(1) it prepares and combines agent solution:
0.344g is dissolved in 1L water (concentration 1mmol/L) by double triazine thiol compound B-11s that preparation example 1 obtains, is added
Enter 12.6g sodium nitrite, obtains bonding agent aqueous solution C1 after mixing.
(2) composite article is prepared:
By Al-alloy metal plate (ZAlSi7Mn aluminium alloy plate, 50mm × 150mm, similarly hereinafter) washes of absolute alcohol, then
The organic film with a thickness of 2000nm is prepared in metal surface using three electrode approach.Specifically, with 50mm × 30mm × 0.3mm
AA5052 as working electrode, using saturated calomel electrode as reference electrode, using SUS304 as auxiliary electrode, it will be cleaned
Al-alloy metal plate afterwards carries out electrochemical filming by cyclic voltammetry in above-mentioned bonding agent aqueous solution C1, and scanning range is
0.8-3.8V, sweep speed 10mV/s.
Being molded PPS on organic film using secondary injection molding technology, (purchased from U.S.'s Ticona company, the trade mark is
1140L6, similarly hereinafter), obtain composite article E1-1 comprising metal layer, organic film and the plastic layer stacked gradually.
Embodiment 2
The embodiment is for illustrating composite article provided by the invention and preparation method thereof.
Composite article is prepared according to the method for embodiment 1, unlike, by PPS using the PC of identical weight part (purchased from visiing
Ear company, the trade mark 1803, similarly hereinafter) substitution, obtain composite article E1-2 comprising metal layer, the organic film stacked gradually
And plastic layer.
Embodiment 3
The embodiment is for illustrating composite article provided by the invention and preparation method thereof.
Composite article is prepared according to the method for embodiment 1, unlike, PPS (is purchased from using the ABS of identical weight part
Taiwan Qi Mei company, trade mark PA-727, similarly hereinafter) substitution, obtains composite article E1-3 comprising the metal layer that stacks gradually,
Organic film and plastic layer.
Embodiment 4
The embodiment is for illustrating composite article provided by the invention and preparation method thereof.
Composite article is prepared according to the method for embodiment 1, unlike, Al-alloy metal plate is used to the magnesium of same size
Alloying metal plate (Mg-Al-Zn alloy sheets, 50mm × 150mm, similarly hereinafter) substitution, obtain composite article E1-4 comprising successively layer
Folded metal layer, organic film and plastic layer.
Embodiment 5
The embodiment is for illustrating composite article provided by the invention and preparation method thereof.
Composite article is prepared according to the method for embodiment 4, unlike, PPS is substituted using the PC of identical weight part, is obtained
To composite article E1-5 comprising metal layer, organic film and the plastic layer stacked gradually.
Embodiment 6
The embodiment is for illustrating composite article provided by the invention and preparation method thereof.
Composite article is prepared according to the method for embodiment 4, unlike, PPS is substituted using the ABS of identical weight part,
Obtain composite article E1-6 comprising metal layer, organic film and the plastic layer stacked gradually.
Embodiment 7
The embodiment is for illustrating composite article provided by the invention and preparation method thereof.
(1) it prepares and combines agent solution:
2.725g is dissolved in 1L water (concentration 8mmol/L) by double triazine thiol compound B2 that preparation example 2 obtains, is added
Enter 50.4g sodium nitrite, obtains bonding agent aqueous solution C2 after mixing.
(2) composite article is prepared:
Composite article is prepared according to the method for embodiment 1, unlike, bonding agent aqueous solution C1 is water-soluble using bonding agent
Liquid C2 substitution, obtains composite article E2-1 comprising metal layer, organic film and the plastic layer stacked gradually.
Embodiment 8
The embodiment is for illustrating composite article provided by the invention and preparation method thereof.
Composite article is prepared according to the method for embodiment 7, unlike, PPS is substituted using the PC of identical weight part, is obtained
To composite article E2-2 comprising metal layer, organic film and the plastic layer stacked gradually.
Embodiment 9
The embodiment is for illustrating composite article provided by the invention and preparation method thereof.
Composite article is prepared according to the method for embodiment 7, unlike, PPS is substituted using the ABS of identical weight part,
Obtain composite article E2-3 comprising metal layer, organic film and the plastic layer stacked gradually.
Embodiment 10
The embodiment is for illustrating composite article provided by the invention and preparation method thereof.
Composite article is prepared according to the method for embodiment 7, unlike, Al-alloy metal plate is used to the magnesium of same size
Alloying metal plate substitution, obtains composite article E2-4 comprising metal layer, organic film and the plastic layer stacked gradually.
Embodiment 11
The embodiment is for illustrating composite article provided by the invention and preparation method thereof.
Composite article is prepared according to the method for embodiment 10, unlike, PPS is substituted using the PC of identical weight part,
Obtain composite article E2-5 comprising metal layer, organic film and the plastic layer stacked gradually.
Embodiment 12
The embodiment is for illustrating composite article provided by the invention and preparation method thereof.
Composite article is prepared according to the method for embodiment 10, unlike, PPS is substituted using the ABS of identical weight part,
Obtain composite article E2-6 comprising metal layer, organic film and the plastic layer stacked gradually.
Comparative example 1
The comparative example is for illustrating composite article of reference and preparation method thereof.
Nano aperture is formed on Al-alloy metal plate using microcosmic roughening method, specifically, by the oil removing of Al-alloy metal plate,
It after washing, is dipped in microetch liquid medicine (the micro-etching agent MC-1026 of Si Jiefu company), time 1min, takes out washing repeatedly, dry
It is dry.Then PPS is molded using secondary injection molding technology on the Al-alloy metal plate with nano aperture, it is compound obtains reference
Product D-1 comprising the metal layer and plastic layer stacked gradually.
Comparative example 2
The comparative example is for illustrating composite article of reference and preparation method thereof.
Composite article is prepared according to the method for comparative example 1, unlike, PPS is substituted using the PC of identical weight part, is obtained
To reference composite article D-2 comprising the metal layer and plastic layer stacked gradually.
Comparative example 3
The comparative example is for illustrating composite article of reference and preparation method thereof.
Composite article is prepared according to the method for comparative example 1, unlike, PPS is substituted using the ABS of identical weight part,
Obtain reference composite article D-3 comprising the metal layer and plastic layer stacked gradually.
Comparative example 4
The comparative example is for illustrating composite article of reference and preparation method thereof.
Composite article is prepared according to the method for comparative example 1, unlike, Al-alloy metal plate is used to the magnesium of same size
Alloying metal plate substitution, obtains reference composite article D-4 comprising the metal layer and plastic layer stacked gradually.
Comparative example 5
The comparative example is for illustrating composite article of reference and preparation method thereof.
Composite article is prepared according to the method for comparative example 4, unlike, PPS is substituted using the PC of identical weight part, is obtained
To reference composite article D-5 comprising the metal layer and plastic layer stacked gradually.
Comparative example 6
The comparative example is for illustrating composite article of reference and preparation method thereof.
Composite article is prepared according to the method for comparative example 4, unlike, PPS is substituted using the ABS of identical weight part,
Obtain reference composite article D-6 comprising the metal layer and plastic layer stacked gradually.
Comparative example 7
The comparative example is for illustrating composite article of reference and preparation method thereof.
(1) it prepares and combines agent solution:
It prepares according to the method for embodiment 1 and combines agent solution, unlike, by double triazine thiol compound B-11s using identical
The 2 of molal quantity, 4,6- tri-thiols -1,3,5,-triazine substitution obtains bonding agent aqueous solution DC1.
(2) composite article is prepared:
Composite article is prepared according to the method for embodiment 1, unlike, the bonding agent aqueous solution is used into bonding agent water
Solution D C1 substitution, obtains composite article D-7 comprising metal layer, organic film and the plastic layer stacked gradually.
Test case
Test case is used to illustrate the test of composite article adhesive property.
According to method specified in GB/T 13936-92 " vulcanized rubber and metal bond tensile shear strength measuring method "
Caking property in composite article between metal layer and plastic layer is measured, the specific method is as follows:
Pass through tensilon (model: CMT5105, producer: Mei Tesi (MTS) industrial system Co., Ltd) stretch-bonded
Metal layer and plastic layer together, when record destroys, the cohesional failure situation on surface.It is 50mm × 50mm's by area
Remaining amount of plastic records cohesional failure index on metal surface, if be recorded as 0% without remnants, illustrates at destruction for metal
Between substrate and plastics, bond effect is worst；If all remaining, it is recorded as 100%, is illustrated at destruction for all plastics inners
Cohesional failure, bond effect is optimal.Acquired results are as shown in table 1.
Table 1
As can be seen from the above results, metal layer and plastic layer are bonded using bonding agent provided by the invention, energy
Enough reach good bond effect.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (17)
1. a kind of bonding agent, which is characterized in that the bonding agent contains double triazine thiol chemical combination with structure shown in formula (1)
Object:
R is C1-C16Linear chain or branched chain alkylidene, C6-C16At least one of segment containing arlydene,
Wherein, double triazine thiols on the basis of the total weight of the bonding agent, with structure shown in formula (1) in the bonding agent
The content of compound is 80 weight % or more.
2. bonding agent according to claim 1, wherein R C1-C10Linear chain or branched chain alkylidene.
3. bonding agent according to claim 2, wherein R C1-C6Linear chain or branched chain alkylidene.
4. bonding agent described in any one of -3 according to claim 1, wherein double triazine thiol compounds are according to following
Method is prepared:
It (1) is NH by Cyanuric Chloride and general formula2-R-NH2Diamino compound carried out at 0-15 DEG C first reaction；
(2) the first reaction product successively second is carried out at 0-10 DEG C later with vulcanized sodium and mixed in hydrochloric acid to react and in reflux condition
Third reaction is carried out under part.
5. bonding agent according to claim 4, wherein the time of first reaction is 1-5 hours, second reaction
Time be 1-3 hour, the time of third reaction is 2-6 hours.
6. bonding agent according to claim 4, wherein the molar ratio of the Cyanuric Chloride and diamino compound is 1-5:
1, the molar ratio of the vulcanized sodium and Cyanuric Chloride is 1-5:1, and the molar ratio of HCl and vulcanized sodium in the hydrochloric acid are 0.5-2:
1。
7. bonding agent described in any one of -3 according to claim 1, wherein on the basis of the total weight of the bonding agent,
The content of double triazine thiol compounds with structure shown in formula (1) in the bonding agent is 90-100 weight %.
8. bonding agent according to claim 7, wherein on the basis of the total weight of the bonding agent, in the bonding agent
The content of double triazine thiol compounds with structure shown in formula (1) is 100 weight %.
9. bonding agent described in any one of claim 1-8 is as the application on the binder between metal and plastics.
10. a kind of composite article, which is characterized in that the composite article includes the metal layer, organic film and plastics stacked gradually
Layer, organic film bonding agent as described in any one of claim 1-8 are formed.
11. composite article according to claim 10, wherein the metal layer be magnesium layer, aluminium layer, layers of copper, aluminium alloy layer,
At least one of magnesium alloy layer and stainless steel layer；The plastic layer is PPS layers, PC layers, abs layer, in pet layer and PP layers extremely
Few one kind.
12. a kind of preparation method of composite article, this method includes being formed on the surface for needing casting resin of metal layer
Machine film layer, then injection-moulded plastic is on the organic film to form plastic layer, and the organic film in claim 1-8 by appointing
Bonding agent described in meaning one is formed.
13. according to the method for claim 12, wherein the method for forming the organic film is spray coating method and/or three electricity
Pole electrolysis method, and electrolyte used by the three electrolysis method is the aqueous solution of the bonding agent.
14. method according to claim 12 or 13, wherein the metal layer be magnesium layer, aluminium layer, layers of copper, aluminium alloy layer,
At least one of magnesium alloy layer and stainless steel layer；The plastic layer is PPS layers, PC layers, abs layer, in pet layer and PP layers extremely
Few one kind.
15. the composite article that the method as described in any one of claim 12-14 is prepared.
16. application of the composite article as electronic product casing described in claim 10,11 or 15.
17. application according to claim 16, wherein the electronic product is mobile phone or notebook.
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| CN103525315A (en) * | 2012-06-29 | 2014-01-22 | 第一毛织株式会社 | Adhesive composition for polarizing plate, polarizing plate using the same, and optical member including the same |
| CN103657587A (en) * | 2013-10-30 | 2014-03-26 | 河南中和矿业有限公司 | Preparation method of triazine ramification inserting layer laminated clay heavy metal catching agent and application |
| CN105440282A (en) * | 2015-12-01 | 2016-03-30 | 苏州至善化学有限公司 | 1,3,5-triazine derivative compounds with high or low polymerization degree and preparation methods |
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| CN103525315A (en) * | 2012-06-29 | 2014-01-22 | 第一毛织株式会社 | Adhesive composition for polarizing plate, polarizing plate using the same, and optical member including the same |
| CN103657587A (en) * | 2013-10-30 | 2014-03-26 | 河南中和矿业有限公司 | Preparation method of triazine ramification inserting layer laminated clay heavy metal catching agent and application |
| CN105440282A (en) * | 2015-12-01 | 2016-03-30 | 苏州至善化学有限公司 | 1,3,5-triazine derivative compounds with high or low polymerization degree and preparation methods |
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