Background
The hot melt adhesive net film is widely applied to the clothing, textile, automobile and electronic industries by virtue of the advantages of no solvent, no pollution, high curing speed, convenient use and the like. The hot melt adhesive net film can be distinguished into various hot melt adhesive net films such as copolyamide, copolyester, EVA, TPU and the like according to different hot melt adhesive matrix resins. Among them, the copolyamide matrix resin has better heat resistance and bonding effect, and the copolyamide hot melt adhesive net film prepared by the copolyamide matrix resin is also popular with customers.
However, in the field of bonding of automobile interior parts, the conventional thermoplastic copolyamide hot melt adhesive net film is difficult to meet the actual application requirements, such as falling off phenomenon at a low temperature of-10 ℃ or a high temperature of 100 ℃, and has poor bonding effect on nonpolar materials such as PE layers and metals. It is therefore desirable to modify it to solve the problems of poor low temperature toughness and brittleness, thereby improving the bond strength to, for example, sheet metal-damping gaskets, etc., for better application to the bonding of automotive interior parts.
When the copolyamide hot melt adhesive net film is modified, a person skilled in the art usually directly modifies the copolyamide hot melt adhesive matrix resin to improve the low temperature resistance or the adhesion performance to a nonpolar material. As disclosed in patent CN103805124B, a preparation method of a low temperature resistant copolyamide hot melt adhesive is mainly composed of a dimer acid type copolyamide hot melt adhesive and its grafted derivative, a crosslinking rubber, a crosslinking agent and an auxiliary agent, wherein the main body of the crosslinking agent is a peroxide crosslinking agent, the component of the system which actually generates a crosslinking reaction is only a crosslinking rubber component, the copolyamide hot melt adhesive does not generate a crosslinking reaction, and the crosslinking rubber and the copolyamide hot melt adhesive have a problem of compatibility, so that the crosslinking agent is difficult to popularize in practical application; meanwhile, the modified copolyamide hot melt adhesive is not suitable for being made into a net film due to the low crosslinking reaction temperature.
Furthermore, copolyamide hot melt adhesives are different from polyolefin or EVA hot melt adhesives, and the crosslinking agents and auxiliary agents commonly used for the latter two are not suitable for curing modification of the former. Therefore, a cross-linking agent suitable for copolyamide hot melt adhesive is found, a using method of the cross-linking agent is researched, and a cross-linked modified copolyamide hot melt adhesive net film suitable for bonding automobile inner parts is successfully manufactured, so that the problem to be solved is solved.
Disclosure of Invention
The invention aims to solve the technical problems and provides a cross-linked modified copolyamide hot melt adhesive net film and a preparation and use method thereof, so that the copolyamide hot melt adhesive net film prepared by the method can be cross-linked and solidified in a hot-pressing state during use, has the characteristics of high temperature resistance and high bonding strength, and is very suitable for bonding of automobile interior parts.
The invention adopts the technical scheme that the cross-linking modified copolyamide hot melt adhesive net film is prepared from copolyamide hot melt adhesive matrix resin and cross-linking agent aqueous solution.
The cross-linking agent aqueous solution is a polyepoxide aqueous solution, and the mass ratio of the cross-linking agent to water is 1:5-10; the addition amount of the cross-linking agent is 3% -6% of the mass of the copolyamide hot melt adhesive matrix resin; the crosslinking agent may be specifically selected from: one of sorbitol polyglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether or pentaerythritol polyglycidyl ether, the cross-linking agent is transparent liquid in appearance, has low viscosity at normal temperature and can be mutually dissolved with water;
the copolyamide hot melt adhesive matrix resin is a conventional copolyamide hot melt adhesive prepared by copolymerizing main raw materials such as caprolactam, nylon 66 salt, nylon 612 salt, nylon 1010 salt and the like under the action of a proper amount of water and stearic acid; the melting point is 90-130 ℃, and the melt index is 20-60 g/10min at 160 ℃; the form may be powder, granule or bar, preferably granule.
The preparation method of the crosslinked modified copolyamide hot melt adhesive net film comprises the following steps:
(1) After the copolyamide hot melt adhesive matrix resin is melted, respectively pumping the molten copolyamide hot melt adhesive matrix resin into two mutually independent first spinneret plates and second spinneret plates;
(2) The method comprises the steps of (1) spraying molten copolyamide hot melt adhesive in a first spinneret plate onto a conveyor belt at a first preset speed under the traction of air flow, and then passing through a first infrared heating area to form a first layer of net film;
(3) A mist spraying device is arranged between the first spinneret plate and the second spinneret plate which are mutually independent, and the cross-linking agent aqueous solution is sprayed out of the mist spraying device and onto the first layer of net film;
(4) The copolyamide hot melt adhesive melted in the second spinneret plate is sprayed onto a conveyor belt at a second preset speed under the traction of air flow, is compounded with a first layer of net film sprayed with a cross-linking agent aqueous solution, and is heated through a second infrared heating area to form a compound net film;
(5) The composite net film is cooled, crystallized and rolled to form the cross-linked modified copolyamide hot melt adhesive net film.
The copolyamide hot melt adhesive matrix resin related in the step (1) is a conventional copolyamide hot melt adhesive prepared by copolymerizing main raw materials such as caprolactam, nylon 66 salt, nylon 612 salt, nylon 1010 salt and the like under the action of a proper amount of water and stearic acid, wherein the melting point is 90-130 ℃, and the melt index is 20-60 g/10min at 160 ℃;
in the step (3), the aqueous solution of the cross-linking agent is an aqueous solution of a polyepoxide compound, and the mass ratio of the cross-linking agent to water is 1:5-10; the cross-linking agent may be specifically selected from: one of sorbitol glycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether or pentaerythritol polyglycidyl ether, the cross-linking agent is transparent liquid in appearance, low in viscosity at normal temperature and capable of being mutually dissolved with water; meanwhile, the addition amount of the cross-linking agent is 3% -6% of the mass of the copolyamide hot melt adhesive matrix resin;
in the steps (2) and (4), parameters of the first spinneret plate and the second spinneret plate are the same, and the temperatures of the two spinneret plates are 180-240 ℃; the first preset spinning speed and the second preset spinning speed are 15-30 m/min. The temperature of the first infrared heating area is 80-120 ℃; the temperature of the second infrared heating zone is lower than that of the first infrared heating zone, specifically 60-90 ℃; the distance between the first spinneret plate and the second spinneret plate can be determined according to actual conditions, and is preferably 1.5-3 m; the conveying speed of the conveying belt is 8 m/min-15 m/min.
When the crosslinked modified copolyamide hot melt adhesive net film is used, the steps are as follows:
(1) Paving the crosslinked modified copolyamide hot melt adhesive net film between two adhered materials to form a blank plate;
(2) The blank plate is sent into a hot press for hot pressing, the hot pressing temperature is 140-170 ℃, the pressure is 0.5-5 MPa, and the hot pressing time is 1-5 min;
(3) Taking out the high Wen Peiban from the hot press, and flatly placing until the temperature is reduced to room temperature.
The innovation of the invention is as follows:
a. the copolyamide contains a large number of polar amide bonds, terminal amino groups and carboxyl groups, so that a cross-linking agent aqueous solution suitable for the copolyamide hot melt adhesive is found, the cross-linking agent aqueous solution is subjected to cross-linking reaction in an amorphous area, and the impact resistance and the thermal performance of the copolyamide hot melt adhesive net film are improved;
b. the cross-linking agent aqueous solution is added in the process of preparing and forming the omentum, but not in the process of preparing the copolyamide hot melt adhesive matrix resin, so that the effect of cross-linking modification is not lost due to the fact that the temperature of a spinneret plate is higher than the cross-linking reaction temperature;
c. the cross-linking agent aqueous solution exists in the whole preparation process of the copolyamide hot melt adhesive net film in a special mode, so that the preparation and the molding of the net film are not affected, and the cross-linking and the solidification are not caused in the processing process, and the special mode is beneficial to the dispersion and the diffusion of the cross-linking agent aqueous solution in the copolyamide hot melt adhesive matrix resin, so that the cross-linking speed and the cross-linking degree in the subsequent use process are further improved;
d. when in subsequent use, the cross-linking reaction is completed in the hot pressing process, and the adhesive property and heat resistance of the product are improved.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
Example 1
The cross-linked modified copolyamide hot melt adhesive net film comprises the following raw materials in parts by weight: 100 parts of copolyamide matrix resin (the melting point of the copolyamide matrix resin is 120 ℃, the melting point is 25g/10min, and the semitransparent particles) and 3 parts of cross-linking agent (specifically glycerol polyglycidyl ether), wherein the cross-linking agent and water are mixed according to the mass ratio of 1:10 to form a cross-linking agent aqueous solution.
The preparation method of the crosslinked modified copolyamide hot melt adhesive net film comprises the following steps:
(1) After the copolyamide hot melt adhesive matrix resin is melted, respectively pumping the molten copolyamide hot melt adhesive matrix resin into two mutually independent first spinneret plates and two mutually independent second spinneret plates, wherein the temperature of heat conduction oil of the two spinneret plates is 200 ℃, the distance between the two spinneret plates is 2m, a conveyor belt works, and the conveying speed of the conveyor belt is adjusted to be 10m/min;
(2) The first spinneret plate is opened, and the copolyamide hot melt adhesive melted in the first spinneret plate is sprayed on a conveyor belt at a speed of 20m/min under the traction of air flow, and passes through a first infrared heating zone with the temperature of 100 ℃ to form a first layer of net film;
(3) A mist spraying device is arranged between the two spinneret plates, and a cross-linking agent aqueous solution is sprayed out of the spraying device and sprayed on the first layer of net film;
(4) The second spinneret plate is opened, the copolyamide hot melt adhesive melted in the second spinneret plate is sprayed on a conveyor belt at a speed of 20m/min under the traction of air flow, and is compounded with the first layer of net film sprayed with the cross-linking agent aqueous solution while the first layer of net film is hot, and then the first layer of net film passes through a second infrared heating area with the temperature of 70 ℃ to form a compound net film;
(5) The composite net film is obtained through cooling, crystallization and rolling.
A sample of the crosslinked modified copolyamide hot melt adhesive web obtained in example 1 was designated A1.
Example 2
The cross-linked modified copolyamide hot melt adhesive net film comprises the following raw materials in parts by weight: 100 parts of copolyamide matrix resin (the melting point of the copolyamide matrix resin is 130 ℃, the melting point is 60g/10min, and the semitransparent particles) and 6 parts of cross-linking agent (specifically sorbitol polyglycidyl ether) are mixed with water according to the mass ratio of 1:8 to form a cross-linking agent aqueous solution.
The preparation method of the crosslinked modified copolyamide hot melt adhesive net film comprises the following steps:
(1) After the copolyamide hot melt adhesive matrix resin is melted, respectively pumping the molten copolyamide hot melt adhesive matrix resin into two mutually independent first spinneret plates and second spinneret plates, wherein the temperature of heat conduction oil of the two spinneret plates is 240 ℃, the distance between the two spinneret plates is 3m, a conveyor belt works, and the conveying speed of the conveyor belt is adjusted to be 15m/min;
(2) The first spinneret plate is opened, and the copolyamide hot melt adhesive melted in the first spinneret plate is sprayed on a conveyor belt at a speed of 30m/min under the traction of air flow, and passes through a first infrared heating zone with the temperature of 120 ℃ to form a first layer of net film;
(3) A mist spraying device is arranged between the two spinneret plates, and a cross-linking agent aqueous solution is sprayed out of the spraying device and sprayed on the first layer of net film;
(4) The second spinneret plate is opened, the copolyamide hot melt adhesive melted in the second spinneret plate is sprayed on a conveyor belt at a speed of 30m/min under the traction of air flow, and is compounded with the first layer of net film sprayed with the cross-linking agent aqueous solution while the first layer of net film is hot, and then the first layer of net film passes through a second infrared heating area with the temperature of 90 ℃ to form a compound net film;
(5) The composite net film is obtained through cooling, crystallization and rolling.
A sample of the crosslinked modified copolyamide hot melt adhesive web obtained in example 2 was designated A2.
Example 3
The cross-linked modified copolyamide hot melt adhesive net film comprises the following raw materials in parts by weight: 100 parts of copolyamide matrix resin (the melting point of the copolyamide matrix resin is 90 ℃, the melting point is 20g/10min, and the semitransparent particles) and 4 parts of cross-linking agent (particularly trimethylolpropane polyglycidyl ether), wherein the cross-linking agent and water are mixed according to the mass ratio of 1:5 to form a cross-linking agent aqueous solution.
The preparation method of the crosslinked modified copolyamide hot melt adhesive net film comprises the following steps:
(1) After the copolyamide hot melt adhesive matrix resin is melted, respectively pumping the molten copolyamide hot melt adhesive matrix resin into two mutually independent first spinneret plates and second spinneret plates, wherein the temperature of heat conduction oil of the two spinneret plates is 240 ℃, the distance between the two spinneret plates is 1.5m, a conveyor belt works, and the conveying speed of the conveyor belt is adjusted to be 8m/min;
(2) The first spinneret plate is opened, and the copolyamide hot melt adhesive melted in the first spinneret plate is sprayed on a conveyor belt at a speed of 15m/min under the traction of air flow, and passes through a first infrared heating zone with the temperature of 80 ℃ to form a first layer of net film;
(3) A mist spraying device is arranged between the two spinneret plates, and a cross-linking agent aqueous solution is sprayed out of the spraying device and sprayed on the first layer of net film;
(4) The second spinneret plate is opened, the copolyamide hot melt adhesive melted in the second spinneret plate is sprayed on a conveyor belt at a speed of 15m/min under the traction of air flow, and is compounded with the first layer of net film sprayed with the cross-linking agent aqueous solution while the first layer of net film is hot, and then the first layer of net film passes through a second infrared heating area with the temperature of 60 ℃ to form a compound net film;
(5) The composite net film is obtained through cooling, crystallization and rolling.
A sample of the crosslinked modified copolyamide hot melt adhesive web obtained in example 3 was designated A3.
Example 4
The cross-linked modified copolyamide hot melt adhesive net film comprises the following raw materials in parts by weight: 100 parts of copolyamide matrix resin (the melting point of the copolyamide matrix resin is 100 ℃, the melting point is 45g/10min, and the semitransparent particles) and 5 parts of cross-linking agent (specifically pentaerythritol polyglycidyl ether) are mixed with water according to the mass ratio of 1:5 to form a cross-linking agent aqueous solution.
The preparation method of the crosslinked modified copolyamide hot melt adhesive net film comprises the following steps:
(1) After the copolyamide hot melt adhesive matrix resin is melted, respectively pumping the molten copolyamide hot melt adhesive matrix resin into two mutually independent first spinneret plates and two mutually independent second spinneret plates, wherein the temperature of heat conduction oil of the two spinneret plates is 180 ℃, the distance between the two spinneret plates is 2m, a conveyor belt works, and the conveying speed of the conveyor belt is adjusted to be 8m/min;
(2) The first spinneret plate is opened, and the copolyamide hot melt adhesive melted in the first spinneret plate is sprayed on a conveyor belt at a speed of 25m/min under the traction of air flow, and passes through a first infrared heating zone with the temperature of 100 ℃ to form a first layer of net film;
(3) A mist spraying device is arranged between the two spinneret plates, and a cross-linking agent aqueous solution is sprayed out of the spraying device and sprayed on the first layer of net film;
(4) The second spinneret plate is opened, the copolyamide hot melt adhesive melted in the second spinneret plate is sprayed on a conveyor belt at a speed of 25m/min under the traction of air flow, and is compounded with the first layer of net film sprayed with the cross-linking agent aqueous solution while the first layer of net film is hot, and then the first layer of net film passes through a second infrared heating area with the temperature of 80 ℃ to form a compound net film;
(5) The composite net film is obtained through cooling, crystallization and rolling.
A sample of the crosslinked modified copolyamide hot melt adhesive web obtained in example 4 was designated A4.
Samples A1 to A4 obtained in the above embodiments and a conventional thermoplastic copolyamide hot melt adhesive net film D are applied to bonding of automobile interior parts, in particular to bonding of a damping gasket for an automobile and a metal steel plate.
When in use, each cross-linked modified copolyamide hot melt adhesive net film and the conventional thermoplastic copolyamide hot melt adhesive net film are respectively arranged between two adhered materials to form a blank plate; respectively feeding the blank plates into a hot press for hot pressing, wherein the hot pressing parameters are as follows: the temperature is 150 ℃, the pressure is 1Mp, and the hot pressing time is 2min; each height Wen Peiban was removed from the press and laid flat until the temperature was reduced to room temperature.
And cutting out small samples of 2.5cm by 20cm from the bonded final products respectively corresponding to the reference numerals A1-A4 and D, and carrying out relevant tests, wherein the specific results are shown in the following table 1.
Table 1: test results for each sample
As apparent from trademark 1, the cross-linked modified copolyamide hot melt adhesive net film prepared by the invention has higher bonding strength, better high-low temperature resistance and obviously improved bonding effect when being applied to bonding of automobile inner parts compared with the conventional thermoplastic copolyamide hot melt adhesive net film.