CN112266759B - Reactive adhesive for hard-to-stick flexible material and application thereof - Google Patents
Reactive adhesive for hard-to-stick flexible material and application thereof Download PDFInfo
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2431/00—Presence of polyvinyl acetate
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2475/00—Presence of polyurethane
Abstract
The invention relates to a reactive adhesive for a difficult-to-adhere flexible material and application thereof, wherein the reactive adhesive for the difficult-to-adhere flexible material comprises the following components in parts by weight: 100 parts of an aqueous polyurethane dispersion; 10-30 parts of vinyl acetate-ethylene copolymer (VAE) emulsion; 5-20 parts of a latent curing agent; 0.5-2 parts of an anti-hydrolysis stabilizer; 0.1-0.5 part of thickening agent; wetting dispersant BYK 1510.05-0.2 parts; wherein the aqueous polyurethane comprises main chemical composition structures of crystalline polyester polyol, amorphous polyester polyol, aliphatic isocyanate and the like, and contains amino (-NH) 2 or-NH-) and hydroxyl (-OH) active groups. The adhesive film made of the reactive adhesive for the difficult-to-adhere flexible material can quickly realize the adhesion of the difficult-to-adhere flexible material at 90-110 ℃, the adhesion strength is high, and the adhered difficult-to-adhere flexible material is resistant to bending and yellowing.
Description
Technical Field
The invention relates to an adhesive, in particular to a reactive adhesive for a difficult-to-adhere flexible material and application thereof.
Background
With people's concerns about quality of life and health data, consumer electronics products such as wearable devices are growing in demand rapidly. In the aspect of material selection, materials applied to the wearable device are in direct contact with human skin, and the wearable device needs to have the characteristics of safety, ventilation, durability, comfort, flexibility, softness, good fitting degree and the like, so that common materials of the wearable device include difficult-to-stick flexible materials such as silica gel, thermoplastic polyurethane elastomer (TPU), synthetic rubber elastomer (TPE) and the like. As a difficult-to-stick flexible material, the adhesion between the materials or with other materials is also a difficult point to be solved urgently by the finished product manufacturing end and the adhesive end.
In the current bonding scheme which is easily thought by people and used for difficult-to-bond flexible materials, the pressure-sensitive adhesive tape has the problem of insufficient bonding strength, and the liquid adhesive has the problems of unclean operation of finished products caused by extrusion of the adhesive, migration of solvent from the adhesive to formed products, harmful organic volatile compounds (VOC) and odor brought by the adhesive and the like. In addition, when the bonded product requires the bonding strength of the semi-structural or structural adhesive, the application of reactive adhesives in liquid adhesives is common, but the obvious disadvantage of long curing time exists. Under the background, technicians develop Heat Activated Film (HAF) for bonding hard-to-stick flexible materials, the HAF is classified into thermoplastic HAF and reactive HAF according to reworkability, and the reactive HAF not only solves the problem of liquid adhesives, but also has the bonding strength of reactive liquid adhesives.
When the reactive HAF is bonded by hot-press bonding, and when the non-adhesive flexible backing such as silica gel, TPU, TPE and the like is bonded by hot-press bonding, the flexible backing is easy to discolor and deform under the action of high temperature and pressure for a long time, so that the lower the temperature is, the better the hot-press bonding time is, the shorter the hot-press bonding time is. Generally, the hot-pressing temperature is required to be lower than 120 ℃, and the hot-pressing time is required to be shorter than 3 min.
The prior reactive HAF mainly comprises three systems of epoxy (or acrylate-epoxy), novolac butyronitrile and polyurethane. Epoxy and phenolic butyronitrile reactive HAF has the problems of high hot bonding temperature (>120 ℃) and long bonding time (>5min), and the cured adhesive film has poor toughness and extensibility, is easy to yellow and is not suitable for light-colored products, so that the epoxy and phenolic butyronitrile reactive HAF is not suitable for flexible backing products such as silica gel, TPU, TPE and the like. And the polyurethane reactive HAF hot bonding temperature is low (90-120 ℃), the bonding time is short (30s-3min), and the toughness and the extensibility of a cured adhesive film are good, so that the polyurethane reactive HAF hot bonding adhesive film is a good choice for bonding flexible backings such as silica gel, TPU, TPE and the like. However, polyurethane reactive HAFs actually have the disadvantages of high thermal bonding temperature, low bonding strength, and easy yellowing when they are used to bond difficult-to-bond flexible backings such as silicone, TPU, and TPE.
Patents CN104185664B, CN106753000A and CN107107548A all disclose that the compound contains-OH and-NH 2 Latent reactive adhesive film comprising a thermoplastic component of radicals and a surface-deactivated isocyanate curing agent component dispersed in the form of particles in the thermoplastic component for bonding anodized aluminum (glass, ceramic, etc.)) And polar plastics. The bonding of the reactive polyurethane HAF to the difficult-to-bond flexible material is not referred to, and how the bonding condition and effect of the reactive polyurethane HAF to the difficult-to-bond flexible material are unknown.
Patent CN111100592A discloses a one-component polyurethane hot melt adhesive film of polyurethane containing-OH groups and blocked isocyanate curing agent. However, the selection of a blocked curing agent has the problem of residual thermally deblocked blocking agent, and the commercial blocked curing agent has the problems of high deblocking and curing temperature and slow curing rate, as disclosed in the patent: when the polyurethane hot melt adhesive film is used for thermally bonding the bonding cloth/aluminum at 150 ℃, the polyurethane hot melt adhesive film needs to be cured for 10 days at 100 ℃, the curing time is long, and the bonding conditions and the effect on the difficult-to-bond flexible materials are unknown.
CN 111234768A discloses a moisture-curing polyurethane hot melt adhesive (PUR) for bonding non-polar materials, which has good bonding strength to non-polar PP, and a preparation method thereof. When the PUR is used, the PUR is coated on a substrate to be bonded by heating to a higher temperature (such as 130 ℃) to form a melt, similar to a liquid adhesive, and although the problems of solvent and VOC are solved, the unclean operation of a finished product caused by extrusion of the adhesive still exists. In addition, the PUR curing mechanism is moisture curing, which generally requires ambient humidity and takes a long time to cure completely, as described in the patent for 72 hours at 25 ℃ and 50% RH.
In conclusion, because the flexible backing is often required to have better bending resistance and less yellowing (meeting the requirements of light-colored products) in consumer electronics applications such as wearable devices, the adhesive strength of the reactive polyurethane HAF to the difficult-to-adhere flexible backing needs to be improved, and the polyurethane reactive HAF which can be adhered to the difficult-to-adhere flexible backing, is bending-resistant and is yellowing-resistant is developed.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide the reactive adhesive for the difficult-to-adhere flexible material and the application thereof.
The first purpose of the invention is to provide a reactive adhesive for difficult-to-stick flexible materials, which comprises the following components in percentage by weight:
wherein the aqueous polyurethane dispersion comprises polyester type aliphatic anionic aqueous polyurethane, the polyester type aliphatic anionic aqueous polyurethane comprises main chemical composition structures of crystalline polyester polyol, amorphous polyester polyol, aliphatic isocyanate and the like, and contains amino (-NH) 2 or-NH-) and hydroxyl (-OH) active groups.
Further, the solid content of the polyester type aliphatic anionic waterborne polyurethane is 40-60 percent; the mass ratio of the crystalline polyester polyol to the amorphous polyester polyol is 100: 5-30.
Further, the mass ratio of the aliphatic isocyanate to the crystalline polyester polyol is 15-35: 100.
Further, the crystalline polyester polyol has a hydroxyl value of 10 to 60mgKOH/g and a molecular weight of 2000-10000. Preferably, the crystalline polyester polyol has a hydroxyl value of 14 to 37mgKOH/g and a molecular weight of 3000-8500. More preferably, the crystalline polyester polyol comprises a polyester polyol
7360. Winning wound
7361. Winning wound
7380. Winning wound
7381. One or more of Huafeng PE-2708, Huafeng 2811 and Huafeng 3030.
Further, the amorphous polyester polyol has a hydroxyl value of 20 to 60mgKOH/g and a molecular weight of 2000-5500. Preferably, it is indefiniteThe polyester polyol has a hydroxyl value of 20-37mgKOH/g and a molecular weight of 3000-5500. More preferably, the amorphous polyester polyol is a winning creation
7111、
7130、
7131、
7210、
7231 and
7250.
Further, the aliphatic isocyanate includes isophorone diisocyanate (IPDI) and/or Hexamethylene Diisocyanate (HDI). The mass ratio of IPDI to HDI is 1:0-7: 5.
Further, the vinyl acetate-ethylene copolymer emulsion has a solid content of 50 to 65%, and preferably, the vinyl acetate-ethylene copolymer emulsion comprises Wacker chemistry
CA5588, CA5320, CA5330, CA5691, EP645, EP701K, 920 or 6300.
Further, the latent curing agent is isophorone diisocyanate type latent curing agent which is subjected to inactivation treatment, the reaction temperature of isocyanate groups (-NCO) in the curing agent is more than 80 ℃, and one of Aqualink D of Aquasspersons in UK or Shanghai Siwa chemical FB-15 is preferably selected.
Further, the hydrolysis-resistant stabilizer is a polymeric carbodiimide, preferably Stahl
XR-5580、XR-13-554、
XR-5508 or Langby technology
220, respectively.
Further, the thickener is an associative polyurethane thickener, preferably selected from Tourette RM-2050D, RM-8W, BYK-425 of Pico chemistry, and OPTIFLO-H600 VF.
The second purpose of the invention is to provide the application of the reactive adhesive for the difficult-to-bond flexible material in bonding the difficult-to-bond flexible material, which comprises the following steps:
preparing a glue film from a difficult-to-adhere flexible material by using a reactive adhesive, and adhering at least two difficult-to-adhere flexible materials on the glue film in a hot pressing mode, wherein the hot pressing mode is to perform hot pressing and adhering for 30s-3min under the conditions that the temperature is 90-110 ℃ and the pressure is 0.1-0.3 MPa.
Further, the preparation method of the adhesive film comprises the following steps:
mixing the components according to the formula of the reactive adhesive, coating the mixture on a temporary carrier glassine release paper, and drying the glassine release paper at 50-70 ℃ for 3-10min to obtain a glue film.
Further, the thickness of the adhesive film is 25-300 μm, wherein when the thickness of the adhesive film is more than 100 μm, the adhesive film can be prepared by thermally laminating a plurality of adhesive films with the thickness of less than 100 μm at 50-70 ℃.
In the present invention, the "hard-to-stick flexible material" refers to a material having a surface energy of less than 30 dyne and capable of being repeatedly bent. More specifically, the hard-to-stick flexible material includes silicone rubber (vulcanized silicone rubber RTV), TPU, TPE, and the like. The reactive adhesive can be applied to the bonding process of consumer electronic products such as wearable equipment.
The reactive adhesive for the difficult-to-adhere flexible material adjusts the wetting or permeation of a reactive adhesive film to a base material during hot lamination and the instant bonding strength after hot lamination through the crystalline polyester polyol and the amorphous polyester polyol in the aqueous polyurethane; vinyl acetate-ethylene copolymer VAE with good compatibility with waterborne polyurethane is introduced into the formula, the polarity of the polyurethane adhesive is adjusted, and the bonding strength of the difficult-to-bond flexible material is improved; the latent curing agent can form chemical bond connection with the surface of the hard-to-stick flexible material under the action of hot pressing, and can react with active groups on VAE to improve the cohesive strength of the adhesive film; the hydrolysis-resistant stabilizer improves the stability of the bonded hard-to-bond flexible material in the product use environment; the aqueous polyurethane dispersion and the aliphatic latent curing agent ensure that the adhesive film is not easy to yellow in hot bonding and use environments, so that the difficult-to-stick flexible material bonded by the reactive adhesive film has the characteristics of excellent bonding strength, bending resistance and difficult yellowing.
By the scheme, the invention at least has the following advantages:
(1) the reactive adhesive disclosed by the invention realizes strong bonding on difficult-to-bond flexible materials such as silica gel, TPU, TPE and the like by utilizing the physical action of a vinyl acetate-ethylene copolymer and the chemical action of an isocyanate group-NCO.
(2) The adhesive film prepared by the reactive adhesive can be stably stored at room temperature, can meet the requirement of a rapid laminating process at a lower temperature of 90-110 ℃, has better yellowing resistance, and avoids yellowing and discoloration of a flexible material in the processes of hot laminating sample preparation and later use.
(3) The reactive adhesive disclosed by the invention still has extensibility matched with a flexible material after a hot bonding reaction and excellent bonding strength, so that a bonded product made of a difficult-to-bond flexible material has excellent bending resistance.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following description is made with reference to the preferred embodiments of the present invention and the accompanying detailed drawings.
Drawings
FIG. 1 is a schematic view of a bending resistance test;
description of reference numerals:
1-test bar; 2-bending machine roller.
Detailed Description
The following examples are given to further illustrate embodiments of the present invention. The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention.
The reactive adhesive film according to the following examples of the present invention is prepared by bonding a hard-to-stick flexible backing by hot-press bonding, and for comparing the physical properties of reactive adhesive films with different formulations, only the data on the physical properties of the adhesive film with the same thickness of 50 μm are provided.
Selecting room temperature vulcanized silicone rubber RTV as the non-sticky flexible backing, and carrying out surface treatment on the to-be-sticky surface of the RTV by using plasma before the reactive adhesive film is bonded. The plasma treatment process comprises the following steps: n is a radical of 2 Under the atmosphere, the power of the device is 500W, the distance between a nozzle for generating plasma in the plasma device and the hard-to-stick flexible backing is 10mm, and the moving speed of the hard-to-stick flexible backing is 4 m/min.
The hot laminating process for preparing the sample by adhering the reactive adhesive film to the hard-to-adhere flexible backing is divided into two procedures of pre-laminating and laminating. The pre-laminating process is that one side of a reactive adhesive film (the other side of the reactive adhesive film is provided with a temporary carrier release paper) is firstly laminated on an RTV under the condition of temperature/pressure/time of 60 ℃/0.1MPa/5s to obtain a pre-laminated part; the laminating process comprises the steps of tearing off the temporary carrier release paper on one side of the reactive glue film on the pre-laminated part, then placing another RTV, and laminating the two RTVs and the reactive glue film arranged between the two RTVs under the condition that the temperature/pressure/time is 100 ℃/0.3MPa/60s to prepare the test sample strip. The test specimens were left for 24 hours at a temperature of 23. + -. 2 ℃ and a humidity of 50. + -. 5%, and then subjected to the physical property test. The bending resistance test method comprises the following steps:
and (3) testing environment: the temperature is 23 +/-2 ℃, and the humidity is 50 +/-5% RH; bending test angle: -180 ° -0 °; radius R of the roller of the bending machine: 1 mm; 1 bending test time: and 5 s.
And (3) judging standard: bending times are 20000 times, the sample strip is not subjected to glue opening and wrinkling, the OK is judged, and the result is recorded as the bending times are more than 20000 times; and (5) judging NG when the bending frequency is less than 20000, and recording the failure frequency. A schematic of the bend test is shown in fig. 1.
Example 1
A reactive adhesive for a hard-to-stick flexible material comprises the following components in percentage by weight:
the solid content of the aqueous polyurethane dispersion used is 60%, and the aqueous polyurethane dispersion contains crystalline polyester polyol, amorphous polyester polyol and aliphatic isocyanate. Wherein the crystalline polyester polyol is wound
7361 the amorphous polyester polyol is a winning ingredient
7111 the mass ratio of the crystalline polyester polyol to the amorphous polyester polyol is 100:30, the aliphatic isocyanate is IPDI and the mass ratio of the aliphatic isocyanate to the crystalline polyester polyol is 35: 100.
The reactive adhesive is used for preparing a reactive adhesive film, the reactive adhesive film is prepared by adding the raw materials according to the formula in sequence and stirring to prepare glue, the obtained glue is coated on glassine paper, and the reactive adhesive film with the thickness of 50 microns is prepared after drying for 10min in a 50 ℃ oven.
Example 2
A reactive adhesive for a hard-to-stick flexible material comprises the following components in percentage by weight:
the aqueous polyurethane dispersion used therein has a solids content of 50% and contains crystalline polyester polyols, amorphous polyester polyols and aliphatic isocyanates. Wherein the crystalline polyester polyol is originated from
7360 and Huafeng PE-3030 at a mass ratio of 1:1, amorphous polyester polyol is used as a winning material
7250 the mass ratio of the crystalline polyester polyol to the amorphous polyester polyol is 100:5, the aliphatic isocyanate is composed of IPDI and HDI, wherein the mass ratio of IPDI/HDI is 2:1, and the mass ratio of the aliphatic isocyanate to the crystalline polyester polyol is 15: 100.
The reactive adhesive is used for preparing a reactive adhesive film, the reactive adhesive film is prepared by adding the raw materials according to the formula in sequence and stirring to prepare glue, the obtained glue is coated on glassine paper, and the obtained glue is dried in an oven at 70 ℃ for 3min to prepare the reactive adhesive film with the thickness of 50 microns.
Example 3
A reactive adhesive for a hard-to-stick flexible material comprises the following components in percentage by weight:
the aqueous polyurethane dispersion used therein has a solids content of 40% and contains crystalline polyester polyols, amorphous polyester polyols and aliphatic isocyanates. Wherein the crystalline polyester polyol is originated from
7380 and Huafeng PE-2811 at a mass ratio of 1:1, the amorphous polyester polyol is a winning wound
7130 the mass ratio of the crystalline polyester polyol to the amorphous polyester polyol is 100:18.5, the aliphatic isocyanate is composed of IPDI and HDI, wherein the mass ratio of IPDI to HDI is 7:5, and the mass ratio of the aliphatic isocyanate to the crystalline polyester polyol is 25:100。
The reactive adhesive is used for preparing a reactive adhesive film, the reactive adhesive film is prepared by adding the raw materials according to the formula in sequence and stirring to prepare glue, the obtained glue is coated on glassine paper, and the obtained glue is dried in an oven at 60 ℃ for 6.5min to prepare the reactive adhesive film with the thickness of 50 microns.
The following is an exemplary comparison of the reactive adhesive compositions and methods of preparation of the prior art to illustrate the present invention.
Comparative example 1
The aqueous polyurethane dispersion used therein has a solids content of 40% and contains crystalline polyester polyols, amorphous polyester polyols and aliphatic isocyanates. Wherein the crystalline polyester polyol is originated from
7380 and Huafeng PE-2811 at a mass ratio of 1:1, the amorphous polyester polyol is a winning wound
7130 the mass ratio of the crystalline polyester polyol to the amorphous polyester polyol is 100:18.5, the aliphatic isocyanate is composed of IPDI and HDI, wherein the mass ratio of IPDI/HDI is 7:5, and the mass ratio of the aliphatic isocyanate to the crystalline polyester polyol is 25: 100.
The reactive adhesive is used for preparing a reactive adhesive film, the reactive adhesive film is prepared by adding the raw materials according to the formula in sequence and stirring to prepare glue, the obtained glue is coated on glassine paper, and the obtained glue is dried in an oven at 60 ℃ for 6.5min to prepare the reactive adhesive film with the thickness of 50 microns.
Comparative example 2
The aqueous polyurethane dispersion used therein has a solids content of 40% and contains crystalline polyester polyols, amorphous polyester polyols and aliphatic isocyanates. Wherein the crystalline polyester polyol is originated from
7380 and Huafeng PE-2811 at a mass ratio of 1:1, the amorphous polyester polyol is a winning wound
7130 the mass ratio of the crystalline polyester polyol to the amorphous polyester polyol is 100:18.5, the aliphatic isocyanate is composed of IPDI and HDI, wherein the mass ratio of IPDI/HDI is 7:5, and the mass ratio of the aliphatic isocyanate to the crystalline polyester polyol is 25: 100.
The reactive adhesive is used for preparing a reactive adhesive film, the reactive adhesive film is prepared by adding the raw materials according to the formula in sequence and stirring to prepare glue, the obtained glue is coated on glassine paper, and the obtained glue is dried in an oven at 60 ℃ for 6.5min to prepare the reactive adhesive film with the thickness of 50 microns.
Comparative example 3
Commercial 50 μm polyurethane reactive adhesive film
EM9002。
Comparative example 4
Commercial 50 μm polyurethane reactive adhesive film
HAF 8710。
Specific performance test data are shown in table 1:
TABLE 1 Performance test results for different adhesive films
As can be seen from the table above, the reactive adhesive film prepared by the formula of the invention has better bonding strength and yellowing resistance to the flexible backing which is difficult to bond with silicon rubber, and the bonded product has good bending resistance.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The reactive adhesive for the difficult-to-bond flexible material is characterized by comprising the following components in percentage by weight:
100 parts of an aqueous polyurethane dispersion;
10-30 parts of vinyl acetate-ethylene copolymer emulsion;
5-20 parts of a latent curing agent;
0.5-2 parts of an anti-hydrolysis stabilizer;
0.1-0.5 part of thickening agent;
wetting dispersant BYK-1510.05-0.2 parts;
wherein the aqueous polyurethane dispersion comprises a polyester type aliphatic anionic aqueous polyurethane comprising a crystalline polyester polyol, an amorphous polyester polyol, and an aliphatic isocyanate;
the latent curing agent is isophorone diisocyanate type latent curing agent subjected to inactivation treatment.
2. The reactive adhesive for a hardly adhesive flexible material according to claim 1, characterized in that: the solid content of the polyester type aliphatic anionic waterborne polyurethane is 40-60%; the mass ratio of the crystalline polyester polyol to the amorphous polyester polyol is 100:5-30, and the mass ratio of the aliphatic isocyanate to the crystalline polyester polyol is 15-35: 100.
3. The reactive adhesive for a hardly adhesive flexible material according to claim 1, characterized in that: the hydroxyl value of the crystalline polyester polyol is 10-60mgKOH/g, and the molecular weight is 2000-10000.
4. The reactive adhesive for a hardly adhesive flexible material according to claim 1, characterized in that: the amorphous polyester polyol has a hydroxyl value of 20-60mgKOH/g and a molecular weight of 2000-5500.
5. The reactive adhesive for a hardly adhesive flexible material according to claim 1, characterized in that: the aliphatic isocyanate comprises isophorone diisocyanate and/or hexamethylene diisocyanate.
6. The reactive adhesive for a hardly adhesive flexible material according to claim 1, characterized in that: the solid content of the vinyl acetate-ethylene copolymer emulsion is 50-65%.
7. The reactive adhesive for a hardly adhesive flexible material according to claim 1, characterized in that: the reaction temperature of the isocyanate groups in the latent curing agent is greater than 80 ℃.
8. The reactive adhesive for a hardly adhesive flexible material according to claim 1, characterized in that: the hydrolysis-resistant stabilizer is polymeric carbodiimide.
9. The reactive adhesive for a hardly adhesive flexible material according to claim 1, characterized in that: the thickening agent is an associated polyurethane thickening agent.
10. Use of a reactive adhesive for a hardly adhesive flexible material according to any one of claims 1 to 9 for bonding a hardly adhesive flexible material, comprising the steps of:
preparing the difficult-to-adhere flexible materials into adhesive films by using a reactive adhesive, and then adhering at least two difficult-to-adhere flexible materials by using the adhesive films in a hot pressing mode, wherein the hot pressing mode is that the materials are laminated for 30s-3min under the conditions that the temperature is 90-110 ℃ and the pressure is 0.1-0.3 MPa.
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Citations (11)
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