CN116179094A - Single-sided rubberizing material and preparation method thereof - Google Patents

Single-sided rubberizing material and preparation method thereof Download PDF

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Publication number
CN116179094A
CN116179094A CN202211726264.6A CN202211726264A CN116179094A CN 116179094 A CN116179094 A CN 116179094A CN 202211726264 A CN202211726264 A CN 202211726264A CN 116179094 A CN116179094 A CN 116179094A
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semi
adhesive layer
sided
temperature
cured adhesive
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CN116179094B (en
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陈健雄
漆小龙
朱扬杰
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Guangdong Ying Hua New Mstar Technology Ltd
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Guangdong Ying Hua New Mstar Technology Ltd
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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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/28—Metal sheet
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • 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
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/10—Presence of inorganic materials
    • C09J2400/16—Metal
    • C09J2400/163—Metal in the substrate
    • 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
    • C09J2463/00—Presence of epoxy resin
    • C09J2463/006—Presence of epoxy resin in the substrate
    • 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
    • C09J2479/00—Presence of polyamine or polyimide
    • C09J2479/08—Presence of polyamine or polyimide polyimide
    • C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention relates to a single-sided rubberizing material and a preparation method thereof. The preparation method of the single-sided rubberizing material comprises the following steps: providing a flexible substrate, and forming a semi-cured adhesive layer on the surface of the flexible substrate to obtain a semi-finished product; pressing the semi-finished product at a temperature T to ensure that the viscosity of the semi-cured adhesive layer at the temperature T is kept between 100 mPa.s and 900 mPa.s for at least 30s, wherein the temperature T is not lower than the softening point of the semi-cured adhesive layer and lower than the curing temperature of the semi-cured adhesive layer. The preparation method can obtain the single-sided rubberizing material with uniformity, no defect and low warpage.

Description

Single-sided rubberizing material and preparation method thereof
Technical Field
The invention relates to the technical field of single-sided rubberizing materials, in particular to a single-sided rubberizing material and a preparation method thereof.
Background
The single-sided rubberizing material comprises a flexible substrate and a semi-cured adhesive layer arranged on one side of the flexible substrate, and can be used for preparing products such as copper-clad plates, reinforcing plates, flexible printed circuit boards (FPC) and the like. If the glue solution adopted for preparing the semi-solidified glue layer contains a higher proportion of volatile solvent or the surface energy of the flexible substrate is uneven, the dried semi-solidified glue layer can form tiny air holes and pits, so that the appearance quality of the glue layer is poor. Meanwhile, the single-sided rubberizing material is often of an asymmetric structure, the thermal expansion coefficients and the mechanical properties of the flexible substrate and the semi-cured adhesive layer are different, internal stress is easily generated in the heating and stretching processes, and the one side of the single-sided rubberizing material is inevitably warped. Serious warping can cause adverse effect on the adhesive property of the single-sided adhesive material, and cause larger error in the alignment and lamination process, thereby affecting the process debugging and the product yield.
Disclosure of Invention
Based on the above, it is necessary to provide a single-sided adhesive material which is uniform, defect-free and low in warpage and a preparation method thereof.
The above object of the present invention is achieved by the following technical solutions:
the invention provides a preparation method of a single-sided rubberizing material, which comprises the following steps:
providing a flexible substrate, and forming a semi-cured adhesive layer on the surface of the flexible substrate to obtain a semi-finished product;
pressing the semi-finished product at a temperature T to ensure that the viscosity of the semi-cured adhesive layer at the temperature T is kept between 100 mPa.s and 900 mPa.s for at least 30s, wherein the temperature T is not lower than the softening point of the semi-cured adhesive layer and lower than the curing temperature of the semi-cured adhesive layer.
In one embodiment, the temperature T is 80-140 ℃.
In one embodiment, the pressing before and/or after further comprises the steps of: heating at the temperature T for 1 s-5 s.
In one embodiment, the pressure application satisfies one or more of the following conditions:
1) The pressing force was 3kgf/cm 2 ～12kgf/cm 2 ；
2) The duration of the pressure application is 5-30 s;
3) The pressing equipment is a roller or a pressing plate.
In one embodiment, the pressing further comprises one or more of the following steps:
1) Covering a release film on the surface of the semi-cured adhesive layer;
2) Coating a release agent on the surface of the roller or the pressing plate;
3) The roller or the pressing plate is made of a release material.
In one embodiment, the release film is one of a PET release film, an OPP release film, and a release paper.
In one embodiment, the thickness of the semi-cured adhesive layer is 10 μm to 100 μm.
In one embodiment, the flexible substrate is one or more of a polymer film, a metal foil, a fiber reinforced composite.
In one embodiment, the preparation method of the semi-cured adhesive layer comprises the following steps: and coating the thermosetting glue solution on one surface of the flexible substrate, and drying the flexible substrate at a temperature below the curing temperature to form the semi-cured glue layer.
In one embodiment, the thermosetting glue meets one or more of the following conditions:
1) The thermosetting glue solution is one or more of epoxy resin glue solution, unsaturated polyester resin glue solution, bismaleimide glue solution and phenolic resin glue solution;
2) The thermosetting glue solution comprises thermosetting resin and a curing agent;
3) The thermosetting glue solution comprises one or more of a curing accelerator, a thermoplastic resin and a solvent.
In a second aspect, the present invention provides a single-sided adhesive material, which is prepared by the preparation method of the single-sided adhesive material.
The temperature T adopted by the invention is not lower than the softening point of the semi-cured adhesive layer and is lower than the curing temperature of the semi-cured adhesive layer, so that the semi-cured adhesive layer can be heated and softened to obtain the semi-cured adhesive layer with lower viscosity and good fluidity, the softened and flowing semi-cured adhesive layer can be tightly attached to a flexible substrate by pressing at the temperature T, and the pits and air holes of the adhesive layer are eliminated by extrusion and filling, so that the appearance quality of the single-sided adhesive material is improved; meanwhile, the heated calendaring process is favorable for smoothly releasing partial internal stress of the semi-cured adhesive layer, and the warping degree of the single-sided adhesive material is effectively reduced, so that the single-sided adhesive material with uniform defect-free and low warping degree is obtained.
Drawings
FIG. 1 is a graph showing the viscosity change of a semi-cured adhesive layer at a temperature T measured by a constant temperature method;
FIG. 2 is an appearance test chart of the single-sided adhesive material prepared in example 1;
FIG. 3 is an appearance test chart of the single-sided adhesive material prepared in comparative example 1;
fig. 4 is a graph showing the viscosity change of the semi-cured adhesive layer outside the temperature T range measured by the constant temperature method.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to the appended drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, whereby the invention is not limited to the specific embodiments disclosed below.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The invention provides a preparation method of a single-sided rubberizing material, which comprises the following steps:
providing a flexible substrate, and forming a semi-cured adhesive layer on the surface of the flexible substrate to obtain a semi-finished product;
pressing the semi-finished product at a temperature T to ensure that the viscosity of the semi-cured adhesive layer at the temperature T is kept between 100 mPa.s and 900 mPa.s for at least 30s, wherein the temperature T is not lower than the softening point of the semi-cured adhesive layer and lower than the curing temperature of the semi-cured adhesive layer.
The temperature T adopted by the invention is not lower than the softening point of the semi-cured adhesive layer and is lower than the curing temperature of the semi-cured adhesive layer, so that the semi-cured adhesive layer can be heated and softened to obtain the semi-cured adhesive layer with lower viscosity and good fluidity, the softened and flowing semi-cured adhesive layer can be tightly attached to a flexible substrate by pressing at the temperature T, and the pits and air holes of the adhesive layer are eliminated by extrusion and filling, so that the appearance quality of the single-sided adhesive material is improved; meanwhile, the heated calendaring process is favorable for smoothly releasing partial internal stress of the semi-cured adhesive layer, and the warping degree of the single-sided adhesive material is effectively reduced, so that the single-sided adhesive material with uniform defect-free and low warping degree is obtained.
In some embodiments, the temperature T is 80to 140 ℃.
The proper heating temperature is selected according to the softening point and the curing temperature of the semi-cured adhesive layer, so that the semi-cured adhesive layer can be softened and flows in a short time, the internal stress can be rapidly released, and the problems of adhesive overflow, complete curing and the like caused by excessively high heating temperature and excessively long time are avoided.
In some embodiments, the pressing before and/or after further comprises the steps of: heating at the temperature T for 1 s-5 s.
Preheating is carried out before pressing or heating post-treatment is carried out after pressing, so that the effects of eliminating defects and releasing internal stress can be enhanced, and the production rate of the single-sided rubberizing material can be improved.
In some embodiments, the pressure application satisfies one or more of the following conditions:
1) The pressing force was 3kgf/cm 2 ～12kgf/cm 2 ；
2) The duration of the pressure application is 5-30 s;
3) The pressing equipment is a roller or a pressing plate.
The pressure is applied in a very short time by adopting lower pressure, so that the phenomenon of glue overflow of the semi-solidified glue layer can be avoided while warpage, bubbles and pits are reduced, and the phenomenon of internal stress increase caused by excessive hot pressing is prevented. In addition, the semi-finished product has different shapes, and the pressing mode or the pressing equipment is different. When the semi-finished product is coiled material, the coiled head of the coiled semi-finished product can be pulled to be coiled out and then pressed by a roller at a certain speed; when the semi-finished product is a sheet, the sheet-shaped semi-finished product can be laid under the pressing plate for pressing.
In some embodiments, the pressing further comprises one or more of the following steps:
1) Covering a release film on the surface of the semi-cured adhesive layer;
2) Coating a release agent on the surface of the roller or the pressing plate;
3) The roller or the pressing plate is made of a release material.
The semi-cured adhesive layer has stronger bonding capability after softening, and the problems that the semi-cured adhesive layer and the pressing equipment are polluted can be solved by covering the release film, coating the release agent and adopting a roller or a pressing plate made of release materials.
In some embodiments, the release film is one of a PET release film, an OPP release film, and a release paper.
In some embodiments, the release agent is a silicone-type release agent and/or a non-silicone-type release agent.
In some embodiments, the release material is polytetrafluoroethylene.
In some embodiments, the thickness of the semi-cured bondline is from 10 μm to 100 μm.
The semi-cured adhesive layer with lower thickness is adopted, so that the volume shrinkage rate of the semi-cured adhesive layer in the form change process can be reduced, partial internal stress is eliminated, and the warping degree of the single-sided adhesive material is further reduced.
In some embodiments, the flexible substrate is one or more of a polymer film, a metal foil, a fiber reinforced composite.
In some more preferred embodiments, the flexible substrate is one or more of a polyimide film, a polyester film, a copper foil, a prepreg, and a cured sheet.
And selecting a proper flexible substrate according to the requirements of products and processes to prepare the single-sided rubberized material with flexibility. Meanwhile, the adoption of the layered flexible substrate without the through holes can ensure that the adhesive layer cannot penetrate to the other side of the flexible substrate to influence the appearance and performance of the single-sided adhesive material.
In some embodiments, the method for preparing the semi-cured adhesive layer includes the following steps: and coating the thermosetting glue solution on one surface of the flexible substrate, and drying the flexible substrate at a temperature below the curing temperature to form the semi-cured glue layer.
In some more preferred embodiments, the method for preparing the semi-cured adhesive layer includes the steps of: and (3) coating the thermosetting glue solution on one surface of the flexible substrate, drying at 80-140 ℃ for 2-5 min, and cooling by air shower to form the semi-cured glue layer.
In some embodiments, the thermoset glue meets one or more of the following conditions:
1) The thermosetting glue solution is one or more of epoxy resin glue solution, unsaturated polyester resin glue solution, bismaleimide glue solution and phenolic resin glue solution;
2) The thermosetting glue solution comprises thermosetting resin and a curing agent;
3) The thermosetting glue solution comprises one or more of a curing accelerator, a thermoplastic resin and a solvent.
In some more preferred embodiments, the epoxy resin glue solution comprises bisphenol a epoxy resin, 4' -diaminodiphenyl sulfone, carboxyl terminated liquid nitrile rubber, N-dimethylformamide, and butanone.
In some more preferred embodiments, the phenolic resin glue solution comprises xylene formaldehyde resin, styrene-butadiene copolymer, N-dimethylaniline and toluene.
The addition of thermoplastic resins such as carboxyl-terminated liquid nitrile rubber and styrene-butadiene copolymer to the thermosetting glue solution can improve the viscosity, toughness, adhesion and other properties of the semi-cured glue layer.
In a second aspect, the present invention provides a single-sided adhesive material, which is prepared by the preparation method of the single-sided adhesive material.
The present invention will be described in further detail with reference to specific examples.
Example 1
(1) Referring to Table 1, according to the mass parts, 100 parts of bisphenol A type epoxy resin, 34.4 parts of 4,4' -diaminodiphenyl sulfone, 20 parts of carboxyl-terminated liquid nitrile rubber, 70 parts of N, N-dimethylformamide and 80 parts of butanone are taken, mixed and stirred to a uniform phase, so as to prepare an epoxy resin glue solution;
TABLE 1 raw materials for preparing Single-sided sizing Material from EXAMPLES 1 to 8
Raw materials CAS number Suppliers (suppliers) Number plate
Bisphenol A type epoxy resin 1675-54-3 NAN YA PLASTICS Corp. NPEL-128
4,4' -diaminodiphenyl sulfone 80-08-0 Shandong blue Shi New Material Co DDS
Carboxyl-terminated liquid nitrile rubber 68891-46-3 Hubei Chengfeng chemical Co Ltd CTBN
N, N-dimethylformamide 68-12-2 BASF SE DMF
Butanone 78-93-3 Baling petrochemical plant MEK
Xylene formaldehyde resin 26139-75-3 SHANDONG SHENGQUAN NEW MATERIAL Co.,Ltd. XR-01
Styrene-butadiene copolymer 9003-55-8 Qilu petrochemical industry SBR1502
N, N-dimethylaniline 121-69-7 Shandong national chemical Co., ltd /
Toluene (toluene) 108-88-3 Constant force petrochemical Co., ltd /
Cured sheet / Guangdong Ying Hua new Mstar Technology Ltd. H-850G
OPP release film / New materials Co.Ltd /
Polyimide film / New Material Co Ltd /
(2) Taking a roll of cured sheet with single-layer thickness of 100 mu m, wherein the cured sheet is a fiber reinforced composite material prepared by impregnating glass fiber cloth with epoxy resin glue solution, drying and curing; coating epoxy resin glue solution on one surface of a cured sheet by a coating machine (manufactured by the mechanical limited company of wenzhou Wei Cheng), drying for 3min at 80-140 ℃, and cooling to form a semi-cured glue layer with the thickness of 25 mu m; covering a layer of OPP release film with 38 μm on the surface of the semi-cured adhesive layer, and heating to 100deg.C under pressure of 4kgf/cm with a hot press compounding machine (manufactured by Winz Wei Cheng mechanical Co., ltd.) 2 Pressing for 3s under the condition of air shower cooling to room temperature to prepare a coiled semi-finished product, wherein the structure of the coiled semi-finished product is an OPP release film/semi-cured adhesive layer/curing sheet, and the coiled semi-finished product is a typical asymmetric structure;
wherein, the softening point of the semi-cured adhesive layer is 80 ℃, and the curing conditions are as follows: heating at 165 ℃ for 4 hours or at 180 ℃ for 2 hours;
(3) The winding head of the rolled semi-finished product is pulled and wound out, and then passed through an infrared radiation oven (MATSUOKA Song mechanical Co., ltd.) preheated to 120 ℃ at a constant speed, and the rolled semi-finished product is subjected to a process ofAny point in the semi-finished product is heated for 10s; heating for 5s, and pressurizing by a roller set (80 t hot press laminator modified by MATSUOKA Song mechanical Co., ltd.) in an infrared radiation oven, wherein the pressure of the roller set is 4kgf/cm 2 The total duration of pressurization is 5s, and then the single-sided rubberized material is obtained after being taken out and naturally cooled to the room temperature.
Before the hot pressing process, the viscosity of the semi-cured adhesive layer is tested by using an Shimadzu CFT-100EX capillary rheometer by using a constant temperature method, wherein the constant temperature is 120 ℃ and the duration is 60 seconds, and the viscosity change curve is shown in figure 1. The appearance test method of the single-sided rubberizing material comprises the following steps: observation is carried out by an Olin Bass BX53M metallographic microscope which is amplified by 25 times, if no air holes and pits exist in the semi-cured adhesive layer and no air bubbles exist between the semi-cured adhesive layer and the release film or the substrate, the semi-cured adhesive layer is judged to be good, otherwise, the semi-cured adhesive layer is judged to be bad, and the appearance test result is shown in figure 2. The method for testing the warping degree of the single-sided rubberizing material comprises the following steps: the single-sided adhesive material was cut into 300mm×200mm samples, the substrates of the samples were placed horizontally downward, and the vertical distance between the horizontal plane of the samples and the highest point of the samples was measured using a height gauge after standing, and the results are shown in table 2.
As can be seen from fig. 1, the viscosity of the semi-cured adhesive layer can be maintained at 300 mpa-700 mpa-s for at least 60s at a constant temperature of 120 ℃, and the adhesive layer has good flowability. As can be seen from fig. 2, the single-sided rubberized material has a good appearance and is uniform and defect-free. As can be seen from table 2, the warpage of the single-sided adhesive material is 2.64mm, which indicates that the internal stress of the releasable part can be reduced by hot pressing, and the warpage of the single-sided adhesive material can be reduced, and bubbles and pits can be eliminated, so that the single-sided adhesive material with uniform and no defects and low warpage can be obtained.
TABLE 2 Hot pressing conditions and test results for examples 1 to 8
Figure BDA0004030082480000091
Example 2
The preparation process of this example is essentially the same as that of example 1, except for the steps ofStep (3): after the winding head of the coiled semi-finished product is pulled to be wound out, the coiled semi-finished product uniformly passes through an infrared radiation oven preheated to 140 ℃, and the total heating time of any point in the coiled semi-finished product is 35s; after heating for 5s, pressurizing by a roller set in an infrared radiation oven, wherein the pressure of the roller set is set to be 12kgf/cm 2 The total time of pressurization is 30s, and then the single-sided rubberized material is obtained after being taken out and naturally cooled to the room temperature.
Viscosity, appearance and warpage tests were carried out according to the method described in example 1, the viscosity change curves are shown in fig. 1, and the appearance and warpage test results are shown in table 2. As can be seen from fig. 1, the viscosity of the semi-cured adhesive layer can be maintained between 200 mpa-s and 600 mpa-s for at least 60s at a constant temperature of 140 ℃, and the adhesive layer has good flowability. As can be seen from table 2, the single-sided adhesive material has a good appearance, and a warpage of 2.87mm, which means that the internal stress of the releasable part of the hot pressing can be reduced by properly increasing the temperature, pressure and time of the hot pressing, and the warpage of the single-sided adhesive material can be reduced, and bubbles and pits can be eliminated, so that the single-sided adhesive material with uniform and no defects and low warpage can be prepared.
Example 3
This example is essentially the same as example 1 except for step (3): after the winding head of the coiled semi-finished product is pulled to be wound out, the coiled semi-finished product uniformly passes through an infrared radiation oven preheated to 80 ℃, and the total heating time of any point in the coiled semi-finished product is 5s; heating and pressurizing by a roller set in an infrared radiation oven, wherein the pressure of the roller set is set to be 3kgf/cm 2 The total duration of pressurization is 5s, and then the single-sided rubberized material is obtained after being taken out and naturally cooled to the room temperature.
Viscosity, appearance and warpage tests were carried out according to the method described in example 1, the viscosity change curves are shown in fig. 1, and the appearance and warpage test results are shown in table 2. As can be seen from fig. 1, the viscosity of the semi-cured adhesive layer can be maintained at 700 mpa-900 mpa-s for at least 60s at a constant temperature of 80 ℃, and the adhesive layer has good flowability. As can be seen from table 2, the single-sided adhesive material has a good appearance, and a warpage of 2.95mm, which means that the temperature, pressure and time of hot pressing are properly reduced to release partial internal stress, so that the warpage of the single-sided adhesive material can be reduced, and bubbles and pits can be eliminated, thereby preparing the single-sided adhesive material with uniformity, no defects and low warpage.
Example 4
This example is essentially the same as example 1 except for step (3): after the winding head of the coiled semi-finished product is pulled and wound out, the coiled semi-finished product is uniformly heated and pressurized by a roller set preheated to 120 ℃ at the same time, and the pressure applied by the roller set is set to be 4kgf/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the For any point in the coiled semi-finished product, the total duration of heating and pressurizing is 5s; and then taking out and naturally cooling to room temperature to obtain the single-sided rubberized material.
Viscosity, appearance and warpage tests were carried out according to the method described in example 1, the viscosity change curves are shown in fig. 1, and the appearance and warpage test results are shown in table 2. As can be seen from fig. 1, the viscosity of the semi-cured adhesive layer can be maintained at 300 mpa-700 mpa-s for at least 60s at a constant temperature of 120 ℃, and the adhesive layer has good flowability. As can be seen from table 2, the single-sided gumming material has a good appearance, a warpage of 2.61mm, and the fact that the preheated roller set is used for hot pressing can release partial internal stress can reduce the warpage of the single-sided gumming material, and is beneficial to eliminating bubbles and pits, so that the single-sided gumming material with uniform defect-free and low warpage is prepared.
Example 5
This example is essentially the same as example 1 except for step (3): cutting the coiled semi-finished product into a sheet semi-finished product with the area of 300mm multiplied by 200 mm; the sheet-like semifinished product was laid down in an opening of a quick press (80 TON Shan Zhangkuai press from Shi Lide mechanical equipments Co., ltd.) preheated to 120℃and immediately applied with 4kgf/cm 2 And (3) hot-pressing, wherein the total time length of heating and pressurizing is 5s, and then taking out and naturally cooling to room temperature to obtain the flaky single-sided rubberizing material.
Viscosity, appearance and warpage tests were carried out according to the method described in example 1, the viscosity change curves are shown in fig. 1, and the appearance and warpage test results are shown in table 2. As can be seen from fig. 1, the viscosity of the semi-cured adhesive layer can be maintained at 300 mpa-700 mpa-s for at least 60s at a constant temperature of 120 ℃, and the adhesive layer has good flowability. As can be seen from table 2, the single-sided gumming material has a good appearance, and a warpage of 2.95mm, which indicates that the use of a hot press to perform hot pressing on the sheet-shaped single-sided gumming material can release partial internal stress, can reduce the warpage of the single-sided gumming material, and is beneficial to eliminating bubbles and pits, thereby preparing the single-sided gumming material with uniformity, no defects and low warpage.
Example 6
The preparation method of this example is basically the same as that of example 1, except that: the thermosetting glue solution is phenolic resin glue solution and the preparation method thereof is as follows: referring to table 1, 100 parts by mass of a xylene formaldehyde resin, 30 parts by mass of a styrene-butadiene copolymer, 8 parts by mass of N, N-dimethylaniline, and 80 parts by mass of toluene were mixed and stirred to a uniform phase to prepare a phenol resin glue solution.
Viscosity, appearance and warpage tests were carried out according to the method described in example 1, the viscosity change curves are shown in fig. 1, and the appearance and warpage test results are shown in table 2. As can be seen from fig. 1, the viscosity of the semi-cured adhesive layer is maintained between 200mpa s and 700mpa s for at least 60s at a constant temperature of 120 ℃, and the adhesive layer has good flowability. As can be seen from table 2, the single-sided adhesive material has a good appearance, and a warpage of 1.78mm, which means that for the semi-cured adhesive layer made of the phenolic resin glue solution, partial internal stress can be released by hot pressing, so that the warpage of the single-sided adhesive material can be reduced, and bubbles and pits can be eliminated, thereby preparing the single-sided adhesive material with uniform defect-free and low warpage.
Example 7
The preparation method of this example is basically the same as that of example 1, except that: referring to Table 1, a polyimide film having a thickness of 0.1mm was used as the substrate.
Viscosity, appearance and warpage tests were carried out according to the method described in example 1, the viscosity change curves are shown in fig. 1, and the appearance and warpage test results are shown in table 2. As can be seen from fig. 1, the viscosity of the semi-cured adhesive layer can be maintained at 300 mpa-700 mpa-s for at least 60s at a constant temperature of 120 ℃, and the adhesive layer has good flowability. As can be seen from table 2, the single-sided adhesive material has a good appearance, and the warpage is 2.28mm, which means that when a polyimide film with a thickness of 0.1mm is used as a flexible substrate, part of internal stress can be released by hot pressing, so that the warpage of the single-sided adhesive material can be reduced, and bubbles and pits can be eliminated, thereby preparing the single-sided adhesive material with uniform defects and low warpage.
Example 8
This example is essentially the same as example 1 except for step (3): after the winding head of the coiled semi-finished product is pulled to be wound out, the coiled semi-finished product uniformly passes through an infrared radiation oven preheated to 120 ℃, and the total heating time of any point in the coiled semi-finished product is 10s; after heating for 5s, pressurizing by a roller set in an infrared radiation oven, wherein the pressure of the roller set is set to be 4kgf/cm 2 The total duration of pressurization is 5s; repeatedly performing the above conditions for 1 time on the coiled semi-finished product, and taking out and naturally cooling to room temperature to obtain the single-sided rubberized material.
Viscosity, appearance and warpage tests were carried out according to the method described in example 1, the viscosity change curves are shown in fig. 1, and the appearance and warpage test results are shown in table 2. As can be seen from fig. 1, the viscosity of the semi-cured adhesive layer can be maintained at 300 mpa-700 mpa-s for at least 60s at a constant temperature of 120 ℃, and the adhesive layer has good flowability. As can be seen from table 2, the single-sided rubberizing material has a good appearance, a warpage of 2.43mm, and it is shown that partial internal stress can be released by multiple hot pressing, so that the warpage of the single-sided rubberizing material can be reduced, and bubbles and pits can be eliminated, thereby preparing a uniform, defect-free, low-warpage single-sided rubberizing material.
Comparative example 1
This comparative example was prepared in substantially the same manner as in example 1 except that: the hot pressing treatment of the step (3) is not carried out.
Appearance and warp tests were performed with reference to the method described in example 1, the appearance test results are shown in fig. 3, and the warp test results are shown in table 3. As shown in table 3, the single-sided adhesive material had a poor appearance, a warpage of 16.92mm, which indicates that the internal stress of the single-sided adhesive material could not be released without hot pressing treatment, the warpage was high, and there were many bubbles and pits, and the appearance quality was poor.
TABLE 3 Hot pressing conditions and test results of comparative examples 1 to 7
Figure BDA0004030082480000131
Comparative example 2
This comparative example was substantially identical to the preparation method of example 1, except for the step (3): and (3) pulling the winding head of the coiled semi-finished product out, enabling the coiled semi-finished product to pass through an infrared radiation oven preheated to 120 ℃ at a constant speed, heating any point in the coiled semi-finished product for 35s, and taking out the coiled semi-finished product and naturally cooling to room temperature to obtain the single-sided rubberized material.
Viscosity, appearance and warpage tests were carried out according to the method described in example 1, the viscosity change curves are shown in fig. 1, and the appearance and warpage test results are shown in table 3. As can be seen from fig. 1, the viscosity of the semi-cured adhesive layer is maintained at 300mpa s to 700mpa s for at least 60s at a constant temperature of 120 ℃, and the adhesive layer has good flowability. As can be seen from table 3, the single-sided adhesive material has a poor appearance, a warpage of 9.41mm, and shows that the semi-cured adhesive layer has good flowability when heated only without pressurization, but cannot be tightly attached to the flexible substrate and the release film, so that bubbles and pits are easily generated, the appearance quality is poor, and the release of the internal stress of the semi-cured adhesive layer is not facilitated, so that the warpage of the single-sided adhesive material is high.
Comparative example 3
This comparative example was substantially identical to the preparation method of example 1, except for the step (3): pulling the winding head of the rolled semi-finished product, and allowing the semi-finished product to pass through the winding head at constant speed with pressure of 4kgf/cm 2 The roller set is pressurized, the total pressurizing time is 5s for any point in the rolled semi-finished product, and then the rolled semi-finished product is taken out and naturally cooled to room temperature, and single-sided rubberizing is preparedA material.
Appearance and warp tests were performed with reference to the method described in example 1, and the results are shown in table 3. As is clear from table 3, the single-sided adhesive material had a poor appearance, and the warpage was 16.78mm, indicating that the semi-cured adhesive layer did not soften by heat and flowed when pressurized alone without heating, and the air holes and pits were not filled, and the internal stress of the semi-cured adhesive layer was not released, resulting in a higher warpage of the single-sided adhesive material and serious appearance.
Comparative example 4
This comparative example was substantially identical to the preparation method of example 1, except for the step (3): after the winding head of the coiled semi-finished product is pulled to be wound out, the coiled semi-finished product uniformly passes through an infrared radiation oven preheated to 160 ℃, and the total heating time of any point in the coiled semi-finished product is 10s; after heating for 5s, pressurizing by a roller set in an infrared radiation oven, wherein the pressure of the roller set is set to be 16kgf/cm 2 The total duration of pressurization is 5s, and then the single-sided rubberized material is obtained after being taken out and naturally cooled to the room temperature.
Viscosity, appearance and warpage tests were carried out according to the method described in example 1, the viscosity change curves are shown in fig. 4, and the appearance and warpage test results are shown in table 3. As can be seen from fig. 4, the viscosity of the semi-cured gel layer was maintained below 100mpa x for at least 30s at a constant temperature of 160 ℃, and the flowability was excessive. As shown in table 3, the single-sided adhesive material has a poor appearance, and a warpage of 8.17mm, which indicates that the phenomenon of glue overflow and curing of the semi-cured adhesive layer can occur when hot pressing is performed at a temperature higher than the curing temperature, which is not beneficial to releasing the internal stress of the semi-cured adhesive layer, and reduces the adhesive capacity and appearance quality of the semi-cured adhesive layer, and contaminates hot pressing equipment.
Comparative example 5
This comparative example was substantially identical to the preparation method of example 1, except for the step (3): the winding head of the coiled semi-finished product is pulled to be wound out, and then the semi-finished product is uniformly passed through the pressure of 4kgf/cm 2 Passing through an infrared radiation oven preheated to 120 ℃ at a constant speed; for any point in the rolled semifinished product, it is pressurizedThe total duration is 5s, and the total duration of heating is 10s; and then taking out and naturally cooling to room temperature to obtain the single-sided rubberized material.
Appearance and warp tests were performed with reference to the method described in example 1, and the results are shown in table 3. As can be seen from table 3, the single-sided adhesive material has a poor appearance, and the warpage degree is 13.47mm, which indicates that the semi-cured adhesive layer can not fill up the defect by flowing when pressurized and can not release the internal stress by casting when heated when pressurized, so that the single-sided adhesive material has a higher warpage degree and a serious poor appearance.
Comparative example 6
This comparative example was substantially identical to the preparation method of example 1, except for the step (3): after the winding head of the coiled semi-finished product is pulled and wound out, the coiled semi-finished product firstly passes through an infrared radiation oven preheated to 120 ℃ at constant speed and then passes through a pressure of 4kgf/cm at constant speed 2 A roller set; for any point in the coiled semi-finished product, the total heating time is 10s, and the total pressurizing time is 5s; and then taking out and naturally cooling to room temperature to obtain the single-sided rubberized material.
Appearance and warp tests were performed with reference to the method described in example 1, and the results are shown in table 3. As can be seen from table 3, the single-sided adhesive material has a poor appearance, and the warpage degree is 8.76mm, which indicates that the semi-cured adhesive layer can not fill up the defect by flowing when being pressurized and can not release the internal stress by casting when being heated, so that the single-sided adhesive material has a higher warpage degree and a serious poor appearance.
Comparative example 7
This comparative example was substantially identical to the preparation method of example 1, except for the step (3): after the winding head of the coiled semi-finished product is pulled to be wound out, the coiled semi-finished product uniformly passes through an infrared radiation oven preheated to 70 ℃, and the total heating time of any point in the coiled semi-finished product is 10s; after heating for 5s, pressurizing by a roller set in an infrared radiation oven, wherein the pressure of the roller set is set to be 4kgf/cm 2 The total duration of pressurization is 5s, and then the single-sided rubberized material is obtained after being taken out and naturally cooled to the room temperature.
Viscosity, appearance and warpage tests were carried out according to the method described in example 1, the viscosity change curves are shown in fig. 4, and the appearance and warpage test results are shown in table 3. As can be seen from fig. 4, in the hot pressing step, the viscosity of the semi-cured adhesive layer was maintained at 1200mpa×s or more, and the fluidity was poor. As can be seen from table 3, the single-sided adhesive material has a poor appearance, and a warpage of 10.74mm, which indicates that the semi-cured adhesive layer is difficult to flow when pressed below the softening point, and is unfavorable for releasing the internal stress of the semi-cured adhesive layer and filling up the defects.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. The scope of the invention is therefore intended to be covered by the appended claims, and the description and drawings may be interpreted in accordance with the contents of the claims.

Claims (11)

1. The preparation method of the single-sided rubberizing material is characterized by comprising the following steps of:
providing a flexible substrate, and forming a semi-cured adhesive layer on the surface of the flexible substrate to obtain a semi-finished product;
pressing the semi-finished product at a temperature T to ensure that the viscosity of the semi-cured adhesive layer at the temperature T is kept between 100 mPa.s and 900 mPa.s for at least 30s, wherein the temperature T is not lower than the softening point of the semi-cured adhesive layer and lower than the curing temperature of the semi-cured adhesive layer.
2. The method for preparing a single-sided sizing material according to claim 1, wherein the temperature T is 80-140 ℃.
3. A method of preparing a single sided sizing material according to claim 2, wherein the pre-and/or post-pressing step further comprises the steps of: heating at the temperature T for 1 s-5 s.
4. The method of preparing a single sided sizing material of claim 1, wherein the pressing meets one or more of the following conditions:
1) The pressing force was 3kgf/cm 2 ～12kgf/cm 2 ；
2) The duration of the pressure application is 5-30 s;
3) The pressing equipment is a roller or a pressing plate.
5. The method of preparing a single sided sizing material of claim 4, wherein the pre-press further comprises one or more of the following steps:
1) Covering a release film on the surface of the semi-cured adhesive layer;
2) Coating a release agent on the surface of the roller or the pressing plate;
3) The roller or the pressing plate is made of a release material.
6. The method of claim 5, wherein the release film is one of a PET release film, an OPP release film, and a release paper.
7. The method for preparing a single-sided sizing material according to claim 1, wherein the thickness of the semi-cured adhesive layer is 10 μm to 100 μm.
8. The method of making a single sided sizing material of claim 1, wherein the flexible substrate is one or more of a polymeric film, a metal foil, a fiber reinforced composite.
9. The method for preparing a single-sided sizing material according to any one of claims 1 to 8, wherein the method for preparing a semi-cured glue layer comprises the steps of: and coating the thermosetting glue solution on the surface of the flexible substrate, and drying the flexible substrate at a temperature below the curing temperature to form the semi-cured glue layer.
10. The method of preparing a single sided sizing material of claim 9, wherein the thermosetting glue meets one or more of the following conditions:
1) The thermosetting glue solution is one or more of epoxy resin glue solution, unsaturated polyester resin glue solution, bismaleimide glue solution and phenolic resin glue solution;
2) The thermosetting glue solution comprises thermosetting resin and a curing agent;
3) The thermosetting glue solution comprises one or more of a curing accelerator, a thermoplastic resin and a solvent.
11. A single-sided sizing material, characterized in that it is produced by the method for producing a single-sided sizing material according to any one of claims 1 to 9.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002226818A (en) * 2001-02-06 2002-08-14 Hitachi Chem Co Ltd Thermosetting adhesive film
CN1685775A (en) * 2003-01-14 2005-10-19 松下电器产业株式会社 Circuit board and process for producing the same
CN101928444A (en) * 2010-08-20 2010-12-29 广东生益科技股份有限公司 Halogen-free thermosetting resin composition, prepreg and metal clad foil laminated plate manufactured by using same
CN103963378A (en) * 2014-03-05 2014-08-06 金安国纪科技股份有限公司 High thermal conductivity type metal-based copper clad laminate and preparation method thereof
CN105082669A (en) * 2015-09-23 2015-11-25 李会录 Production method of epoxy glass fiber cloth copper-clad plate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002226818A (en) * 2001-02-06 2002-08-14 Hitachi Chem Co Ltd Thermosetting adhesive film
CN1685775A (en) * 2003-01-14 2005-10-19 松下电器产业株式会社 Circuit board and process for producing the same
CN101928444A (en) * 2010-08-20 2010-12-29 广东生益科技股份有限公司 Halogen-free thermosetting resin composition, prepreg and metal clad foil laminated plate manufactured by using same
CN103963378A (en) * 2014-03-05 2014-08-06 金安国纪科技股份有限公司 High thermal conductivity type metal-based copper clad laminate and preparation method thereof
CN105082669A (en) * 2015-09-23 2015-11-25 李会录 Production method of epoxy glass fiber cloth copper-clad plate

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