CN114907804B - High-temperature-resistant high-heat-conductivity high-reflection flame-retardant structural adhesive and application thereof - Google Patents

High-temperature-resistant high-heat-conductivity high-reflection flame-retardant structural adhesive and application thereof Download PDF

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CN114907804B
CN114907804B CN202210753747.9A CN202210753747A CN114907804B CN 114907804 B CN114907804 B CN 114907804B CN 202210753747 A CN202210753747 A CN 202210753747A CN 114907804 B CN114907804 B CN 114907804B
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parts
structural adhesive
heat
flame
component
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CN114907804A (en
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聂彪
吕鹏
张梓晗
王勇
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Hefei Vigon Material Technologies Co ltd
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Hefei Vigon Material Technologies Co 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/017—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of aluminium or an aluminium alloy, another layer being formed of an alloy based on a non ferrous metal other than aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
    • 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
    • C09J11/04—Non-macromolecular additives inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/62—Arrangements for conducting electric current to or from the semiconductor body, e.g. lead-frames, wire-bonds or solder balls
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
    • H01L2933/0008—Processes
    • H01L2933/0033—Processes relating to semiconductor body packages
    • H01L2933/0066—Processes relating to semiconductor body packages relating to arrangements for conducting electric current to or from the semiconductor body

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  • Microelectronics & Electronic Packaging (AREA)
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Abstract

The invention discloses a high-temperature-resistant high-heat-conductivity high-reflection flame-retardant structural adhesive and application thereof, wherein the flame-retardant structural adhesive is prepared by mixing 3, 4-epoxy cyclohexane carboxylic acid-3 ',4' -epoxy cyclohexane methyl ester and epoxy polybutadiene resin with silicone rubber, and adding a heat-conducting filler, a flame retardant, titanium pigment, organic bentonite, phthalic anhydride, a boron trifluoride amine complex accelerator and some auxiliary agents. The flame-retardant structural adhesive can be used for glass-based minisize LED substrates, aluminum substrates and PCB boards, can firmly adhere copper foil and glass, copper foil and aluminum plates and PCB boards, and has the advantages of high heat conductivity and emissivity, good flame retardance, high temperature yellowing resistance, adjustable viscosity and wide applicability.

Description

High-temperature-resistant high-heat-conductivity high-reflection flame-retardant structural adhesive and application thereof
Technical Field
The invention relates to the field of electronic structural adhesives, in particular to a high-temperature-resistant high-heat-conductivity high-reflection flame-retardant structural adhesive.
Background
The structural adhesive is widely applied in the electronic field, can adhere glass and copper foil, metal and copper foil, and then etches a required circuit on the copper, and is used for manufacturing a circuit board of a glass substrate or an aluminum substrate.
The existing structural adhesives are usually cured by bisphenol a epoxy resins and amines, and have the following problems: contains a large amount of benzene ring double bonds and chlorides, has poor ageing resistance and high temperature resistance, and has serious yellowing when being contacted with air for 10 minutes at the temperature exceeding 200 ℃, the adhesive force is reduced and the adhesive is inflammable, and can not meet the application requirements of the display field of the high-end electronic industry; the epoxy resin and the amine have fast curing reaction and short operable time; the viscosity is high, the diluent is required to be added, the production efficiency is greatly reduced, and the environment is polluted.
In addition, the conventional structural adhesive has low thermal conductivity, poor heat dissipation in the using process, low reflectivity and great defects in the display field.
Therefore, research on the high-temperature-resistant high-heat-conductivity high-reflection structural adhesive applicable to the display field has important significance.
Disclosure of Invention
Based on the problems in the prior art, the invention provides the flame-retardant structural adhesive, and the structural adhesive has excellent high temperature resistance, high heat conduction and high reflection performance by regulating and controlling a formula system, so that the structural adhesive can be applied to the display field of high-end electronic industries such as miniLEDs, PCBs and the like.
The invention adopts the following technical scheme for realizing the purpose:
the utility model provides a fire-retardant structural adhesive of high temperature resistant high heat conduction high reflection which characterized in that: the structural adhesive consists of a component A and a component B:
the component A comprises the following raw materials in parts by mass:
10-30 parts of alicyclic epoxy resin,
10-30 parts of alicyclic epoxy resin II,
5-10 parts of silicon rubber,
20-40 parts of a heat conducting filler,
10-20 parts of a flame retardant agent,
8-16 parts of titanium dioxide,
0.1-1 part of leveling agent,
0.1 to 0.3 part of defoaming agent,
2-10 parts of a silane coupling agent,
1-3 parts of dispersing agent,
1-3 parts of organic bentonite;
the component B comprises the following raw materials in parts by mass:
99.5 to 99.9 portions of phthalic anhydride,
0.1-0.5 part of boron trifluoride amine complex accelerator;
the first alicyclic epoxy resin is 3, 4-epoxy cyclohexane carboxylic acid-3 ',4' -epoxy cyclohexane methyl ester, and the second alicyclic epoxy resin is epoxidized polybutadiene resin.
Further, the heat conducting filler is composed of diamond and modified spherical alumina according to the mass ratio of 1-1.5:1. The spherical alumina treated by the coupling agent can improve the wettability of the resin to powder and improve the anti-settling property. The conventional heat conductive filler in the adhesive has the disadvantages of small addition amount, low heat conductivity and large addition amount. The invention uses the powder diamond and the modified spherical alumina to match with the rutile type titanium dioxide filler, can have synergistic effect, can reach high heat conductivity 2W/(m.K) and high reflectivity with less serious adhesive force drop reaching 2kg/25mm under proper addition, and solves the pain points of poor heat conduction and low reflectivity of the adhesive in the high-end field.
Further, the flame retardant consists of aluminum hydroxide and nano antimony trioxide according to the mass ratio of 1.5-2.5:1. The flame retardant commonly used in the existing binder is halogen-containing, especially bromine-containing resin, which is yellow in color, and becomes more serious after high temperature, and phosphorus-containing and plasticizer volatilize at 290 ℃. The invention uses titanium dioxide with certain flame retardance and modified spherical alumina to produce synergistic effect by combining flame retardant aluminum hydroxide with high temperature resistance and no color change with nano antimony trioxide. Meanwhile, the silicon rubber resin generates silicon dioxide after being burnt, and has incombustibility. According to the invention, the silicon rubber is used for toughening and improving flame retardance, and the heat conduction powder and the flame retardant are matched to achieve the effects of high heat conduction, high reflection and flame retardance.
Further, the phthalic anhydride is at least one of methyltetrahydrophthalic anhydride MeTHPA, methylhexahydrophthalic anhydride MeHHPA and methylnadic anhydride MNA.
Further, the boron trifluoride amine complex accelerator is at least one of boron trifluoride-benzylamine complex and boron trifluoride-2, 4-dimethylaniline complex.
The configuration method of the flame-retardant structural adhesive comprises the following steps:
under the stirring state, firstly mixing the alicyclic epoxy resin I and the alicyclic epoxy resin II, heating to be dissolved at 80 ℃, then adding silicon rubber, heating to be dehydrated and condensed at 120 ℃ for 2 hours, then adding a silane coupling agent, a dispersing agent, organic bentonite, a leveling agent, a defoaming agent, titanium pigment, a heat-conducting filler and a flame retardant, uniformly stirring, and filtering to obtain a component A;
mixing phthalic anhydride and boron trifluoride amine complex, heating to dissolve at 80 ℃, and filtering to obtain a component B;
when in use, the component A and the component B are mixed according to the mass ratio of 1: and 0.3, uniformly mixing to obtain the high-temperature-resistant high-heat-conductivity high-reflection flame-retardant structural adhesive.
The flame-retardant structural adhesive can be used for bonding copper foil and a glass substrate, copper foil and an aluminum substrate or as an adhesive of a PCB.
Based on the flame-retardant structural adhesive, the invention further provides the glass-based minisize LED substrate, and the glass and the copper foil of the glass-based minisize LED substrate are bonded through the flame-retardant structural adhesive.
The beneficial effects of the invention are as follows:
1. in the formulation system of the present invention: the alicyclic epoxy resin I and the alicyclic epoxy resin II are obtained by oxidizing and modifying butadiene resin, all contain epoxy groups, and after being crosslinked with phthalic anhydride curing agents, the prepared polymer does not contain yellowing groups and is resistant to heating at 290 ℃ for 10 minutes and does not yellow. Because the flexible structure of the silicone rubber has incombustibility, after the silicone rubber is introduced into a molecular structure, the polymer has a strong rigid structure of the epoxy resin and has toughness and incombustibility of the silicone rubber by forming high-temperature-resistant resin with high Tg point, so that the stamping resistance after construction is improved, and the heat resistance and flame retardant property of the epoxy resin are improved. Meanwhile, the titanium dioxide and the heat conducting filler have interaction enhancement function and flame retardant effect, and aluminum hydroxide and nano antimony trioxide are matched, so that the heat conductivity and the reflection performance of the system are improved to a great extent, and the system has flame retardance. The structural adhesive solves the problem of serious yellowing caused by high-temperature heating in the existing adhesive, and solves the problems of poor adhesive property after a large amount of heat-conducting reflective filler is added or insufficient heat conductivity and low reflectivity after the heat-conducting reflective filler is added.
2. The structural adhesive has good adhesion to copper, glass, copper and aluminum plates, and has the thermal conductivity reaching 2W/(m.K), the reflectivity being higher than 80 percent and no yellowing after reflow soldering for 10 minutes at 290 ℃.
3. The solid content of the structural adhesive reaches more than 99 percent, and the structural adhesive almost has no VOC emission.
4. The structural adhesive A, B provided by the invention has long service life after being mixed and can be used within 24 hours.
5. The structural adhesive of the invention can be adjusted, is suitable for different construction processes such as roller coating, screen printing and the like, and has wide applicability. The adhesive can be made into low viscosity, glass fiber cloth is immersed in the adhesive in a dip-coating mode, is solidified for 10 minutes at 100 ℃ and is in a solid state but not solidified completely, then the dipped glass fiber cloth can be placed between a glass base, an aluminum substrate and a copper foil or replaces the structural adhesive used by the traditional PCB when the adhesive needs to be bonded, then the adhesive can be adhered under the same hot-pressing condition at 180 ℃ for 10 minutes, and the tensile strength after copper coating can be improved. The adhesive can also be made into a low-viscosity adhesive with a roller coating mode for constructing the copper foil, the glass substrate and the aluminum substrate, the adhesive is transferred to the glass and the aluminum plate by using a roller, the copper foil is covered on the glass and the aluminum plate, the vacuum is pumped for removing bubbles, and the adhesive can be cured after baking for 10 minutes at 180 ℃ to generate excellent adhesion. The high viscosity can also be adjusted to be constructed in a screen printing mode, copper foil is coated on glass and an aluminum plate to be vacuumized and bubble-removed, and the glass and aluminum plate can be cured after being baked for 10 minutes at 180 ℃ to generate excellent adhesion.
Detailed Description
The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
Reagents and apparatus used in the examples described below are commercially available.
In the following examples:
the silicone rubber may be selected from 107 silicone rubbers of hydroxyl terminated viscosity 5000cps from Shenzhen Ji Peng silicon fluorine materials Co., ltd.
The heat conducting filler is modified spherical alumina BED-011 of 3000 mesh powder diamond W5 of the company of the middle-hard abrasive mill, and the company of the new technology of Belde, suzhou.
The flame retardant is selected from aluminum hydroxide of Shandong morning Xue New Material Co., ltd and nano antimony trioxide of Shandong morning Xue New Material Co., ltd.
The phthalic anhydride is at least one of methyl tetrahydrophthalic anhydride MeTHPA (Zhejiang Shuangma Fine chemical Co., ltd.), methyl hexahydrophthalic anhydride MeHHPA (Jiaxing Co., ltd.) and methyl nadic anhydride MNA (Yongtaifeng chemical Co., ltd.).
The titanium dioxide is selected from DuPont R-902+.
The leveling agent is at least one selected from Digao 450 and Pick BYK-333.
The defoamer is at least one selected from the group consisting of Pick BYK-066N, BYK-057 and BYK-368N.
The silane coupling agent is at least one selected from KH-550 (3-aminopropyl triethoxysilane), KH-560 (3-glycidoxy trimethoxysilane), KH-570 (gamma- (methacryloyloxy) propyl trimethoxysilane), KH-580 (3-mercaptopropyl trimethoxysilane) and KH-590 (3-mercaptopropyl triethoxysilane) of new materials, wuhan An Ruike.
The dispersant is at least one of deep bamboo SN-2011, SN-2311 and SN-2041A.
The organic bentonite is at least one selected from Haimines SD-2 and Crimines 62.
The boron trifluoride amine complex promoter is selected from boron trifluoride-benzylamine complex (H600 of Hui Cheng, chuzhou), boron trifluoride-2, 4-dimethylaniline complex (H602 of Hui Cheng, chuzhou)
The alicyclic epoxy resin is prepared by heating and pressurizing butadiene and acrolein to synthesize cyclohexene formaldehyde, and performing disproportionation esterification and epoxidation reaction, wherein the synthesis steps are as follows: in a 1000mL beaker, 2.18. 2.18g H are added in turn 3 PO 4 、1.48g NaH 2 PO 4 ·2H 2 O、12.0gNa 2 WO 4 ·2H 2 O、360mL H 2 O 2 (35%) and stirring at room temperature for 10min to dissolveTransfer to a constant pressure dropping funnel after all. 200.0g of 3, 4-cyclohexenyl methyl formate, 680mL of toluene and 9.10g of dodecyl trimethyl ammonium bisulfate are sequentially put into a 2000mL three-neck flask, the stirring speed is 1200 turns/min, the temperature is raised to 90 ℃, the mixed liquid in a dropping funnel is started to be dropped for 2 hours, and the reaction is continued for 3 hours after the dropping. After the reaction, the mixture was transferred to a 2L separating liquid and was drained, an organic phase was separated, and the mixture was washed with 200mL of water for 15 minutes, the organic phase was separated, and was spin-distilled to remove the solvent (6 mmHg,50 ℃ C.), and the colorless liquid was obtained by vacuum distillation at 175 to 185 ℃ C. By a mechanical pump, which was about 182g, and 3, 4-epoxycyclohexane carboxylic acid-3 ',4' -epoxycyclohexane methyl ester was designated as alicyclic epoxy resin I.
The alicyclic epoxy resin II is obtained by epoxidation of double bonds in liquid polybutadiene resin molecules with relative molecular mass of 3000-5000, and the synthesis steps are as follows: 300.0g of liquid polybutadiene resin with low average relative molecular weight, 860mL of toluene and 10.90g of dodecyl trimethyl ammonium bisulfate are sequentially put into a 2000mL three-neck flask, the stirring speed is 1200 revolutions per minute, the temperature is raised to 100 ℃, and 2.18g H is started to be added dropwise 3 PO 4 、1.48g NaH 2 PO 4 ·2H 2 O、12.0g Na 2 WO 4 ·2H 2 O、360mLH 2 O 2 (35%) of the mixed liquid was added dropwise for 2 hours, and the reaction was continued for 3 hours after the addition. After the reaction, the mixture was transferred to a 2L separating liquid and was drained, an organic phase was separated, the mixture was washed with 300mL of water for 20 minutes, the organic phase was separated, the mixture was spin-distilled to remove the solvent (6 mmHg,50 ℃ C.), the colorless liquid was obtained by distillation under reduced pressure at 175 to 185 ℃ C. By a mechanical pump, about 272g of the alicyclic resin was filled in a 500mL beaker, and the solid alicyclic epoxy resin epoxidized polybutadiene resin was obtained after cooling, and was designated as alicyclic epoxy resin II. The molecular structure of the epoxy resin has epoxy group, hydroxyl group and ester side chain as linear macromolecules, and simultaneously has polybutadiene rubber structure and epoxy resin structure, so that the epoxy resin has good impact toughness and bonding property, small viscosity after being mixed with a curing agent, convenient operation and good manufacturability, the cured product has good heat resistance, the thermal deformation temperature can reach more than 200 ℃, and the strength retention rate is very outstanding at high temperature.
The method for preparing the flame-retardant structural adhesive in the following embodiment comprises the following steps:
in a three-neck flask, the alicyclic epoxy resin I and the alicyclic epoxy resin II are firstly mixed and heated to be dissolved at 80 ℃ (stirring at a high speed in the process), then the silicone rubber is added, and the mixture is heated, dehydrated and condensed at 120 ℃ for 2 hours (stirring at a high speed in the process), so that transparent liquid is obtained. And (3) placing the obtained transparent liquid in a corrosion-resistant tank, placing under a dispersing machine, rotating the dispersing machine for 1000 revolutions per minute, and then adding a silane coupling agent, a dispersing agent, organic bentonite, a leveling agent, a defoaming agent, titanium pigment, a heat-conducting filler and a flame retardant. After the addition is completed, the rotating speed of a dispersing machine is increased to 2000 rpm, the dispersion is carried out for 30 minutes, and then a 100-mesh filter cloth is used for filtering, so that the component A is obtained.
Phthalic anhydride and boron trifluoride amine complex were mixed and heated to dissolve at 80℃and filtered through 200 mesh filter cloth to obtain component B.
When in use, the component A and the component B are mixed according to the mass ratio of 1: and 0.3, uniformly mixing to obtain the high-temperature-resistant high-heat-conductivity high-reflection flame-retardant structural adhesive.
Example 1
The embodiment provides a flame-retardant structural adhesive suitable for dip-coating glass fiber cloth to prepare prepregs, which comprises the following formula:
the component A comprises the following raw materials in parts by mass:
30 parts of alicyclic epoxy resin,
10 parts of alicyclic epoxy resin II,
5 parts of hydroxyl-terminated silicone rubber,
22 parts of heat-conducting filler (11 parts of powder diamond, 11 parts of modified spherical alumina powder),
16 parts of flame retardant (11 parts of aluminum hydroxide powder, 5 parts of nano antimony trioxide powder),
11 parts of R-902+ titanium dioxide,
0.3 part of BYK-333 leveling agent,
BYK-057 defoamer 0.1 part,
2 parts of KH-560 coupling agent,
1.8 parts of SN-2311 dispersing agent,
SD-2 organic bentonite 1.8 parts.
The component B comprises the following raw materials in parts by mass:
99.8 parts of methyl hexahydrophthalic anhydride,
0.2 part of boron trifluoride-benzylamine complex.
Example 2
The embodiment provides a flame-retardant structural adhesive with high thermal conductivity suitable for dip-coating glass fiber cloth to manufacture prepregs, which comprises the following formula:
the component A comprises the following raw materials in parts by mass:
30 parts of alicyclic epoxy resin,
10 parts of alicyclic epoxy resin II,
5 parts of hydroxyl-terminated silicone rubber,
25 parts of heat-conducting filler (14 parts of powder diamond, 11 parts of modified spherical alumina powder),
15 parts of flame retardant (10 parts of aluminum hydroxide powder, 5 parts of nano antimony trioxide powder),
9 parts of R-902+ titanium dioxide,
0.3 part of BYK-333 leveling agent,
BYK-057 defoamer 0.1 part,
2 parts of KH-560 coupling agent,
1.8 parts of SN-2311 dispersing agent,
SD-2 organic bentonite 1.8 parts.
The component B comprises the following raw materials in parts by mass:
99.8 parts of methyl hexahydrophthalic anhydride,
0.2 part of boron trifluoride-benzylamine complex.
Example 3
The embodiment provides a flame-retardant structural adhesive with high reflectivity, which is suitable for dip-coating glass fiber cloth to manufacture prepregs, and comprises the following components in percentage by weight:
the component A comprises the following raw materials in parts by mass:
30 parts of alicyclic epoxy resin,
10 parts of alicyclic epoxy resin II,
5 parts of hydroxyl-terminated silicone rubber,
20 parts of heat-conducting filler (10 parts of powder diamond and 10 parts of modified spherical alumina powder),
15 parts of flame retardant (10 parts of aluminum hydroxide powder, 5 parts of nano antimony trioxide powder),
14 parts of R-902+titanium dioxide,
0.3 part of BYK-333 leveling agent,
BYK-057 defoamer 0.1 part,
2 parts of KH-560 coupling agent,
1.8 parts of SN-2311 dispersing agent,
SD-2 organic bentonite 1.8 parts.
The component B comprises the following raw materials in parts by mass:
99.8 parts of methyl hexahydrophthalic anhydride,
0.2 part of boron trifluoride-benzylamine complex.
Example 4
The embodiment provides a flame-retardant structural adhesive with good flame-retardant effect, which is suitable for dip-coating glass fiber cloth to prepare prepregs, and comprises the following formula:
the component A comprises the following raw materials in parts by mass:
30 parts of alicyclic epoxy resin,
10 parts of alicyclic epoxy resin II,
5 parts of hydroxyl-terminated silicone rubber,
20 parts of heat-conducting filler (10 parts of powder diamond and 10 parts of modified spherical alumina powder),
19 parts of flame retardant (12.5 parts of aluminum hydroxide powder, 6.5 parts of nano antimony trioxide powder),
10 parts of R-902+ titanium dioxide,
0.3 part of BYK-333 leveling agent,
BYK-057 defoamer 0.1 part,
2 parts of KH-560 coupling agent,
1.8 parts of SN-2311 dispersing agent,
SD-2 organic bentonite 1.8 parts.
The component B comprises the following raw materials in parts by mass:
99.8 parts of methyl hexahydrophthalic anhydride,
0.2 part of boron trifluoride-benzylamine complex.
Example 5
The embodiment provides a flame-retardant structural adhesive suitable for roller coating, which comprises the following components in percentage by weight:
the component A comprises the following raw materials in parts by mass:
23 parts of alicyclic epoxy resin,
17 parts of alicyclic epoxy resin II,
5 parts of hydroxyl-terminated silicone rubber,
22 parts of heat-conducting filler (11 parts of powder diamond, 11 parts of modified spherical alumina powder),
16 parts of flame retardant (11 parts of aluminum hydroxide powder, 5 parts of nano antimony trioxide powder),
11 parts of R-902+ titanium dioxide,
0.25 part of BYK-333 leveling agent,
BYK-057 defoamer 0.15 parts,
2 parts of KH-560 coupling agent,
1.8 parts of SN-2311 dispersing agent,
SD-2 organic bentonite 1.8 parts.
The component B comprises the following raw materials in parts by mass:
99.8 parts of methyl hexahydrophthalic anhydride,
0.2 part of boron trifluoride-benzylamine complex.
Example 6
The embodiment provides a flame-retardant structural adhesive with high thermal conductivity, which is suitable for roller coating, and comprises the following components in percentage by weight:
the component A comprises the following raw materials in parts by mass:
23 parts of alicyclic epoxy resin,
17 parts of alicyclic epoxy resin II,
5 parts of hydroxyl-terminated silicone rubber,
25 parts of heat-conducting filler (14 parts of powder diamond, 11 parts of modified spherical alumina powder),
15 parts of flame retardant (10 parts of aluminum hydroxide powder, 5 parts of nano antimony trioxide powder),
9 parts of R-902+ titanium dioxide,
0.25 part of BYK-333 leveling agent,
BYK-057 defoamer 0.15 parts,
2 parts of KH-560 coupling agent,
1.8 parts of SN-2311 dispersing agent,
SD-2 organic bentonite 1.8 parts.
The component B comprises the following raw materials in parts by mass:
99.8 parts of methyl hexahydrophthalic anhydride,
0.2 part of boron trifluoride-benzylamine complex.
Example 7
The embodiment provides a high-reflectivity flame-retardant structural adhesive suitable for roller coating, which comprises the following components in percentage by weight:
the component A comprises the following raw materials in parts by mass:
23 parts of alicyclic epoxy resin,
17 parts of alicyclic epoxy resin II,
5 parts of hydroxyl-terminated silicone rubber,
20 parts of heat-conducting filler (10 parts of powder diamond and 10 parts of modified spherical alumina powder),
15 parts of flame retardant (10 parts of aluminum hydroxide powder, 5 parts of nano antimony trioxide powder),
14 parts of R-902+titanium dioxide,
0.25 part of BYK-333 leveling agent,
BYK-057 defoamer 0.15 parts,
2 parts of KH-560 coupling agent,
1.8 parts of SN-2311 dispersing agent,
SD-2 organic bentonite 1.8 parts.
The component B comprises the following raw materials in parts by mass:
99.8 parts of methyl hexahydrophthalic anhydride,
0.2 part of boron trifluoride-benzylamine complex.
Example 8
The embodiment provides a flame-retardant structural adhesive with good flame-retardant effect, which is suitable for roller coating, and comprises the following components in percentage by weight:
the component A comprises the following raw materials in parts by mass:
30 parts of alicyclic epoxy resin,
10 parts of alicyclic epoxy resin II,
5 parts of hydroxyl-terminated silicone rubber,
20 parts of heat-conducting filler (10 parts of powder diamond and 10 parts of modified spherical alumina powder),
19 parts of flame retardant (12.5 parts of aluminum hydroxide powder, 6.5 parts of nano antimony trioxide powder),
10 parts of R-902+ titanium dioxide,
0.25 part of BYK-333 leveling agent,
BYK-057 defoamer 0.15 parts,
2 parts of KH-560 coupling agent,
1.8 parts of SN-2311 dispersing agent,
SD-2 organic bentonite 1.8 parts.
The component B comprises the following raw materials in parts by mass:
99.8 parts of methyl hexahydrophthalic anhydride,
0.2 part of boron trifluoride-benzylamine complex.
Example 9
The embodiment provides a flame-retardant structural adhesive suitable for screen printing, which comprises the following components in percentage by weight:
the component A comprises the following raw materials in parts by mass:
16 parts of alicyclic epoxy resin,
24 parts of alicyclic epoxy resin II,
5 parts of hydroxyl-terminated silicone rubber,
22 parts of heat-conducting filler (11 parts of powder diamond, 11 parts of modified spherical alumina powder),
16 parts of flame retardant (11 parts of aluminum hydroxide powder, 5 parts of nano antimony trioxide powder),
11 parts of R-902+ titanium dioxide,
0.2 part of Digao 450 flatting agent,
0.2 part of BYK-066N defoamer,
2 parts of KH-560 coupling agent,
1.8 parts of SN-2311 dispersing agent,
1.8 parts of SD-2 organic bentonite;
the component B comprises the following raw materials in parts by mass:
99.8 parts of methyl hexahydrophthalic anhydride,
0.2 part of boron trifluoride-benzylamine complex.
Example 10
The embodiment provides a flame-retardant structural adhesive with high thermal conductivity, which is suitable for screen printing, and comprises the following components in percentage by weight:
the component A comprises the following raw materials in parts by mass:
16 parts of alicyclic epoxy resin,
24 parts of alicyclic epoxy resin II,
5 parts of hydroxyl-terminated silicone rubber,
25 parts of heat-conducting filler (14 parts of powder diamond, 11 parts of modified spherical alumina powder),
15 parts of flame retardant (10 parts of aluminum hydroxide powder, 5 parts of nano antimony trioxide powder),
9 parts of R-902+ titanium dioxide,
0.2 part of Digao 450 flatting agent,
0.2 part of BYK-066N defoamer,
2 parts of KH-560 coupling agent,
1.8 parts of SN-2311 dispersing agent,
SD-2 organic bentonite 1.8 parts.
The component B comprises the following raw materials in parts by mass:
99.8 parts of methyl hexahydrophthalic anhydride,
0.2 part of boron trifluoride-benzylamine complex.
Example 11
The embodiment provides a flame-retardant structural adhesive with high reflectivity, which is suitable for screen printing, and the formula of the flame-retardant structural adhesive is as follows:
the component A comprises the following raw materials in parts by mass:
16 parts of alicyclic epoxy resin,
24 parts of alicyclic epoxy resin II,
5 parts of hydroxyl-terminated silicone rubber,
20 parts of heat-conducting filler (10 parts of powder diamond and 10 parts of modified spherical alumina powder),
15 parts of flame retardant (10 parts of aluminum hydroxide powder, 5 parts of nano antimony trioxide powder),
14 parts of R-902+titanium dioxide,
0.2 part of Digao 450 flatting agent,
0.2 part of BYK-066N defoamer,
2 parts of KH-560 coupling agent,
1.8 parts of SN-2311 dispersing agent,
1.8 parts of SD-2 organic bentonite;
the component B comprises the following raw materials in parts by mass:
99.8 parts of methyl hexahydrophthalic anhydride,
0.2 part of boron trifluoride-benzylamine complex.
Example 12
The embodiment provides a flame-retardant structural adhesive with outstanding flame-retardant effect, which is suitable for dip-coating glass fiber cloth, and comprises the following formula:
the component A comprises the following raw materials in parts by mass:
16 parts of alicyclic epoxy resin,
24 parts of alicyclic epoxy resin II,
5 parts of hydroxyl-terminated silicone rubber,
20 parts of heat-conducting filler (10 parts of powder diamond and 10 parts of modified spherical alumina powder),
19 parts of flame retardant (12.5 parts of aluminum hydroxide powder, 6.5 parts of nano antimony trioxide powder),
10 parts of R-902+ titanium dioxide,
0.2 part of Digao 450 flatting agent,
0.2 part of BYK-066N defoamer,
2 parts of KH-560 coupling agent,
1.8 parts of SN-2311 dispersing agent,
1.8 parts of SD-2 organic bentonite;
the component B comprises the following raw materials in parts by mass:
99.8 parts of methyl hexahydrophthalic anhydride,
0.2 part of boron trifluoride-benzylamine complex.
Example 13
The embodiment provides a flame-retardant structural adhesive suitable for dip-coating glass fiber cloth to prepare prepregs, which comprises the following formula:
the component A comprises the following raw materials in parts by mass:
30 parts of alicyclic epoxy resin,
10 parts of alicyclic epoxy resin II,
5 parts of hydroxyl-terminated silicone rubber,
22 parts of a heat-conducting filler, namely powder diamond,
16 parts of flame retardant, namely aluminum hydroxide powder,
11 parts of R-902+ titanium dioxide,
0.3 part of BYK-333 leveling agent,
BYK-057 defoamer 0.1 part,
2 parts of KH-560 coupling agent,
1.8 parts of SN-2311 dispersing agent,
1.8 parts of SD-2 organic bentonite;
the component B comprises the following raw materials in parts by mass:
99.8 parts of methyl hexahydrophthalic anhydride,
0.2 part of boron trifluoride-benzylamine complex.
Example 14
The embodiment provides a flame-retardant structural adhesive suitable for dip-coating glass fiber cloth to prepare prepregs, which comprises the following formula:
the component A comprises the following raw materials in parts by mass:
30 parts of alicyclic epoxy resin,
10 parts of alicyclic epoxy resin II,
5 parts of hydroxyl-terminated silicone rubber,
22 parts of heat-conducting filler and modified spherical alumina powder,
16 parts of flame retardant nano antimony trioxide powder,
11 parts of R-902+ titanium dioxide,
0.3 part of BYK-333 leveling agent,
BYK-057 defoamer 0.1 part,
2 parts of KH-560 coupling agent,
1.8 parts of SN-2311 dispersing agent,
SD-2 organic bentonite 1.8 parts.
The component B comprises the following raw materials in parts by mass:
99.8 parts of methyl hexahydrophthalic anhydride,
0.2 part of boron trifluoride-benzylamine complex.
Example 15
The embodiment provides a flame-retardant structural adhesive suitable for roller coating, which comprises the following components in percentage by weight:
the component A comprises the following raw materials in parts by mass:
23 parts of alicyclic epoxy resin,
17 parts of alicyclic epoxy resin II,
5 parts of hydroxyl-terminated silicone rubber,
22 parts of a heat-conducting filler, namely powder diamond,
16 parts of flame retardant aluminum hydroxide powder,
11 parts of R-902+ titanium dioxide,
0.25 part of BYK-333 leveling agent,
BYK-057 defoamer 0.15 parts,
2 parts of KH-560 coupling agent,
1.8 parts of SN-2311 dispersing agent,
SD-2 organic bentonite 1.8 parts.
The component B comprises the following raw materials in parts by mass:
99.8 parts of methyl hexahydrophthalic anhydride,
0.2 part of boron trifluoride-benzylamine complex,
0.2 part of boron trifluoride-benzylamine complex.
Example 16
The embodiment provides a flame-retardant structural adhesive suitable for roller coating, which comprises the following components in percentage by weight:
the component A comprises the following raw materials in parts by mass:
23 parts of alicyclic epoxy resin,
17 parts of alicyclic epoxy resin II,
5 parts of hydroxyl-terminated silicone rubber,
22 parts of heat-conducting filler and modified spherical alumina powder,
16 parts of flame retardant nano antimony trioxide powder,
11 parts of R-902+ titanium dioxide,
0.25 part of BYK-333 leveling agent,
BYK-057 defoamer 0.15 parts,
2 parts of KH-560 coupling agent,
1.8 parts of SN-2311 dispersing agent,
1.8 parts of SD-2 organic bentonite;
the component B comprises the following raw materials in parts by mass:
99.8 parts of methyl hexahydrophthalic anhydride,
0.2 part of boron trifluoride-benzylamine complex,
0.2 part of boron trifluoride-benzylamine complex.
Example 17
The embodiment provides a flame-retardant structural adhesive suitable for screen printing, which comprises the following components in percentage by weight:
the component A comprises the following raw materials in parts by mass:
16 parts of alicyclic epoxy resin,
24 parts of alicyclic epoxy resin II,
5 parts of hydroxyl-terminated silicone rubber,
22 parts of a heat-conducting filler, namely powder diamond,
16 parts of flame retardant aluminum hydroxide powder,
11 parts of R-902+ titanium dioxide,
0.2 part of Digao 450 flatting agent,
0.2 part of BYK-066N defoamer,
2 parts of KH-560 coupling agent,
1.8 parts of SN-2311 dispersing agent,
1.8 parts of SD-2 organic bentonite;
the component B comprises the following raw materials in parts by mass:
99.8 parts of methyl hexahydrophthalic anhydride,
0.2 part of boron trifluoride-benzylamine complex.
Example 18
The embodiment provides a flame-retardant structural adhesive suitable for screen printing, which comprises the following components in percentage by weight:
the component A comprises the following raw materials in parts by mass:
16 parts of alicyclic epoxy resin,
24 parts of alicyclic epoxy resin II,
5 parts of hydroxyl-terminated silicone rubber,
22 parts of heat-conducting filler and modified spherical alumina powder,
16 parts of flame retardant nano antimony trioxide powder,
11 parts of R-902+ titanium dioxide,
0.2 part of Digao 450 flatting agent,
0.2 part of BYK-066N defoamer,
2 parts of KH-560 coupling agent,
1.8 parts of SN-2311 dispersing agent,
SD-2 organic bentonite 1.8 parts.
The component B comprises the following raw materials in parts by mass:
99.8 parts of methyl hexahydrophthalic anhydride,
0.2 part of boron trifluoride-benzylamine complex.
The mass ratio of the component A to the component B in the embodiment is 1: and 0.3, mixing and stirring uniformly.
The performance test methods of the gums obtained in examples 1, 2, 3,4, 13 and 14 were as follows: and (3) soaking glass fiber cloth into glue, taking out for semi-curing, cutting into strips with the width of 25mm, hot-pressing between copper foil and glass or between the copper foil and an aluminum plate subjected to oil removal, acid washing and passivation at 180 ℃, curing for 10 minutes, and testing the 180-degree peeling strength. The reflectivity was measured on glass substrates, which were coated onto 2 glass sheets by roll coating, one sheet cured at 180℃for 10 minutes, one sheet baked at 290℃for 10 minutes, and the reflectivity was measured for 10 minutes in comparison with 10 minutes for 290℃and 10 minutes for 180 ℃. The color difference was applied to 2 aluminum plates by roll coating, one sheet cured at 180℃for 10 minutes, one sheet baked at 290℃for 10 minutes, and color difference values of 10 minutes at 290℃and 10 minutes at 180℃were compared.
The performance test methods of the gums obtained in examples 5, 6, 7, 8, 15 and 16 were as follows: and (3) coating the glass and the aluminum plate subjected to oil removal, acid washing and passivation by using a coil bar roller, respectively coating a copper foil with the thickness of 25mm, vacuumizing and defoaming, placing the copper foil for baking at 180 ℃ for 10 minutes, and testing 180 DEG peel strength after cooling. The reflectivity was measured on glass substrates, which were coated onto 2 glass sheets by roll coating, one sheet cured at 180℃for 10 minutes, one sheet baked at 290℃for 10 minutes, and the reflectivity was measured for 10 minutes in comparison with 10 minutes for 290℃and 10 minutes for 180 ℃. Color difference test roller is coated on an aluminum plate, 2 pieces of the aluminum plate are not coated with copper foil, the aluminum plate is cured for 10 minutes at 180 ℃, and one piece of the aluminum plate is baked for 10 minutes at 290 ℃ to compare the reflectivity and yellowing of the aluminum plate with normal curing.
The performance test methods of the gums obtained in examples 9, 10, 11, 12, 17 and 18 were as follows: screen printing on glass and aluminium plate with 150 mesh screen, vacuum defoaming with 25mm copper foil, baking at 180 deg.c for 10min, cooling and testing 180 deg.c peeling strength. Reflectivity was measured on glass substrates using 150 mesh screen printing on 2 sheets of glass, one sheet cured at 180 ℃ for 10 minutes, one sheet baked at 290 ℃ for 10 minutes, and the reflectivity was compared to 10 minutes for 290 ℃ and 10 minutes for 180 ℃. Color difference test 150 mesh screen printing was performed on 2 sheets of non-copper foil coated aluminum plate, cured at 180 ℃ for 10 minutes, and one sheet was baked at 290 ℃ for 10 minutes to compare reflectance and yellowing with normal curing. Wherein the thickness of the 150-mesh printing adhesive is 18+/-1 mu m, and the thickness of the roller adhesive is equal to the thickness of the 16-20 mu m range by adjusting the roller coating process to compare the reflectivity and the yellowing.
The thermal conductivity of all the examples is that glue blocks with the thickness higher than 1cm are cast in a mould with the thickness of 10cm multiplied by 10cm, after the solidification is completed, the surface is ground to be smooth by a grinding machine, a layer of heat conduction silicone grease is coated on the upper surface and the lower surface, and the heat conduction silicone grease is placed in a thermal conductivity meter for testing the thermal conductivity. All examples flame retardant test samples were made 5mm thick, 13mm wide and 125mm long.
The test results are shown in the following table:
Figure BDA0003719111680000161
Figure BDA0003719111680000171
in the table:
1. the viscosity test method comprises the following steps: viscosity was measured using a six-speed rotational viscometer of the epoxy adhesive system at 25℃using a Shanghai Di also Mum NDJ-8S digital display viscometer.
2. 180 DEG peel strength test method: the 180℃peel strength measurement was performed in accordance with GB/T2790-1995 standard. Testing was performed using a wisdom ZQ-990LA universal tester.
In the examples, the 180 DEG peel strength exceeded 2kg/25mm, which is an excellent peel strength.
3. The thermal conductivity testing method comprises the following steps: the measurement of thermal conductivity is performed in accordance with ASTM D5470 standard. The test was performed using a DRPL-2 thermal conductivity tester of the Hunan family. In the examples, a composite heat-conducting filler and a single heat-conducting filler were used, respectively, and the thermal conductivity of the examples of the composite heat-conducting filler was more than 2W/(mK).
Compared with the embodiment, the heat conductivity of the heat conducting filler is reduced by singly using the heat conducting filler, and the powder with different particle sizes is matched with each other to achieve better effect. The powder diamond has high heat conductivity but large particle size, the gap between the powder and the powder after solidification is large and the heat conductivity is low, the particle size of the modified alumina powder is small but the heat conductivity is inferior to that of the powder diamond, the two powder are compounded, and the modified alumina powder can be filled around the powder diamond to improve the heat conductivity. The thermal conductivity of the composite heat conducting powder meets the use requirement of high-end electronic products, and solves the problem that most adhesives have poor heat conduction in the electronic products and cause aging deformation due to slow heat dissipation and local high temperature.
4. The reflectivity testing method comprises the following steps: the preparation of the test sample is carried out strictly in accordance with the specifications of the relevant national standard GB 9271-1988. The measurement was carried out using a smart Cogeneration C84-III reflectometer. After reflow soldering for 10 minutes at 290 ℃, the reflectivity is slightly reduced, and the heat resistance and the oxidation resistance are good.
5. The flame retardant test method comprises the following steps: UL94 flame retardance testing method
HB grade, horizontal combustion test;
V0-V2 grade, vertical combustion test;
HB: the lowest flame retardant rating in the UL94 standard. It is required that for samples 3 to 13mm thick, the burn rate is less than 40 mm per minute; a sample less than 3mm thick, a burn rate of less than 70 mm per minute; or extinguished before a 100 mm mark;
v-2: after two 10 second burn tests on the samples, the flame extinguished within 60 seconds. The cotton wool below 30cm can be ignited.
V-1: after two 10 second burn tests on the samples, the flame extinguished within 60 seconds. The cotton wool below 30cm cannot be ignited.
V-0: after two 10 second burn tests on the samples, the flame extinguished within 10 seconds.
By comparing different flame retardant powder composites with single use, aluminum hydroxide has better flame retardance, and nano antimony trioxide is an auxiliary flame retardant which can play better flame retardant effect only by matching with other flame retardant materials. The flame retardance after compounding is better than the effect of singly using one flame retardant.
6. The color difference testing method comprises the following steps: the color of the coating film was measured by a color difference meter according to GB 11186.1-1989. The test was performed using a Sanen time SC-10 color difference meter. Δe represents the magnitude of the total color difference:
ΔE in the range of 0-0.25 represents very little or no, an ideal match;
ΔE in the range of 0.25-0.5 represents a slight, acceptable match;
ΔE in the range of 0.5-1.0 represents tiny to medium, acceptable in some applications;
ΔE in the range of 1.0-2.0 represents moderate, acceptable in a particular application;
ΔE represents a gap in the range of 2.0-4.0, which is acceptable in a particular application;
ΔE above 4.0 represents a very large, unacceptable in most applications.
It can be seen that the sample wafer subjected to reflow soldering at 290 ℃ has small integrated chromatic aberration compared with the sample wafer not subjected to reflow soldering, and is acceptable.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.

Claims (6)

1. The utility model provides a fire-retardant structural adhesive of high temperature resistant high heat conduction high reflection which characterized in that: the structural adhesive consists of a component A and a component B:
the component A comprises the following raw materials in parts by mass:
10-30 parts of alicyclic epoxy resin,
10-30 parts of alicyclic epoxy resin II,
5-10 parts of silicon rubber,
20-40 parts of a heat conducting filler,
10-20 parts of a flame retardant agent,
8-16 parts of titanium dioxide,
0.1-1 part of leveling agent,
0.1 to 0.3 part of defoaming agent,
2-10 parts of a silane coupling agent,
1-3 parts of dispersing agent,
1-3 parts of organic bentonite;
the component B comprises the following raw materials in parts by mass:
99.5 to 99.9 portions of phthalic anhydride,
0.1-0.5 part of boron trifluoride amine complex accelerator;
the first alicyclic epoxy resin is 3, 4-epoxycyclohexane carboxylic acid-3 ',4' -epoxycyclohexane methyl ester, and the second alicyclic epoxy resin is epoxidized polybutadiene resin;
the heat-conducting filler consists of diamond and modified spherical alumina according to the mass ratio of 1-1.5:1;
the flame retardant consists of aluminum hydroxide and nano antimony trioxide according to the mass ratio of 1.5-2.5:1.
2. The high temperature and heat resistant high reflection flame retardant structural adhesive of claim 1, wherein: the phthalic anhydride is at least one of methyl tetrahydrophthalic anhydride MeTHPA, methyl hexahydrophthalic anhydride MeHHPA and methyl nadic anhydride MNA.
3. The high temperature and heat resistant high reflection flame retardant structural adhesive of claim 1, wherein: the boron trifluoride amine complex accelerator is at least one of boron trifluoride-benzylamine complex and boron trifluoride-2, 4-dimethylaniline complex.
4. A method for preparing the flame retardant structural adhesive according to any one of claims 1 to 3, characterized in that:
under the stirring state, firstly mixing the alicyclic epoxy resin I and the alicyclic epoxy resin II, heating to be dissolved at 80 ℃, then adding silicon rubber, heating to be dehydrated and condensed at 120 ℃ for 2 hours, then adding a silane coupling agent, a dispersing agent, organic bentonite, a leveling agent, a defoaming agent, titanium pigment, a heat-conducting filler and a flame retardant, uniformly stirring, and filtering to obtain a component A;
mixing phthalic anhydride and boron trifluoride amine complex, heating to dissolve at 80 ℃, and filtering to obtain a component B;
when in use, the component A and the component B are mixed according to the mass ratio of 1: and 0.3, uniformly mixing to obtain the high-temperature-resistant high-heat-conductivity high-reflection flame-retardant structural adhesive.
5. Use of a flame retardant structural adhesive according to any one of claims 1 to 3, characterized in that: the adhesive is used for bonding the copper foil and the glass substrate, the copper foil and the aluminum substrate or being used as an adhesive of a PCB.
6. The utility model provides a glass base miniLED base plate which characterized in that: the glass and copper foil of the glass-based minisiniLED substrate are bonded through the flame-retardant structural adhesive of any one of claims 1-3.
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CN111040698B (en) * 2019-12-18 2022-05-03 镇江利德尔复合材料有限公司 Epoxy resin pouring sealant, preparation method and novel electric drive motor

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