Low-shrinkage high-bonding-strength photo-thermal dual-solid packaging material and preparation method and application thereof

Abstract

The invention relates to the technical field of packaging materials, in particular to a photo-thermal dual-solid packaging material with low shrinkage and high bonding strength as well as a preparation method and application of the photo-thermal dual-solid packaging material. The invention discloses a photo-thermal dual-curing packaging material with low shrinkage and high bonding strength, which is prepared from the following raw materials in parts by weight: 12 to 18 parts of organic silicon modified epoxy spiro resin, 10 to 15 parts of photo-thermal dual-curing resin, 5 to 8 parts of rubber modified epoxy toughened resin, 4 to 6 parts of flexible epoxy resin, 10 to 15 parts of epoxy diluent and 1.5 to 3 parts of novolac epoxy resin. The coating is prepared from the following components in parts by weight: 1-1.5 parts of a silane coupling agent, 70-85 parts of modified silica powder, 1-3 parts of fumed silica, 0.5 part of a defoaming agent, 0.5-1 part of a photoinitiator, 1 part of a thermal initiator, 0.2-0.5 part of a stabilizer and 0.05-0.2 part of a photosensitizer. The photo-thermal dual-solid packaging material provided by the invention solves the problems of large curing shrinkage, insufficient bonding strength, poor toughness, poor aging performance and the like existing in a traditional electronic packaging material.

Description

Technical Field

[0001] The present invention relates to the technical field of packaging materials, and in particular to a light-heat dual-solid packaging material with low shrinkage and high bonding strength, and a preparation method and application thereof. Background Art

[0002] In the field of electronic packaging materials, with the development trend of miniaturization, lightweight and high performance of electronic products, the performance requirements for packaging materials are becoming increasingly stringent. In recent years, low shrinkage and high bonding strength photothermal dual-solid electronic packaging materials have gradually become the focus of market attention. This type of material can not only effectively reduce the shrinkage rate during the packaging process and improve the dimensional stability and reliability of the packaged parts, but also achieve a fast and efficient packaging process through the photothermal dual curing mechanism, meeting the high efficiency and energy-saving needs of electronic product production.

[0003] Although the current photothermal dual-solid electronic packaging materials have achieved certain technical results, there are still some problems that need to be solved. First, some materials still have a certain shrinkage rate during the curing process. Although it is an improvement over traditional materials, it is still difficult to meet the requirements of high-precision electronic packaging. Secondly, although the bonding strength of some materials is relatively high, their stability and reliability still need to be further improved when facing complex and changeable packaging environments. In addition, although the current materials perform better than traditional materials in terms of toughness and drop resistance, there is still room for further improvement.

[0004] To this end, the present application provides a light-thermal dual-solid packaging material with low shrinkage and high bonding strength, and a preparation method and application thereof. Summary of the invention

[0005] In order to overcome the shortcomings of the prior art, the present invention provides a photothermal dual-curing packaging material with low shrinkage and high bonding strength. The material adopts a independently synthesized silicone-modified epoxy spiro resin, and adds raw materials such as photothermal dual-curing resin and rubber-modified epoxy toughening resin. By optimizing the proportion of each component and selecting suitable auxiliary materials, the present invention solves the problems of large curing shrinkage, insufficient bonding strength, poor toughness and poor aging performance existing in traditional electronic packaging materials.

[0006] The technical solution adopted by the present invention to solve its technical problem is:

[0007] In a first aspect, the present application provides a light-thermal dual-solid packaging material with low shrinkage and high bonding strength, comprising the following raw materials in parts by weight:

[0008] 12-18 parts of organosilicon-modified epoxy spirocyclic resin, 10-15 parts of photothermal dual-curing resin, 5-8 parts of rubber-modified epoxy toughening resin, 4-6 parts of flexible epoxy resin, 10-15 parts of epoxy diluent, 1.5-3 parts of phenolic epoxy resin, 1-1.5 parts of silane coupling agent, 70-85 parts of modified silicon micropowder, 1-3 parts of fumed silica, 0.5 parts of defoamer, 0.5-1 parts of photoinitiator, 1 part of thermal initiator, 0.2-0.5 parts of stabilizer, 0.05-0.2 parts of photosensitizer;

[0009] The preparation method of organosilicon-modified epoxy spiro resin comprises the following steps:

[0010] Add bisphenol A epoxy resin and 3-isocyanate propyltrimethoxysilane into a reaction kettle, then add phosphoric acid, stir evenly, heat and raise the temperature to 75°C; react at 75°C for 3h to obtain reactant A;

[0011] The reactant A and 6-caprolactone obtained above were added into a reaction kettle, and then dichloromethane was added to dilute and stir evenly, and the temperature was raised to 75°C, and then boron trifluoride ether was added as a catalyst, and the polycondensation reaction was carried out at 75°C for 4 hours, and then the reaction was washed with alkali and dried to obtain an organosilicon-modified epoxy spiro resin.

[0012] In some specific embodiments, the photothermal dual-curing resin is aliphatic epoxy resin 2021P.

[0013] In some specific embodiments, the rubber-modified epoxy toughening resin is rubber-modified epoxy resin EPP-175.

[0014] In some specific embodiments, the flexible epoxy resin is flexible epoxy resin EPICLON EXA-4850.

[0015] In some specific embodiments, the epoxy diluent is any one or any combination of oxane, dioxane, oxetane, and 3,3'-[oxybismethylene]bis[3-ethyl]oxetane.

[0016] In some specific embodiments, the phenolic epoxy resin is any one or more of phenolic epoxy resin DEN-431, phenolic epoxy resin DEN-438, phenolic epoxy resin EPALLOY 8250, and phenolic epoxy resin EPALLOY 1180.

[0017] In some specific embodiments, the silane coupling agent is γ-glycidyloxypropyltrimethoxysilane.

[0018] In some specific embodiments, the photoinitiator is any one or more of benzophenone 1-hydroxycyclohexyl phenyl ketone, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-isopropylthioxanthone and diaryliodonium salts.

[0019] In a second aspect, the present application provides a method for preparing the light-thermal dual-solid packaging material according to the first aspect, comprising the following steps:

[0020] S1. Add the silicone-modified spirocyclic resin, the photothermal dual-curing resin, the rubber-modified epoxy resin, the flexible epoxy resin, and the phenolic epoxy resin to the reactor in order by mass, raise the temperature to 100 ° C, mix and dissolve them thoroughly, and obtain a mixture A;

[0021] S2. The temperature of the mixture A is lowered to 52°C. After the temperature of the mixture A is stabilized, epoxy diluent, stabilizer, photoinitiator, and thermal initiator are added in order by mass and mixed thoroughly to obtain a mixture B;

[0022] S3. Then lower the temperature of the mixture B to 25°C, and then add the silane coupling agent, defoamer, sensitizer, modified silicon powder, and fumed silica in order by mass, and mix them thoroughly to obtain a mixture C;

[0023] S4. Grind the mixed material C to obtain a photothermal dual-solid packaging material.

[0024] In a third aspect, the present application provides an application of a photothermal dual-solid packaging material, wherein the photothermal dual-solid packaging material described in the first aspect or the photothermal dual-solid packaging material prepared by the preparation method described in the second aspect is applied to the packaging of electronic products.

[0025] The beneficial effects of the present invention are:

[0026] The photothermal dual-solid packaging material described in this application exhibits extremely low curing shrinkage, excellent bonding strength, good toughness and drop resistance, and outstanding long-term stability, and is suitable for the application needs of various high-end electronic packaging components. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] The present invention is further described below in conjunction with the accompanying drawings and embodiments.

[0028] Figure 1-Figure 2 This is a summary diagram of the test results of Examples 1 to 4 of the present application.

[0029] Figure 3-Figure 4 This is a summary of the test results of Comparative Examples 1 to 4 of the present application. DETAILED DESCRIPTION

[0030] In order to facilitate the understanding of those skilled in the art, the present invention is further described below in conjunction with embodiments, and the contents mentioned in the implementation modes are not intended to limit the present invention.

[0031] As used herein, "and / or" includes the term of any and all combinations of one or more associated listed items. The terms used herein are only used to describe specific embodiments and are not intended to limit the present invention. As used herein, the singular forms "a", "an", "an" and "the" are also intended to include the plural forms, unless the context clearly indicates otherwise. It is further understood that "including", when used in this specification, specifies the stated features, integers, steps, operations, elements and / or compositions, but does not exclude the existence or addition of one or more other features, integers, steps, operations, elements, compositions and / or combinations thereof.

[0032] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention belongs. It is further understood that terms, such as defined in commonly used dictionaries, are interpreted in accordance with their meanings in the context of the relevant art and are not in an idealized or overly formal sense unless explicitly so defined herein.

[0033] The exemplary invention described herein may appropriately lack any one or more element limitations that are not specifically disclosed herein. Therefore, the terms "comprise", "include", "contain", etc. should be understood broadly and non-restrictively. In addition, the terminology used herein is used as a description, not a limitation, and it is unintentional to use these terminology expressions that do not include any equivalent characteristics, but only describe some of their characteristics, but various modifications are possible within the scope of the present invention according to the rights. Therefore, although the present invention has been specifically disclosed by preferred embodiments and optional features, the modifications disclosed herein to embody the changes of the present invention may be recorded by those skilled in the art, and such modifications and changes will be considered to be within the scope of the present invention.

[0034] The raw materials or reagents used in the embodiments of the present invention and the comparative examples are all purchased from mainstream manufacturers in the market. Those without indicating the manufacturer or the concentration are all analytically pure raw materials or reagents that can be routinely obtained, as long as they can play the expected role, there is no particular restriction. The instruments and equipment such as the reactor and rotary evaporator used in the present embodiment are all purchased from major manufacturers in the market, as long as they can play the expected role, there is no particular restriction. If specific techniques or conditions are not indicated in the present embodiment, the techniques or conditions described in the literature in this area or according to the product specification are carried out.

[0035] A light-heat dual-solid packaging material with low shrinkage and high bonding strength, comprising the following raw materials in parts by weight:

[0036] 12-18 parts of organosilicon-modified epoxy spirocyclic resin, 10-15 parts of photothermal dual-curing resin, 5-8 parts of rubber-modified epoxy toughening resin, 4-6 parts of flexible epoxy resin, 10-15 parts of epoxy diluent, 1.5-3 parts of phenolic epoxy resin, 1-1.5 parts of silane coupling agent, 70-85 parts of modified silicon micropowder, 1-3 parts of fumed silica, 0.5 parts of defoamer, 0.5-1 parts of photoinitiator, 1 part of thermal initiator, 0.2-0.5 parts of stabilizer, 0.05-0.2 parts of photosensitizer;

[0037] The preparation method of organosilicon-modified epoxy spiro resin comprises the following steps:

[0038] Step 1) bisphenol A epoxy resin and 3-isocyanate propyltrimethoxysilane are added to a reaction kettle, and then phosphoric acid is added, stirred evenly, and heated to 75° C.; reacted at 75° C. for 3 hours to obtain reactant A;

[0039] Step 2) Add the reactant A obtained above and 6-caprolactone into a reaction kettle, then add dichloromethane to dilute and stir evenly, heat to raise the temperature to 75°C, then add boron trifluoride etherate as a catalyst, carry out a condensation reaction at 75°C for 4 hours, then wash with alkali and dry to obtain an organosilicon-modified epoxy spiro resin.

[0040] The chemical reaction process involved in the above-mentioned organosilicon-modified epoxy spiro resin is as follows:

[0041]

[0042] Specifically, in step 1), the epoxy resin is modified with organosilicon, and the prepared organosilicon-modified epoxy resin is subjected to infrared spectrum detection. The data show that 2200 cm -1 The isocyanate absorption peak near 1700 cm -1 、1530cm -1 、3200cm -1 The appearance of the absorption peak of the polyurethane structure indicates that the isocyanate structure reacts with the alcohol hydroxyl group in the spiro-modified epoxy resin structure, proving that the silicone is grafted onto the polymer molecular chain to obtain the silicone-modified epoxy resin.

[0043] The organosilicon-modified epoxy spirocyclic resin obtained in step 2) was subjected to infrared spectrum detection, and the test results showed that 913 cm -1 The epoxy characteristic functional group disappears, which is due to the double ring-opening reaction; the epoxy group and 6-caprolactone open the ring at the same time and then react, and the epoxy group disappears; at the same time, at 1060cm -1 and 1250cm -1 A chain ether bond absorption peak appears at the position, which further proves that the 6-caprolactone ring-opening is successful, and a double ring-opening reaction is carried out with the epoxy functional group to form an organosilicon-modified epoxy spiro resin.

[0044] Specifically, the organosilicon-modified epoxy spiro resin can significantly reduce volume shrinkage during the curing process and provide excellent bonding strength and chemical resistance.

[0045] Specifically, the photothermal dual-curing resin is the aliphatic epoxy resin 2021P produced by Japan Daicel, which contains both epoxy groups and double bond groups that can be used for cationic photocuring reactions. The photocuring reaction can be initiated by a photoinitiator, and the thermal curing polymerization reaction can be initiated by a thermal initiator. The dual-curing method facilitates the process production.

[0046] Specifically, the rubber-modified epoxy toughening resin is modified by grafting and polymerization of rubber masterbatch and epoxy resin. The resin can provide excellent toughness, reduce internal stress, and enhance adhesion to plastics. In the present application, the rubber-modified epoxy toughening resin is the rubber-modified epoxy resin EPP-175 produced by Luhe High-tech Materials Co., Ltd.

[0047] Specifically, the flexible epoxy resin is a new liquid flexible epoxy resin EPICLON EXA-4850 produced by DIC, which can provide higher toughness and heat and impact resistance.

[0048] Specifically, the epoxy diluent is any one or any combination of oxane, dioxane, oxetane, and 3,3'-[oxybismethylene]bis[3-ethyl]oxetane; the epoxy diluent can increase the photocuring reaction speed and dilute the epoxy resin to improve wettability.

[0049] Specifically, the phenolic epoxy resin is any one or more of DEN-431 and DEN-438 of Dow Chemical; EPALLOY 8250 and EPALLOY 1180 of Huntsman; and the phenolic epoxy resin can improve heat resistance and chemical resistance.

[0050] Specifically, the silane coupling agent is γ-glycidyloxypropyltrimethoxysilane; γ-glycidyloxypropyltrimethoxysilane is an organic silicon compound whose chemical structure has functional groups such as epoxy, hydroxyl and amino groups, so it has good thermal stability and weather resistance, as well as excellent electrical and mechanical properties.

[0051] Specifically, photoinitiators are mainly used in photocuring reactions, generating free radicals or ions by absorbing light energy, thereby initiating polymerization or crosslinking reactions. Common photoinitiators include benzoin and its derivatives, benzyls, alkyl phenones, acylphosphine oxides and benzophenones. In the present application, the photoinitiator is selected from any one or several of benzophenone 1-hydroxycyclohexyl benzophenone, phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2-isopropylthioxanthone and diaryliodonium salts.

[0052] Specifically, a thermal curing agent is a substance that can initiate a polymerization reaction at a certain temperature. Common thermal curing agents include peroxides, organic acid anhydrides, and amine compounds. These curing agents react with active groups in epoxy resins to form a three-dimensional network structure, thereby achieving curing. In the present application, the thermal curing agent is selected from any one of ammonium-blocked Lewis salt Vicbase TC3632 and ammonium-blocked Lewis salt Vicbase TC1612 produced by Shenzhen Kaiji.

[0053] Specifically, the stabilizer is mainly used to improve the stability and long-term storage performance of the product; the corresponding stabilizer is mainly added according to the reaction type of the glue curing agent; in the present application, barbituric acid is selected as the stabilizer.

[0054] Specifically, silicon micropowder is micro powder of silicon dioxide. In the application, the particle size of silicon micropowder is 5 to 7 μm.

[0055] Specifically, fumed silica is a fine, special amorphous silica product made by high-temperature hydrolysis of halosilanes in a oxyhydrogen flame. It is a multifunctional additive widely used in the coatings industry, and can play the role of thickening, thixotropy, matting, and anti-settling. Fumed SiO2 generally has two types of products: hydrophilic and hydrophobic. This application uses hydrophobic fumed silica, which is any one of Evonik's hydrophobic fumed silica R202, Evonik's hydrophobic fumed silica R972, Evonik's hydrophobic fumed silica R974, and Cabot's hydrophobic fumed silica 720.

[0056] Specifically, the defoamer is a substance that can reduce the surface tension of water, solution, suspension, etc., prevent the formation of foam, or reduce or eliminate the original foam. The defoamer used in the present invention is BYK-1760 produced by BYK Chemical.

[0057] Specifically, a photosensitizer is a chemical reagent that can improve the sensitivity and resolution of a target object. Photosensitizers have the advantages of good optical sensitivity, ability to absorb ultraviolet rays of a certain wavelength, and ability to accelerate system curing3; photosensitizers are rich in variety, including di-n-butylamine, n-butylamine, 4,4-di(N,N′-dimethyl-amino)benzophenone (EMK), 9-phenylacridine (9-PA), 5-nitroacenaphthene, etc. Amine monomers have the characteristics of being able to improve the activity of photoinitiators and not absorbing radiation. The photosensitizer used in this application is any one of the photosensitizers GC-6225 and photosensitizer EMK of Guangchuan Electronic Materials.

[0058] More specifically, the various raw materials interact with each other through different mechanisms in the low-shrinkage and high-bonding-strength photothermal dual-solid electronic packaging material to form a synergistic system, thereby achieving excellent overall performance.

[0059] 1. Silicone modified epoxy spiro resin and photothermal dual curing resin

[0060] The silicone-modified epoxy spiro resin provides the basis for low shrinkage and high bonding strength, while the light-heat dual-curing resin realizes the dual curing mechanism of light curing and heat curing. This combination not only improves the curing efficiency, but also reduces the risk of incomplete curing caused by a single curing method.

[0061] Under the combined action of silicone-modified epoxy spiro resin and photothermal dual-curing resin, the photothermal dual-curing electronic packaging material can be cured in a short time and maintain a low volume shrinkage rate, reducing the risk of internal stress and cracking.

[0062] 2. Rubber modified epoxy toughening resin and flexible epoxy resin

[0063] Rubber-modified epoxy resin enhances the toughness of the material and reduces internal stress; flexible epoxy resin further improves the flexibility and impact resistance of the photothermal dual-solid electronic packaging material. The synergistic use of rubber-modified epoxy toughening resin and flexible epoxy resin makes the material have both good mechanical strength and sufficient elasticity.

[0064] The synergistic effect of rubber-modified epoxy toughening resin and flexible epoxy resin significantly improves the material's anti-drop performance, making it more durable and less susceptible to damage when subjected to external impact.

[0065] Phenolic epoxy resin and inorganic filler (modified silica powder, fumed silica)

[0066] Phenolic epoxy resin improves the material's heat resistance and chemical corrosion resistance, while inorganic fillers such as modified silica powder and fumed silica increase the material's hardness, reduce the coefficient of thermal expansion, and help disperse stress.

[0067] This combination ensures that the material can maintain stable physical properties in high temperature environments, and effectively controls the thermal expansion of the material, reducing deformation caused by temperature changes.

[0068] 4. Silane coupling agent and inorganic filler

[0069] Silane coupling agent improves the interfacial bonding force between inorganic fillers and organic polymers, promotes the uniform dispersion between the two, and enhances the overall mechanical properties of the composite material.

[0070] This combination improves the mechanical strength of the material by enhancing the interface bonding, and shows better results especially when bonding different materials.

[0071] 5. Photoinitiators, thermal initiators, stabilizers and photosensitizers

[0072] Photoinitiators and thermal initiators are responsible for the initiation of photocuring and thermal curing respectively, ensuring the smooth progress of the curing process; stabilizers extend the storage life of the product; photosensitizers increase photosensitivity and accelerate the speed of photocuring reaction.

[0073] This combination ensures an efficient and stable curing process without affecting the long-term performance of the material.

[0074] The method for preparing the above-mentioned light-thermal dual-solid packaging material comprises the following steps:

[0075] S1. Add the silicone-modified spirocyclic resin, the photothermal dual-curing resin, the rubber-modified epoxy resin, the flexible epoxy resin, and the phenolic epoxy resin to the reactor in order by mass, raise the temperature to 100 ° C, mix and dissolve them thoroughly, and obtain a mixture A;

[0076] S2. The temperature of the mixture A is lowered to 52°C. After the temperature of the mixture A is stabilized, epoxy diluent, stabilizer, photoinitiator, and thermal initiator are added in order by mass and mixed thoroughly to obtain a mixture B;

[0077] S3. Then lower the temperature of the mixture B to 25°C, and then add the silane coupling agent, defoamer, sensitizer, modified silicon powder, and fumed silica in order by mass, and mix them thoroughly to obtain a mixture C;

[0078] S4. Grind the mixed material C to obtain a photothermal dual-solid packaging material.

[0079] The light-thermal dual-solid packaging material described in the present application is further described through the following preparation examples, embodiments and comparative examples.

[0080] Preparation Example 1

[0081] The preparation method of the organosilicon-modified spirocyclic resin comprises the following steps:

[0082] Add bisphenol A epoxy resin and 3-isocyanate propyltrimethoxysilane into a reaction kettle, then add phosphoric acid, stir evenly, heat to raise the temperature to 75° C., and react at 75° C. for 3 hours; and perform polycondensation reaction to obtain modified silicone-modified epoxy resin.

[0083] The above-obtained organosilicon-modified epoxy resin and 6-caprolactone are added into a reaction kettle, and then dichloromethane is added to dilute and stir evenly, and the temperature is raised to 75°C, and then boron trifluoride ether is added as a catalyst, and the reaction is carried out at 75°C for 4 hours, and then the temperature is cooled to room temperature, and an alkali washing treatment is carried out to remove excess chloride ions. After drying, the organosilicon-modified epoxy spiro resin can be obtained.

[0084] Example 1

[0085] A light-heat dual-solid packaging material with low shrinkage and high bonding strength, comprising the following raw materials in parts by weight:

[0086]

[0087]

[0088] Example 2

[0089] A light-heat dual-solid packaging material with low shrinkage and high bonding strength, comprising the following raw materials in parts by weight:

[0090]

[0091] Example 3

[0092] A light-heat dual-solid packaging material with low shrinkage and high bonding strength, comprising the following raw materials in parts by weight:

[0093]

[0094] Example 4

[0095] A light-heat dual-solid packaging material with low shrinkage and high bonding strength, comprising the following raw materials in parts by weight:

[0096]

[0097]

[0098] Comparative Example 1

[0099] A light-heat dual-solid packaging material with low shrinkage and high bonding strength, comprising the following raw materials in parts by weight:

[0100]

[0101] The remaining conditions are the same as those in Example 1.

[0102] Comparative Example 2

[0103] A light-heat dual-solid packaging material with low shrinkage and high bonding strength, comprising the following raw materials in parts by weight:

[0104]

[0105] The remaining conditions are the same as those in Example 1.

[0106] Comparative Example 3

[0107] A light-heat dual-solid packaging material with low shrinkage and high bonding strength, comprising the following raw materials in parts by weight:

[0108]

[0109]

[0110] The remaining conditions are the same as those in Example 1.

[0111] Comparative Example 4

[0112] A light-heat dual-solid packaging material with low shrinkage and high bonding strength, comprising the following raw materials in parts by weight:

[0113]

[0114] The remaining conditions are the same as those in Example 1.

[0115] Wherein: the organosilicon-modified spirocyclic resin in the above-mentioned embodiments and comparative examples is from Preparation Example 1;

[0116] The specific preparation method of the embodiment and comparative example comprises the following steps:

[0117] S1. Add the organosilicon-modified spirocyclic resin, the photothermal dual-curing resin, the rubber-modified epoxy resin, the flexible epoxy resin, and the phenolic epoxy resin to the reactor in order by mass, raise the temperature to 100 ° C, dissolve and blend and stir evenly to obtain a mixture A;

[0118] S2. The temperature of the mixture A is lowered to 52°C. After the temperature of the mixture is stabilized, epoxy diluent, stabilizer, photoinitiator, and thermal initiator are added in order by mass, dissolved, blended and stirred uniformly to obtain a mixture B;

[0119] S3. Then lower the temperature of the mixture B to 25°C, and then add the silane coupling agent, defoamer, sensitizer, modified silicon powder, and fumed silica in order by mass and stir evenly to obtain a mixture C;

[0120] S4. Grind the mixed material C after stirring evenly for 2 times with the front roller distance of 35um, the rear roller distance of 70um and the roller speed of 150RPM to obtain the finished product.

[0121] The light-heat dual-solid packaging materials prepared in the above examples and comparative examples were subjected to the following performance tests, and the test results are summarized in Figure 1-Figure 4 middle.

[0122] 1. Bond strength: universal tensile testing machine, GB / T 7124-2008.

[0123] (Base material: glass beads-stainless steel (SUS-GLASS), Kovar gold-glass beads (Au-GLASS))

[0124] 2. Tensile strength / elongation at break: universal tensile testing machine, GB / T 1040.1-2018.

[0125] 3. Thermal expansion coefficient / glass transition temperature: static thermomechanical analyzer (TMA450, TA Company, USA), GB / T4339-2008.

[0126] 4. Storage modulus: Dynamic mechanical analyzer (DMA), GB / T 40396-2021

[0127] 5. Curing shrinkage: (ρ2-ρ1) / (ρ2*100) (%). ρ1 is the density of the adhesive before curing, and ρ2 is the density of the adhesive after curing.

[0128] 6. Double 85 test conditions: 85% humidity, temperature 85℃.

[0129] 7. Thermal shock test conditions: low temperature TA: -40℃, high temperature TB: 120℃, GB 2423.22-87.

[0130] By comparing the formula ratio differences between Example 1 and Comparative Example 1, Example 2 and Comparative Example 2, Example 3 and Comparative Example 3, and Example 4 and Comparative Example 4, and analyzing the data Figure 1-Figure 4 , it can be seen that

[0131] After introducing the organosilicon-modified spirocyclic resin, Example 1 can effectively reduce curing shrinkage, improve material toughness, reduce internal stress (modulus reduction), and significantly improve its resistance to moisture and heat aging.

[0132] Although the introduction of phenolic resin in Example 2 slightly reduces the toughness of the material, its high temperature resistance is greatly improved.

[0133] In Example 3, after the epoxy diluent is introduced, the photocuring reaction speed can be greatly increased, and the initial bonding strength after the photocuring reaction can be increased.

[0134] After the introduction of flexible epoxy resin and rubber modified resin, the tensile properties and impact aging resistance of Example 4 are greatly improved.

[0135] The above embodiments are preferred implementation schemes of the present invention. In addition, the present invention may also be implemented in other ways. Any obvious replacement without departing from the concept of the present invention is within the protection scope of the present invention.

Claims

1. A light-thermal dual-solid packaging material with low shrinkage and high bonding strength, characterized in that: In parts by weight, the following raw materials are included: 12-18 parts of organosilicon-modified epoxy spirocyclic resin, 10-15 parts of photothermal dual-curing resin, 5-8 parts of rubber-modified epoxy toughening resin, 4-6 parts of flexible epoxy resin, 10-15 parts of epoxy diluent, 1.5-3 parts of phenolic epoxy resin, 1-1.5 parts of silane coupling agent, 70-85 parts of modified silicon micropowder, 1-3 parts of fumed silica, 0.5 parts of defoamer, 0.5-1 parts of photoinitiator, 1 part of thermal initiator, 0.2-0.5 parts of stabilizer, 0.05-0.2 parts of photosensitizer; The preparation method of organosilicon-modified epoxy spirocyclic resin comprises the following steps: Add bisphenol A epoxy resin and 3-isocyanate propyltrimethoxysilane into a reaction kettle, then add phosphoric acid, stir evenly, heat and raise the temperature to 75°C; react at 75°C for 3h to obtain reactant A; The reactant A and 6-caprolactone obtained above were added into a reaction kettle, and then dichloromethane was added to dilute and stir evenly, and the temperature was raised to 75°C, and then boron trifluoride ether was added as a catalyst, and the polycondensation reaction was carried out at 75°C for 4 hours, and then the reaction was washed with alkali and dried to obtain an organosilicon-modified epoxy spiro resin.

2. The light-thermal dual-solid packaging material according to claim 1, characterized in that: The photothermal dual-curing resin is aliphatic epoxy resin 2021P.

3. The light-thermal dual-solid packaging material according to claim 1, characterized in that: The rubber modified epoxy toughening resin is rubber modified epoxy resin EPP-175.

4. The light-thermal dual-solid packaging material according to claim 1, characterized in that: The flexible epoxy resin is flexible epoxy resin EPICLON EXA-4850.

5. The light-thermal dual-solid packaging material according to claim 1, characterized in that: The epoxy diluent is any one or any combination of oxane, dioxane, oxetane, and 3,3'-[oxybismethylene]bis[3-ethyl]oxetane.

6. The light-thermal dual-solid packaging material according to claim 1, characterized in that: The phenolic epoxy resin is any one or more of phenolic epoxy resin DEN-431, phenolic epoxy resin DEN-438, phenolic epoxy resin EPALLOY 8250, and phenolic epoxy resin EPALLOY1180.

7. The light-thermal dual-solid packaging material according to claim 1, characterized in that: The silane coupling agent is γ-glycidyloxypropyltrimethoxysilane.

8. The light-thermal dual-solid packaging material according to claim 1, characterized in that: The photoinitiator is any one or more of benzophenone 1-hydroxycyclohexyl phenyl ketone, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-isopropylthioxanthone and diaryliodonium salt.

9. The method for preparing the photothermal dual-solid packaging material according to any one of claims 1 to 8, characterized in that: The following steps are involved: S1. Add the silicone-modified spirocyclic resin, the photothermal dual-curing resin, the rubber-modified epoxy resin, the flexible epoxy resin, and the phenolic epoxy resin to the reactor in order by mass, raise the temperature to 100 ° C, mix and dissolve them thoroughly, and obtain a mixture A; S2. The temperature of the mixture A is lowered to 52°C. After the temperature of the mixture A is stabilized, epoxy diluent, stabilizer, photoinitiator, and thermal initiator are added in order by mass and mixed thoroughly to obtain a mixture B; S3. Then lower the temperature of the mixture B to 25°C, and then add the silane coupling agent, defoamer, sensitizer, modified silicon powder, and fumed silica in order by mass, and mix them thoroughly to obtain a mixture C; S4. Grind the mixed material C to obtain a photothermal dual-solid packaging material.

10. Application of light-thermal dual-solid packaging material, characterized in that: The photothermal dual-solid packaging material described in any one of claims 1 to 8 or the photothermal dual-solid packaging material prepared by the preparation method described in claim 9 is applied to the packaging of electronic products.

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