Resin composition, adhesive film and metal substrate

Abstract

The invention relates to a resin composition, an adhesive film and a metal substrate, the resin composition comprises a mixed resin, a filler and a curing agent, the mixed resin comprises a hydrocarbon resin, a flexible resin and a modified polyhedral oligomeric silsesquioxane resin; the glass transition temperature of the hydrocarbon resin is less than or equal to-10 DEG C; the flexible resin is selected from epoxy modified flexible resin or pre-reaction flexible resin prepared by reacting the epoxy modified flexible resin with an epoxy curing agent, and the epoxy equivalent of the epoxy modified flexible resin is 150g / mol to 300g / mol; at least four vertex angles in eight vertex angles of the modified polyhedral oligomeric silsesquioxane are grafted with flexible chain segments, and end groups of the flexible chain segments are selected from functional groups capable of reacting with hydrocarbon resin. When the resin composition is used for preparing an adhesive film and a metal substrate, the adhesive film and a dielectric layer in the metal substrate have excellent flexibility, toughness and heat resistance, and the dielectric layer and a conductive layer have excellent peel strength.

Description

Technical Field

[0001] The present invention relates to the technical field of electronic industry, and in particular to a resin composition, an adhesive film and a metal substrate. Background Art

[0002] With the maturity of LED (Light Emitting Diode) technology, the integration of LED lamp beads has increased, the number has increased, and the power has become larger. The heat generated during operation is huge, which causes the LED chip to be in an alternating hot and cold environment for a long time. Due to the mismatch between the thermal expansion and contraction of the LED chip and the metal substrate, tensile or compressive stress is generated at the connection of the pad, which in turn causes the fragile pad to crack, affecting the normal use of the LED product.

[0003] To address this problem, the traditional technical solution is to add silicone-modified, acrylic-modified, polyurethane-modified, or rubber-modified flexible epoxy resins to the resin composition, or to add toughening rubbers such as nitrile, core-shell rubber, and acrylate rubber to improve the flexibility of the dielectric layer in the adhesive film and the metal substrate to improve the pad cracking problem. However, these methods have limited effect on improving the flexibility of the dielectric layer in the adhesive film and the metal substrate; and the metal substrate has poor heat resistance; in addition, although adding hydrocarbon resin to the resin composition improves flexibility, the polarity of hydrocarbon resin is low and the peel strength is poor, and the copper foil in the metal substrate will fall off during use, which cannot meet the use requirements. Summary of the invention

[0004] Based on this, it is necessary to provide a resin composition, an adhesive film and a metal substrate to address the above problems. The resin composition is used to prepare the adhesive film and the metal substrate, which not only makes the dielectric layer in the adhesive film and the metal substrate have excellent flexibility, toughness and heat resistance, but also makes the dielectric layer and the conductive layer have excellent peel strength.

[0005] The present invention discloses a resin composition, comprising a mixed resin, a filler and a curing agent, wherein the mixed resin comprises a hydrocarbon resin, a flexible resin and a modified cage-type polysilsesquioxane resin;

[0006] Wherein, the glass transition temperature of the hydrocarbon resin is less than or equal to -10°C;

[0007] The flexible resin is selected from epoxy-modified flexible resin or pre-reacted flexible resin obtained by reacting epoxy-modified flexible resin with epoxy curing agent, and the epoxy equivalent of the epoxy-modified flexible resin is 150 g / mol-300 g / mol;

[0008] Among the eight vertices in the modified cage-type polysilsesquioxane, at least four vertices are grafted with flexible segments, and the end groups of the flexible segments are selected from functional groups that can react with the hydrocarbon resin.

[0009] In one embodiment, the hydrocarbon resin further satisfies at least one of the following conditions:

[0010] (1) The number average molecular weight of the hydrocarbon resin is 2000 g / mol-10000 g / mol;

[0011] (2) The functionality of the carbon-carbon unsaturated bonds of the hydrocarbon resin is 50-200;

[0012] (3) The hydrocarbon resin contains a branched chain, and the carbon-carbon unsaturated bonds on the branched chain account for 60% to 95% of the total number of carbon-carbon unsaturated bonds on the hydrocarbon resin;

[0013] (4) The hydrocarbon resin contains a branched chain, and the number of carbon atoms in any branched chain is less than or equal to 7.

[0014] In one embodiment, the hydrocarbon resin includes at least one of polybutadiene, polyisoprene, ethylene propylene diene monomer rubber, propylene dimethyl butadiene copolymer, butadiene nonene copolymer or butadiene dodecene copolymer.

[0015] In one embodiment, the epoxy modified flexible resin further satisfies at least one of the following conditions:

[0016] (1) The glass transition temperature of the epoxy modified flexible resin is less than or equal to 10°C;

[0017] (2) The number average molecular weight of the epoxy modified flexible resin is 500 g / mol-5000 g / mol.

[0018] In one embodiment, the epoxy-modified flexible resin includes at least one of epoxy-modified silicone resin, epoxy-modified hydrocarbon resin, epoxy-modified polyethylene glycol or epoxy-modified acrylic resin.

[0019] In one embodiment, the residual rate of epoxy groups in the pre-reacted flexible resin is less than or equal to 10%;

[0020] And / or, the epoxy curing agent is selected from a bifunctional curing agent;

[0021] And / or, the molecular weight of the epoxy curing agent is 80 g / mol-200 g / mol.

[0022] In one embodiment, the modified cage-type polysilsesquioxane further satisfies at least one of the following conditions:

[0023] (1) The number average molecular weight of the soft segment is 150 g / mol-300 g / mol;

[0024] (2) When the flexible segment contains branches, the number of atoms on any branch is less than or equal to 12.

[0025] In one embodiment, the soft segment is selected from at least one of a long-chain olefin, a polyethylene glycol chain, a polysiloxane chain, a long-chain acrylate, or a long-chain polylactic acid.

[0026] In one embodiment, based on 100 parts by weight of the hydrocarbon resin, the amount of the flexible resin is 20 parts by weight to 50 parts by weight, the amount of the modified cage-type polysilsesquioxane is 30 parts by weight to 60 parts by weight, the amount of the filler is 700 parts by weight to 1800 parts by weight, and the amount of the curing agent is 10 parts by weight to 30 parts by weight.

[0027] An adhesive film comprises a carrier layer and a dielectric layer which are stacked in sequence, wherein the dielectric layer is made of the above-mentioned resin composition.

[0028] A metal substrate comprises a conductive layer, a dielectric layer and a metal plate which are stacked in sequence, wherein the dielectric layer is made of the above-mentioned resin composition.

[0029] In the resin composition provided by the present invention, a specific hydrocarbon resin, a specific flexible resin and a specific modified cage-type polysilsesquioxane resin cooperate with each other. When the resin composition is used to prepare an adhesive film and a metal substrate, the hydrocarbon resin makes the dielectric layer in the adhesive film and the metal substrate have excellent flexibility; the flexible resin can further improve the flexibility of the dielectric layer, while ensuring that the dielectric layer and the conductive layer in the metal substrate have sufficient peeling strength; the modified cage-type polysilsesquioxane resin not only improves the flexibility and toughness of the dielectric layer, but also improves the heat resistance of the dielectric layer; in addition, when the flexible resin is selected from the pre-reacted flexible resin, the heat resistance of the dielectric layer is further improved. Thus, on the one hand, the prepared adhesive film has excellent flexibility, toughness and heat resistance, and on the other hand, not only the dielectric layer in the prepared metal substrate has excellent flexibility, toughness and heat resistance, but also the dielectric layer and the conductive layer have sufficient peeling strength, so that the metal substrate can be better used in electronic devices. DETAILED DESCRIPTION

[0030] For ease of understanding of the present invention, the present invention will be described in more detail below. However, it should be understood that the present invention can be implemented in many different forms and is not limited to the embodiments or examples described herein. On the contrary, the purpose of providing these embodiments or examples is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0031] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific implementation methods or embodiments, and are not intended to limit the present invention. The optional scope of the term "and / or" used herein includes any one of two or more related listed items, and also includes any and all combinations of related listed items, and the combinations include any two related listed items, any more related listed items, or all related listed items.

[0032] The resin composition provided by the present invention can be used to prepare a dielectric layer in a metal substrate or a dielectric layer in an adhesive film, etc.; specifically, the resin composition includes a mixed resin, a filler and a curing agent, wherein the mixed resin includes a hydrocarbon resin, a flexible resin and a modified cage-type polysilsesquioxane resin.

[0033] The present invention uses a specific hydrocarbon resin, a specific flexible resin and a specific modified cage-type polysilsesquioxane resin in a compound form. Specifically, the glass transition temperature of the hydrocarbon resin is less than or equal to -10°C. The hydrocarbon resin enables the metal substrate and the dielectric layer in the adhesive film to have excellent flexibility.

[0034] The flexible resin is selected from epoxy-modified flexible resin or pre-reacted flexible resin obtained by reacting epoxy-modified flexible resin with epoxy curing agent, and the epoxy equivalent of epoxy-modified flexible resin is 150g / mol-300g / mol; it should be noted that the main chain of the flexible resin is composed of repeating structural units, and the repeating structural units are selected from at least one of CC bond, non-conjugated double bond, CO bond, Si-O bond or CN bond, and the flexible resin may contain side chains or no side chains. When the flexible resin contains side chains, the side chains do not contain conjugated π bonds and heterocycles; the flexible resin further improves the flexibility of the dielectric layer, while ensuring that the dielectric layer and the conductive layer of the metal substrate have sufficient peeling strength. In addition, when the flexible resin is selected from the pre-reacted flexible resin obtained by reacting epoxy-modified flexible resin with epoxy curing agent, the curing rates of hydrocarbon resin and flexible resin are closer, thereby further improving the heat resistance and toughness of the dielectric layer.

[0035] Among the eight vertices in the modified cage-type polysilsesquioxane, at least four vertices are grafted with flexible segments, and the end groups of the flexible segments are selected from functional groups that can react with hydrocarbon resins; it should be noted that the flexible segment refers to a straight chain whose main chain is composed of only one or at least two of CC bonds, non-conjugated double bonds, CO bonds, Si-O bonds or CN bonds, and the flexible segment may contain branches. When the flexible segment contains branches, the branches do not contain conjugated π bonds and heterocycles; the center of the modified cage-type polysilsesquioxane is a silicon-oxygen octahedral skeleton structure with Si-O alternately connected, which has high structural stability and can improve the toughness of the dielectric layer. The grafted flexible segments have a large activity space and degree of freedom, and the steric hindrance of internal rotation is small, giving the dielectric layer better flexibility. Therefore, the modified cage-type polysilsesquioxane resin not only improves the flexibility of the dielectric layer, but also improves the heat resistance of the dielectric layer.

[0036] Therefore, the adhesive film and metal substrate prepared by using the resin composition have excellent flexibility, toughness and heat resistance.

[0037] In one embodiment, the number average molecular weight of the hydrocarbon resin is 2000g / mol-10000g / mol, including but not limited to 2000g / mol, 3000g / mol, 4000g / mol, 5000g / mol, 6000g / mol, 7000g / mol, 8000g / mol, 9000g / mol or 10000g / mol; on the one hand, it is beneficial to make the dielectric layer have better flexibility, and on the other hand, it enables the hydrocarbon resin to be better dispersed in the resin composition, so that the resin composition has better processability.

[0038] In order to make the dielectric layer have better flexibility, toughness and heat resistance, in one embodiment, the functionality of the carbon-carbon unsaturated bond of the hydrocarbon resin is 50-200, including but not limited to 50, 80, 100, 150 or 200.

[0039] Compared with the carbon-carbon unsaturated bonds on the main chain of the hydrocarbon resin, the carbon-carbon unsaturated bonds on the side chains of the hydrocarbon resin are more reactive. When the hydrocarbon resin containing side chains undergoes a cross-linking reaction, the residual carbon-carbon unsaturated bonds in the product account for a lower proportion, and the cross-linking degree of the cross-linked product is high, thereby making the metal substrate and the dielectric layer in the film more heat-resistant. Therefore, preferably, the hydrocarbon resin contains side chains.

[0040] When the hydrocarbon resin contains side chains, the carbon-carbon unsaturated bonds on the side chains preferably account for 60%-95% of the total carbon-carbon unsaturated bonds on the hydrocarbon resin, including but not limited to 60%, 70%, 80%, 90% or 95%; thereby making the cross-linking degree of the cross-linked product moderate, and thus making the metal substrate and the dielectric layer in the film have excellent flexibility and heat resistance.

[0041] In addition, when the hydrocarbon resin contains side chains, the number of carbon atoms on any side chain is less than or equal to 7, thereby further improving the flexibility of the metal substrate and the dielectric layer in the adhesive film.

[0042] In one embodiment, the hydrocarbon resin includes at least one of polybutadiene, polyisoprene, ethylene propylene diene monomer rubber, propylene dimethyl butadiene copolymer, butadiene nonene copolymer or butadiene dodecene copolymer; specifically, the polybutadiene is preferably selected from polybutadiene B3000 (Nippon Sooda), polybutadiene B2000 (Nippon Sooda), polybutadiene RICON142 (Cray Valley) or polybutadiene RICON147 (Cray Valley). Valley); polyisoprene is preferably selected from polyisoprene LIR5000 (Minnesota Rubber and Plastics); EPDM rubber is preferably selected from EPDM rubber HD10000 (Shanghai Fuyou); propylene dimethyl butadiene copolymer is preferably selected from propylene dimethyl butadiene copolymer C904 (Tianyuan Aviation Materials); butadiene nonene copolymer is preferably selected from butadiene nonene copolymer P-BN3000 (Tianyuan Aviation Materials); butadiene dodecene copolymer is preferably selected from butadiene dodecene copolymer P-BL3000 (Tianyuan Aviation Materials).

[0043] In order to further improve the flexibility of the metal substrate and the dielectric layer in the adhesive film, the glass transition temperature of the epoxy-modified flexible resin is preferably less than or equal to 10°C.

[0044] In one embodiment, the number average molecular weight of the epoxy modified flexible resin is 500 g / mol-5000 g / mol, including but not limited to 500 g / mol, 1000 g / mol, 2000 g / mol, 3000 g / mol, 4000 g / mol, and 5000 g / mol, which further improves the flexibility of the metal substrate and the dielectric layer in the film.

[0045] In one embodiment, the epoxy-modified flexible resin includes at least one of epoxy-modified silicone resin, epoxy-modified hydrocarbon resin, epoxy-modified polyethylene glycol, or epoxy-modified acrylic resin. Specifically, the epoxy-modified silicone resin is preferably selected from epoxy-modified polysiloxane SI-203 (Huizhou Aike New Materials); the epoxy-modified hydrocarbon resin is preferably selected from epoxy-modified polybutadiene JP-200 (Nippon Sooda); the epoxy-modified polyethylene glycol is preferably selected from epoxy-modified polyethylene glycol EPPEG4500 (Tesco Chemical), epoxy-modified polyethylene glycol EPPEG4800 (Tesco Chemical) or epoxy-modified polyethylene glycol EPPEG600 (Tesco Chemical); the epoxy-modified acrylic resin is preferably selected from epoxy-modified acrylic resin UG-4010 (Jingyi Chemical) or epoxy-modified acrylic resin F-303 (Jingyi Chemical).

[0046] Since the curing reaction of the epoxy group has a different reaction rate compared to the free radical reaction of the carbon-carbon unsaturated bond, if the two reactions are carried out simultaneously, the reaction will be incomplete and the product performance will be uneven; therefore, preferably, the flexible resin is selected from a pre-reacted flexible resin prepared by reacting an epoxy-modified flexible resin with an epoxy curing agent, and further preferably, the residual rate of epoxy groups in the pre-reacted flexible resin is less than or equal to 10%, including but not limited to, the residual rate of epoxy groups in the pre-reacted flexible resin is 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.

[0047] In one embodiment, the preparation method of the pre-reacted flexible resin comprises the following steps: mixing the epoxy modified flexible resin, epoxy curing agent, catalyst and free radical reaction inhibitor, performing a reflux reaction, and then post-treating the reaction solution to separate and obtain the pre-reacted flexible resin. The residual rate of epoxy groups in the pre-reacted flexible resin can be adjusted by adjusting the reaction time and reaction temperature of the reflux reaction. Preferably, the reaction temperature is 150°C-200°C and the reaction time is 60min-90min.

[0048] In order to allow the resins to fully react and crosslink and improve the heat resistance of the metal substrate, the epoxy curing agent is preferably selected from a bifunctional curing agent, for example, one of the functional groups is selected from a carbon-carbon double bond or a carbon-carbon triple bond, and the other functional group is selected from one of a hydroxyl group (-OH), an amino group (-NH2) or a thiol group (-SH).

[0049] In order to make the metal substrate and the dielectric layer in the film have excellent flexibility and heat resistance, preferably, the molecular weight of the epoxy curing agent is 80g / mol-200g / mol, including but not limited to 80g / mol, 100g / mol, 120g / mol, 140g / mol, 160g / mol, 180g / mol or 200g / mol.

[0050] In one embodiment, in the modified cage-type polysilsesquioxane, the number average molecular weight of the flexible segment is 150 g / mol-300 g / mol, so that the metal substrate and the dielectric layer in the adhesive film have both better flexibility and heat resistance.

[0051] It should be noted that when the flexible chain segment contains branches, the number of atoms on any branch is preferably less than or equal to 12, so as to further enhance the flexibility of the metal substrate and the dielectric layer in the adhesive film.

[0052] In one embodiment, the flexible chain segment is selected from at least one of a long chain olefin, a polyethylene glycol chain, a polysiloxane chain, a long acrylate chain or a long polylactic acid chain. Specifically, the long chain olefin is preferably selected from at least one of pentadecene, modified pentadecene, dodecene, modified dodecene, undecene or modified undecene. The number of repeating structural units of the polyethylene glycol chain is preferably 3-7, and the number of repeating structural units of the polysiloxane chain is preferably 4-6.

[0053] In one embodiment, the filler includes at least one of aluminum oxide, aluminum nitride, boron nitride, silicon nitride, silicon dioxide, silicon nitride, or diamond powder.

[0054] In one embodiment, the curing agent includes at least one of an epoxy curing agent, a peroxide or an azo compound initiator.

[0055] In order to fully exert the synergistic effect of each component in the resin composition and further enhance the flexibility, toughness and heat resistance of the metal substrate and the dielectric layer in the film, in one embodiment, based on 100 parts by weight of hydrocarbon resin, the amount of flexible resin is 20 parts by weight to 50 parts by weight, the amount of modified cage-type polysilsesquioxane is 30 parts by weight to 60 parts by weight, the amount of filler is 700 parts by weight to 1800 parts by weight, and the amount of curing agent is 10 parts by weight to 30 parts by weight.

[0056] In one embodiment, the resin composition further includes an auxiliary agent, including but not limited to at least one of an antioxidant, a leveling agent or a coupling agent; in addition, based on 100 parts by weight of hydrocarbon resin, the amount of the auxiliary agent is less than or equal to 15 parts by weight, preferably 1 part by weight to 15 parts by weight.

[0057] The present invention also provides an adhesive film, comprising a carrier layer and a dielectric layer which are stacked in sequence, wherein the dielectric layer is made of the above-mentioned resin composition.

[0058] The dielectric layer in the adhesive film provided by the present invention has excellent flexibility, toughness and heat resistance, so that the adhesive film has excellent flexibility, toughness and heat resistance.

[0059] In one embodiment, the carrier layer is selected from polyester film (PET film), polyetheretherketone film (PEEK film), polyetherimide film (PEI film), polyimide film (PI film), polycarbonate film (PC film, release paper or coated paper.

[0060] The present invention also provides a metal substrate, comprising a conductive layer, a dielectric layer and a metal plate which are stacked in sequence, wherein the dielectric layer is made of the above-mentioned resin composition.

[0061] The dielectric layer in the metal substrate of the present invention has excellent flexibility, toughness and heat resistance. At the same time, there is sufficient peeling strength between the dielectric layer and the conductive layer. Therefore, the metal substrate provided by the present invention can be better applied to electronic devices.

[0062] In one embodiment, the conductive layer is preferably selected from copper foil; and the metal plate is preferably selected from aluminum plate, copper plate or copper-aluminum alloy.

[0063] The present invention does not limit the preparation method of the metal substrate, including but not limited to, the metal substrate provided by the present invention can be prepared by the following two methods: one is to directly form the resin composition on the surface of the metal plate by a method such as scraping or silk screen printing, and then dry it to form a dielectric layer, and then cover the surface of the dielectric layer away from the metal plate with a conductive layer, and finally press it to obtain the metal substrate;

[0064] The other method is to first prepare the resin composition into a film, and then use the film to prepare the metal substrate. The specific preparation method includes the following steps: coating the resin composition on the surface of the PET film, baking at 85°C to obtain the film, removing the carrier layer and then laminating it on the metal plate so that the dielectric layer contacts the metal plate, and then covering the surface of the dielectric layer with a conductive layer.

[0065] Hereinafter, the resin composition, the adhesive film and the metal substrate will be further described through the following specific examples.

[0066] Example 1

[0067] 30 parts by weight of epoxy-modified polybutadiene (brand name JP-200, main chain is non-conjugated carbon-carbon double bond and CC bond, epoxy equivalent is 200, glass transition temperature Tg is -7°C, molecular weight is 1500), 15 parts by weight of allyl alcohol polyoxyethylene ether (epoxy curing agent, brand name APEG100, functional groups are carbon-carbon double bond, hydroxyl group, molecular weight is 102, Tg is -30°C) are dissolved in xylene solvent, after complete dissolution, 0.4 parts by weight of 2,5-di-tert-butylhydroquinone (free radical reaction inhibitor) is added, the temperature is raised to 180°C and refluxed for 80 minutes. The reaction solution is concentrated by rotary evaporation, the obtained concentrated solution is added dropwise to petroleum ether, and the pre-reacted flexible resin is obtained by precipitation, and the residual rate of epoxy group is measured to be 3%.

[0068] 100 parts by weight of polybutadiene (brand name B3000, Nippon Sooda, functionality 60, molecular weight 3050, Tg -21°C, non-main chain carbon-carbon unsaturated bonds account for 87%, and the number of carbon atoms on any branch chain is 2), 50 parts by weight of pentadecene-modified cage-type polysilsesquioxane (brand name 5PS200POSS, Laiyang Shengbang Silicone, 5 vertices grafted with pentadecene, repeating structural unit is CC bond, single flexible chain segment molecular weight is 200, and flexible chain segment does not contain branch chain), and 45 parts by weight of pre-reacted flexible resin are dissolved in xylene solvent, and after complete dissolution and dispersion, 2 parts of peroxide (2,4-di-tert-butyl peroxide isopropylbenzene, BIBP), 1 part of polyacrylate leveling agent, 1 part of antioxidant 1010, and 10 parts of silane coupling agent (KH570) are added to disperse into a uniform phase. 900 parts by weight of aluminum oxide (brand AX3-32, Nippon Steel) was added and dispersed at a high speed of 1800 r / min for 30 minutes to obtain a resin composition.

[0069] The resin composition was coated on the surface of the metal plate (aluminum plate) using a flat plate coating device and baked at 85°C for 3 minutes. A 2oz HTE copper foil was placed on the surface of the dielectric layer away from the metal plate and pressed using a vacuum press (temperature 240°C, pressure 50kg) to obtain a metal substrate.

[0070] The T288 of the metal substrate of this embodiment and the peel strength between the dielectric layer and the conductive layer are shown in Table 1. The flexibility and toughness of the dielectric layer in the metal substrate of this embodiment are characterized by the Young's modulus and impact strength of the insulating sheet after the resin composition is made into an insulating sheet. The specific results are shown in Table 1. The test process is as follows: the resin composition is coated on the surface of the PET film, baked at 85°C to obtain a film, the PET film on the surface of the film is removed, and multiple layers are stacked, and an insulating sheet with a thickness of 1 mm is obtained by vacuum pressing. The flexibility and toughness of the dielectric layer in the metal substrate are characterized by testing the Young's modulus and impact strength of the insulating sheet.

[0071] Example 2

[0072] Example 2 is carried out with reference to Example 1, except that the epoxy-modified polybutadiene (brand name JP-200, Nippon Soda, main chain is non-conjugated carbon-carbon double bond and CC bond, epoxy equivalent is 200, glass transition temperature Tg is -7°C, molecular weight is 1500) is not pre-reacted with allyl alcohol polyoxyethylene ether (epoxy curing agent, functional groups are carbon-carbon double bond, hydroxyl group, molecular weight is 102, Tg is -30°C), but is directly added to the resin composition, the mass of the epoxy-modified polybutadiene is 30 parts by weight, and the mass of the allyl alcohol polyoxyethylene ether is 15 parts by weight.

[0073] The Young's modulus, impact strength, T288 of the dielectric layer in the metal substrate of this embodiment, and the peel strength between the dielectric layer and the conductive layer are shown in Table 1.

[0074] Comparative Example 1

[0075] Comparative Example 1 is carried out with reference to Example 1, except that the hydrocarbon resin in the resin composition is replaced by propylene dimethyl butadiene copolymer (brand name C904, Tianyuan Aerospace Materials, functionality 60, molecular weight 3050, Tg 0°C, non-main chain carbon-carbon unsaturated bonds accounting for 87%, and the number of carbon atoms on any branch chain is 2).

[0076] The Young's modulus, impact strength, T288 of the dielectric layer of the metal substrate of this comparative example and the peel strength between the dielectric layer and the conductive layer are shown in Table 1.

[0077] Comparative Example 2

[0078] Comparative Example 2 was carried out with reference to Example 1, except that the epoxy-modified polybutadiene was replaced with epoxy-modified polyethylene glycol (brand name EPPEG600, Tesco Chemical, the repeating units of the main chain were CC bonds and CO bonds, the epoxy equivalent was 120, the glass transition temperature Tg was -40°C, and the molecular weight was 600), and the amount of allyl alcohol polyoxyethylene ether was increased to 25 parts by weight. At the same time, the amount of the pre-reacted flexible resin in the resin composition was 55 parts by weight.

[0079] The Young's modulus, impact strength, T288 of the dielectric layer of the metal substrate of this comparative example and the peel strength between the dielectric layer and the conductive layer are shown in Table 1.

[0080] Comparative Example 3

[0081] Comparative Example 3 was carried out with reference to Example 1, except that the epoxy-modified polybutadiene was replaced with epoxy-modified polyethylene glycol (brand name EPPEG4800, Tesco Chemical, the repeating units of the main chain were CC bonds and CO bonds, the epoxy equivalent was 480, the glass transition temperature Tg was -25°C, and the molecular weight was 4800), and the amount of allyl alcohol polyoxyethylene ether was reduced to 6 parts by weight. At the same time, the amount of the pre-reacted flexible resin in the resin composition was 36 parts by weight.

[0082] The Young's modulus, impact strength, T288 of the dielectric layer of the metal substrate of this comparative example and the peel strength between the dielectric layer and the conductive layer are shown in Table 1.

[0083] Comparative Example 4

[0084] Comparative Example 4 was carried out with reference to Example 1, except that the pentadecene-modified cage-type polysilsesquioxane in the resin composition was replaced with cage-type polysilsesquioxane (brand number POSS105, Qiyue Biopharmaceuticals).

[0085] The Young's modulus, impact strength, T288 of the dielectric layer of the metal substrate of this comparative example and the peel strength between the dielectric layer and the conductive layer are shown in Table 1.

[0086] Comparative Example 5

[0087] Comparative Example 5 was carried out with reference to Example 1, except that the pentadecene-modified cage-type polysilsesquioxane in the resin composition had pentadecene grafted on only three vertices (brand name 3PS200POSS, Laiyang Shengbang Silicone).

[0088] The Young's modulus, impact strength, T288 of the dielectric layer of the metal substrate of this comparative example and the peel strength between the dielectric layer and the conductive layer are shown in Table 1.

[0089] Table 1

[0090]

[0091] Example 3

[0092] Example 3 is carried out with reference to Example 1, except that the hydrocarbon resin in the resin composition is replaced by polybutadiene (brand name B2000, Nippon Soda, functionality 60, molecular weight 2010, Tg -29°C, non-main chain carbon-carbon unsaturated bonds accounting for 92%, and the number of carbon atoms in any branch chain is 2).

[0093] The Young's modulus, impact strength, T288 of the dielectric layer of the metal substrate of this embodiment, and the peel strength between the dielectric layer and the conductive layer are shown in Table 2.

[0094] Example 4

[0095] Example 4 is carried out with reference to Example 1, except that the hydrocarbon resin in the resin composition is replaced by ethylene propylene diene monomer rubber (brand name: HD10000, Shanghai Fuyou, functionality: 60, molecular weight: 10000, Tg: -74°C, non-main chain carbon-carbon unsaturated bonds: 60%, and the number of carbon atoms in any branch chain: 2).

[0096] The Young's modulus, impact strength, T288 of the dielectric layer of the metal substrate of this embodiment, and the peel strength between the dielectric layer and the conductive layer are shown in Table 2.

[0097] Example 5

[0098] Example 5 is carried out with reference to Example 1, except that the hydrocarbon resin in the resin composition is replaced by a butadiene nonene copolymer (brand name P-BN3000, Tianyuan Aerospace Materials, functionality 60, molecular weight 3050, Tg -20°C, non-main chain carbon-carbon unsaturated bonds accounting for 87%, and the number of carbon atoms in any branch chain is 6).

[0099] The Young's modulus, impact strength, T288 of the dielectric layer of the metal substrate of this embodiment, and the peel strength between the dielectric layer and the conductive layer are shown in Table 2.

[0100] Example 6

[0101] Example 6 is carried out with reference to Example 1, except that the hydrocarbon resin in the resin composition is replaced by a butadiene dodecene copolymer (brand name P-BL3000, Tianyuan Aerospace Materials, functionality 60, molecular weight 3050, Tg -13°C, non-main chain carbon-carbon unsaturated bonds accounting for 87%, and the number of carbon atoms on any side chain is 10).

[0102] The Young's modulus, impact strength, T288 of the dielectric layer of the metal substrate of this embodiment, and the peel strength between the dielectric layer and the conductive layer are shown in Table 2.

[0103] Example 7

[0104] Example 7 is carried out with reference to Example 1, except that the hydrocarbon resin in the resin composition is replaced by polybutadiene (brand name RICON142, Cray Valley, functionality 20, molecular weight 3000, Tg -17°C, non-main chain carbon-carbon unsaturated bonds accounting for 87%, and the number of carbon atoms on any branch chain is 2).

[0105] The Young's modulus, impact strength, T288 of the dielectric layer of the metal substrate of this embodiment, and the peel strength between the dielectric layer and the conductive layer are shown in Table 2.

[0106] Example 8

[0107] Example 8 is carried out with reference to Example 1, except that the hydrocarbon resin in the resin composition is replaced by polybutadiene (brand name RICON147, Cray Valley, functionality of 200, molecular weight of 6000, Tg of -25°C, non-main chain carbon-carbon unsaturated bonds accounting for 87%, and the number of carbon atoms on any branch chain is 2).

[0108] The Young's modulus, impact strength, T288 of the dielectric layer of the metal substrate of this embodiment, and the peel strength between the dielectric layer and the conductive layer are shown in Table 2.

[0109] Table 2

[0110] Young's modulus Impact strength T288 Peel strength Example 3 1.1 73 >2 2.1 Example 4 0.9 65 1.6 2 Example 5 1.1 72 >2 2.2 Example 6 1.4 73 >2 2.2 Example 7 1.3 73 >2 2.1 Example 8 0.8 69 1.7 2

[0111] Example 9

[0112] Example 9 is carried out with reference to Example 1, except that the epoxy-modified polybutadiene is replaced by an epoxy-modified acrylic resin (brand name UG-4010, Jingyi Chemical, the repeating units of the main chain are non-conjugated carbon-carbon double bonds and CC bonds, the epoxy equivalent is 200, the glass transition temperature Tg is 9°C, and the molecular weight is 1800).

[0113] The Young's modulus, impact strength, T288 of the dielectric layer of the metal substrate of this embodiment, and the peel strength between the dielectric layer and the conductive layer are shown in Table 3.

[0114] Example 10

[0115] Example 10 is carried out with reference to Example 1, except that the epoxy-modified polybutadiene is replaced by an epoxy-modified acrylic resin (brand F-303, Jingyi Chemical, the repeating units of the main chain are non-conjugated carbon-carbon double bonds and CC bonds, the epoxy equivalent is 200, the glass transition temperature Tg is 21°C, and the molecular weight is 600).

[0116] The Young's modulus, impact strength, T288 of the dielectric layer of the metal substrate of this embodiment, and the peel strength between the dielectric layer and the conductive layer are shown in Table 3.

[0117] Embodiment 11

[0118] Example 11 was carried out with reference to Example 1, except that the epoxy-modified polybutadiene was replaced with epoxy-modified polysiloxane (brand name SI-203, Huizhou Aike New Materials, repeating units of the main chain were CC bond, CO bond, Si-O bond, epoxy equivalent was 280, glass transition temperature Tg was -9°C, molecular weight was 560), and the amount of allyl alcohol polyoxyethylene ether was reduced to 11 parts by weight. At the same time, the amount of pre-reacted flexible resin in the resin composition was 41 parts by weight.

[0119] The Young's modulus, impact strength, T288 of the dielectric layer of the metal substrate of this embodiment, and the peel strength between the dielectric layer and the conductive layer are shown in Table 3.

[0120] Example 12

[0121] Example 12 is carried out with reference to Example 1, except that the epoxy-modified polybutadiene is replaced by epoxy-modified polyethylene glycol (brand name EPPEG4500, Tesco Chemical, the repeating units of the main chain are CC bond and CO bond, the epoxy equivalent is 300, the glass transition temperature Tg is -22°C, and the molecular weight is 4500), and the amount of allyl alcohol polyoxyethylene ether is reduced to 10 parts by weight. At the same time, the amount of pre-reacted flexible resin in the resin composition is 40 parts by weight.

[0122] The Young's modulus, impact strength, T288 of the dielectric layer of the metal substrate of this embodiment, and the peel strength between the dielectric layer and the conductive layer are shown in Table 3.

[0123] Table 3

[0124] Young's modulus Impact strength T288 Peel strength Example 9 1.2 72 >2 2.1 Example 10 1.4 74 >2 2.1 Embodiment 11 1.1 69 >2 1.9 Example 12 0.8 64 >2 1.7

[0125] Example 13

[0126] Example 13 was carried out with reference to Example 1, except that the pentadecene-modified cage-type polysilsesquioxane in the resin composition was replaced with heptyl acrylate-modified cage-type polysilsesquioxane (brand number: POSS1008, Qiyue Bio, has heptyl acrylate grafted on the 5 vertices, the repeating structural units are CC bonds and CO bonds, the molecular weight of a single flexible chain segment is 153, and the flexible chain segment does not contain branches).

[0127] The Young's modulus, impact strength, T288 of the dielectric layer of the metal substrate of this embodiment, and the peel strength between the dielectric layer and the conductive layer are shown in Table 4.

[0128] Embodiment 14

[0129] Example 14 was carried out with reference to Example 1, except that the pentadecene-modified cage-type polysilsesquioxane in the resin composition was replaced with vinyl polysiloxane-modified cage-type polysilsesquioxane (brand number: POSS1019, Qiyue Bio, has 5 vertices grafted with vinyl polysiloxane, the repeating structural units are CC bond, CO bond, Si-O bond, the molecular weight of a single flexible chain segment is 300, and the flexible chain segment does not contain branches).

[0130] The Young's modulus, impact strength, T288 of the dielectric layer of the metal substrate of this embodiment, and the peel strength between the dielectric layer and the conductive layer are shown in Table 4.

[0131] Embodiment 15

[0132] Example 15 is carried out with reference to Example 1, except that the pentadecene-modified cage-type polysilsesquioxane in the resin composition is replaced by dodecene-modified cage-type polysilsesquioxane (brand name: PSL200POSS, Laiyang Shengbang Silicone, with dodecene grafted at 5 vertices, a repeating structural unit of CC bond, a molecular weight of a single flexible chain segment of 200, and the number of atoms on any branch chain of 10).

[0133] The Young's modulus, impact strength, T288 of the dielectric layer of the metal substrate of this embodiment, and the peel strength between the dielectric layer and the conductive layer are shown in Table 4.

[0134] Example 16

[0135] Example 16 is carried out with reference to Example 1, except that the pentadecene-modified cage-type polysilsesquioxane in the resin composition is replaced by undecene-modified cage-type polysilsesquioxane (brand name: PSH200POSS, Laiyang Shengbang Silicone, with undecene grafted at 5 vertices, a repeating structural unit of CC bond, a molecular weight of a single flexible chain segment of 200, and the number of atoms on any branch chain of 13).

[0136] The Young's modulus, impact strength, T288 of the dielectric layer of the metal substrate of this embodiment, and the peel strength between the dielectric layer and the conductive layer are shown in Table 4.

[0137] Table 4

[0138] Young's modulus Impact strength T288 Peel strength Example 13 1.1 70 >2 2.3 Embodiment 14 0.7 65 1.9 2.1 Embodiment 15 1.1 72 >2 2.1 Example 16 1.4 72 >2 2.2

[0139] In the above embodiments and comparative examples, the performance test standards of the metal substrate are shown in Table 5.

[0140] Table 5

[0141]

[0142] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0143] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A resin composition, characterized in that It comprises a mixed resin, a filler and a curing agent, wherein the mixed resin comprises a hydrocarbon resin, a flexible resin and a modified cage-type polysilsesquioxane resin; Wherein, the glass transition temperature of the hydrocarbon resin is less than or equal to -10°C; The flexible resin is selected from epoxy-modified flexible resin or pre-reacted flexible resin obtained by reacting epoxy-modified flexible resin with epoxy curing agent, and the epoxy equivalent of the epoxy-modified flexible resin is 150 g / mol-300 g / mol; Among the eight vertices in the modified cage-type polysilsesquioxane, at least four vertices are grafted with flexible segments, and the end groups of the flexible segments are selected from functional groups that can react with the hydrocarbon resin.

2. The resin composition according to claim 1, characterized in that The hydrocarbon resin also satisfies at least one of the following conditions: (1) The number average molecular weight of the hydrocarbon resin is 2000 g / mol-10000 g / mol; (2) The functionality of the carbon-carbon unsaturated bonds of the hydrocarbon resin is 50-200; (3) The hydrocarbon resin contains a branched chain, and the carbon-carbon unsaturated bonds on the branched chain account for 60% to 95% of the total number of carbon-carbon unsaturated bonds on the hydrocarbon resin; (4) The hydrocarbon resin contains a branched chain, and the number of carbon atoms in any branched chain is less than or equal to 7.

3. The resin composition according to claim 2, characterized in that The hydrocarbon resin includes at least one of polybutadiene, polyisoprene, ethylene propylene diene monomer rubber, propylene dimethyl butadiene copolymer, butadiene nonene copolymer or butadiene dodecene copolymer.

4. The resin composition according to claim 1, characterized in that The epoxy modified flexible resin also satisfies at least one of the following conditions: (1) The glass transition temperature of the epoxy modified flexible resin is less than or equal to 10°C; (2) The number average molecular weight of the epoxy modified flexible resin is 500 g / mol-5000 g / mol.

5. The resin composition according to claim 4, characterized in that The epoxy-modified flexible resin includes at least one of epoxy-modified silicone resin, epoxy-modified hydrocarbon resin, epoxy-modified polyethylene glycol or epoxy-modified acrylic resin.

6. The resin composition according to claim 1, characterized in that The residual rate of epoxy groups in the pre-reacted flexible resin is less than or equal to 10%; And / or, the epoxy curing agent is selected from a bifunctional curing agent; And / or, the molecular weight of the epoxy curing agent is 80 g / mol-200 g / mol.

7. The resin composition according to claim 1, characterized in that The modified cage-type polysilsesquioxane further satisfies at least one of the following conditions: (1) The number average molecular weight of the soft segment is 150 g / mol-300 g / mol; (2) When the flexible segment contains branches, the number of atoms in any branch is less than or equal to 12.

8. The resin composition according to claim 7, characterized in that The flexible chain segment is selected from at least one of a long-chain olefin, a polyethylene glycol chain, a polysiloxane chain, a long-chain acrylate or a long-chain polylactic acid.

9. The resin composition according to any one of claims 1 to 8, characterized in that Based on 100 parts by weight of the hydrocarbon resin, the amount of the flexible resin is 20 parts by weight to 50 parts by weight, the amount of the modified cage-type polysilsesquioxane is 30 parts by weight to 60 parts by weight, the amount of the filler is 700 parts by weight to 1800 parts by weight, and the amount of the curing agent is 10 parts by weight to 30 parts by weight.

10. An adhesive film, comprising a carrier layer and a dielectric layer stacked in sequence, characterized in that: The dielectric layer is made of the resin composition according to any one of claims 1 to 9.

11. A metal substrate, comprising a conductive layer, a dielectric layer and a metal plate stacked in sequence, characterized in that: The dielectric layer is made of the resin composition according to any one of claims 1 to 9.

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