Resin composition as well as preparation method and application thereof

Abstract

The invention provides a resin composition and a preparation method and application thereof.The resin composition comprises epoxidized rubber, a styrene thermoplastic elastomer and a curing agent, the curing agent comprises one or more of a ketimine curing agent and an aldimine curing agent, the resin composition has insulativity, and when the resin composition is suitable for a glass base material or a polyimide base material, the resin composition can be used for curing a glass substrate or a polyimide substrate. Good water resistance and moisture resistance are realized.

Description

Technical Field

[0001] The present invention relates to the field of electronic component packaging, and in particular to a resin composition and a preparation method and application thereof. Background Art

[0002] In the manufacturing process of electronic equipment, in order to protect electronic components from moisture, dust and corrosive gases, an insulating resin composition is applied to electronic components (such as mounted circuit boards and electrodes). Commonly used resin compositions include ultraviolet curable resin compositions (such as acrylic resin compositions), moisture curable resin compositions (such as silicone resin compositions), solvent drying resin compositions (such as styrene block copolymer resin compositions), etc.

[0003] The earliest insulating resin composition used was silica gel in the silicone resin composition, but silica gel has low cohesive strength and is difficult to repair. In addition, silica gel is moisture permeable, so silica gel must be applied very thickly to protect the metal of the circuit and electrode. After the acrylic resin composition is cured, it is difficult to meet the water resistance requirements of the glass substrate or polyimide substrate interface in the circuit board. Although the solvent-dried resin composition currently used in the market can be used for electrode protection requirements, it will cause cracks or the glue layer to fall off under high temperature and high humidity conditions, and moisture will penetrate the glue film or enter the glue layer along the substrate interface, causing corrosion of the electrode.

[0004] Based on this, there is an urgent need to develop a resin composition with insulating properties, which has good water resistance and moisture resistance when applied to a glass substrate or a polyimide substrate. Summary of the invention

[0005] The invention provides a resin composition and a preparation method and application thereof. The resin composition has insulation properties and, when suitable for a glass substrate or a polyimide substrate, has good water resistance and moisture resistance, thus overcoming the defects of the prior art.

[0006] One aspect of the present invention provides a resin composition, comprising epoxidized rubber, a styrene-based thermoplastic elastomer, and a curing agent, wherein the curing agent comprises one or more of a ketimine curing agent and an aldimine curing agent.

[0007] According to one embodiment of the present invention, the mass percentage of the curing agent in the resin composition is 0.5% to 10%.

[0008] According to one embodiment of the present invention, the ketimine curing agent includes a dehydration condensation product of a ketone compound and a polyamine; and / or the aldimine curing agent includes a dehydration condensation product of an aldehyde compound and a polyamine.

[0009] According to one embodiment of the present invention, the ketone compound includes one or more of acetone, butanone, methyl isobutyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, and acetophenone; and / or, the aldehyde compound includes one or more of benzaldehyde, phenylacetaldehyde, n-butyraldehyde, isobutyraldehyde, isovaleraldehyde, and 2,2-dimethyl-3-lauroyloxy-propionaldehyde; and / or, the polyprimary amine includes one or more of 1,2-dimethylaminocyclohexane, 1,3-dimethylaminocyclohexane, 1,4-dimethylaminocyclohexane, 1,2-dimethylamino-4-methylcyclohexane, 1,3-dimethylamino-5-methylcyclohexane, 1,4-dimethylamino-2-methylcyclohexane, 1,2-dimethylamino-4-ethylcyclohexane, and 1,3-dimethylamino-5-ethylcyclohexane.

[0010] According to one embodiment of the present invention, the epoxidized rubber includes one or more of epoxidized polybutadiene, epoxidized styrene-butadiene rubber, epoxidized natural rubber, epoxidized synthetic polyisoprene, epoxidized isoprene-butadiene rubber, epoxidized carboxylated nitrile rubber, and epoxidized ethylene-propylene-diene monomer rubber; and / or, the epoxidized rubber has an epoxide equivalent of 100 to 5000 g / eq; and / or, the epoxidized rubber accounts for 1% to 20% by mass of the resin composition.

[0011] According to one embodiment of the present invention, the styrene-based thermoplastic elastomer includes one or more of a styrene-butadiene block copolymer elastomer, a styrene-isoprene block copolymer elastomer, a styrene-ethylene / butylene block copolymer elastomer, and a styrene-ethylene / propylene block copolymer elastomer; and / or, the mass percentage of the styrene-based thermoplastic elastomer in the resin composition is 5% to 30%.

[0012] According to one embodiment of the present invention, the resin composition further includes a tackifier; preferably, the tackifier includes one or more of a petroleum resin tackifier, a terpene resin tackifier, a rosin resin tackifier, a coumarone resin tackifier, and a styrene resin tackifier; preferably, the mass percentage of the tackifier in the resin composition is 1% to 10%.

[0013] According to one embodiment of the present invention, the resin composition further includes a solvent, and the solvent includes one or more of acetate solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, and halogenated alkane solvents. The aliphatic hydrocarbon solvent includes one or more of a first aliphatic hydrocarbon solvent and a second aliphatic hydrocarbon solvent. The boiling point of the first aliphatic hydrocarbon solvent is 80~110°C, and the boiling point of the second aliphatic hydrocarbon solvent is 110~140°C; preferably, the mass percentage of the solvent in the resin composition is 40%~80%.

[0014] Another aspect of the present invention provides a method for preparing the above-mentioned resin composition, comprising the following steps: mixing the epoxidized rubber, the styrene-based thermoplastic elastomer and the curing agent to obtain the resin composition; preferably, the process of mixing the epoxidized rubber, the styrene-based thermoplastic elastomer and the curing agent comprises: mixing the epoxidized rubber, the styrene-based thermoplastic elastomer, the curing agent, the tackifier and the solvent to obtain the resin composition.

[0015] Another aspect of the present invention provides a structural part, comprising an electronic component and a protective layer disposed on the surface of the electronic component, wherein the protective layer is formed by curing the above resin composition or a resin composition prepared according to the preparation method of the above resin composition.

[0016] The resin composition of the present invention comprises an epoxidized rubber, a styrene-based thermoplastic elastomer, and a curing agent, wherein the curing agent comprises one or more of a ketimine curing agent and an aldimine curing agent. The resin composition has insulating properties and, when applied to a glass substrate or a polyimide substrate, has good water resistance, moisture resistance, tight adhesion, and long-term insulation reliability. In addition, the resin composition also has excellent mechanical properties and thermal stability. DETAILED DESCRIPTION

[0017] In order to enable those skilled in the art to better understand the scheme of the present invention, the present invention is further described in detail below. The specific implementation methods listed below are only for describing the principles and features of the present invention. The examples are only used to explain the present invention and are not intended to limit the scope of the present invention. Based on the embodiments of the present invention, all other implementation methods obtained by ordinary technicians in the field without creative work are within the scope of protection of the present invention.

[0018] The embodiment of the present invention provides a resin composition (or moisture-activated epoxy resin composition), including epoxidized rubber, styrene-based thermoplastic elastomer, and curing agent, wherein the curing agent includes one or more of ketimine curing agent and aldimine curing agent. The resin composition has insulating properties and has good water resistance, moisture resistance, tight adhesion and long-term insulation reliability when applied to glass substrates or polyimide substrates. In addition, the resin composition of the present invention has a suitable viscosity, which is conducive to coating by coating methods such as dispensing machines, improves coating uniformity, improves production efficiency, and reduces production costs.

[0019] In the above resin composition, the styrene-based thermoplastic elastomer is a block copolymer, and no chemical reaction occurs during the curing process of the resin composition. However, hydrogen bonds exist between the hard segments (styrene segments) of the styrene-based thermoplastic elastomer, and physical crosslinking occurs, which is beneficial to improving the moisture resistance and insulation of the resin composition. The epoxidized rubber and the curing agent produce chemical crosslinking, and at the same time, the epoxidized rubber and the hard segments of the styrene-based thermoplastic elastomer also have physical crosslinking, which further improves the strength, water resistance and moisture resistance of the resin composition.

[0020] In some embodiments, the curing agent includes a compound represented by Formula 1:

[0021] Formula 1,

[0022] Wherein, R is selected from one or more of hydrogen atom, aliphatic hydrocarbon group, aromatic hydrocarbon group, R' is selected from one or more of aliphatic hydrocarbon group, aromatic hydrocarbon group, R'' is selected from one or more of aliphatic hydrocarbon group, aromatic hydrocarbon group, and the group shown in formula 2,

[0023] Formula 2,

[0024] Among them, the aliphatic hydrocarbon group is an electron-pushing group, and the aromatic hydrocarbon group is an electron-withdrawing group. The presence of the electron-withdrawing group is beneficial to reducing the hydrolysis rate of the curing agent and improving the stability of the curing agent.

[0025] When R is selected from one or more of aliphatic hydrocarbon groups and aromatic hydrocarbon groups, R' is selected from one or more of aliphatic hydrocarbon groups and aromatic hydrocarbon groups, and R'' is selected from one or more of aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by Formula 2, the curing agent is a ketimine curing agent.

[0026] In the above system, the ketone compound and the primary amine are dehydrated and condensed to be converted into the corresponding ketimine curing agent, thereby temporarily blocking the reactivity of the primary amino group in the primary amine. The ketimine curing agent absorbs water and decomposes in a humid environment to release the primary amine and ketone compound with curing effect. Since the water absorption and decomposition rate of the ketimine curing agent is relatively slow, it is beneficial to appropriately extend the curing time of the resin composition and improve the operability of the curing process. For example, for the compound shown in Formula 1, when R is selected from one or more of aliphatic hydrocarbon groups and aromatic hydrocarbon groups, R' is selected from one or more of aliphatic hydrocarbon groups and aromatic hydrocarbon groups, and R'' is selected from one or more of aliphatic hydrocarbon groups and aromatic hydrocarbon groups, the reaction process of the ketone compound and the primary amine being dehydrated and condensed to be converted into the corresponding ketimine curing agent is shown in Reaction Formula 1, and the reaction process of the ketimine curing agent absorbing water and decomposing in a humid environment to release the primary amine and ketone compound with curing effect is shown in Reaction Formula 2:

[0027] Reaction 1:

[0028] Reaction formula 2.

[0029] When R is a hydrogen atom, R' is selected from one or more of aliphatic hydrocarbon groups and aromatic hydrocarbon groups, and R'' is selected from one or more of aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups shown in Formula 2, the curing agent is an aldimine curing agent. Compared with a ketimine curing agent, the aldimine curing agent has a lower hydrolysis rate and higher stability.

[0030] In the above system, the aldehyde compound and the primary amine are dehydrated and condensed to be converted into the corresponding aldimine curing agent, thereby temporarily blocking the reactivity of the primary amino group in the primary amine. The aldimine curing agent absorbs water and decomposes in a humid environment to release the primary amine and aldehyde compound with a curing effect. Compared with the ketimine curing agent, the aldimine curing agent absorbs water and decomposes more slowly, which is conducive to further extending the curing time of the resin composition and improving the operability of the curing process. For example, for the compound shown in Formula 1, when R is a hydrogen atom, R' is selected from one or more of aliphatic hydrocarbon groups and aromatic hydrocarbon groups, and R'' is selected from one or more of aliphatic hydrocarbon groups and aromatic hydrocarbon groups, the reaction process of the aldehyde compound and the primary amine being dehydrated and condensed to be converted into the corresponding aldimine curing agent is shown in Reaction Formula 1, and the reaction process of the aldimine curing agent absorbing water and decomposing in a humid environment to release the primary amine and aldehyde compound with a curing effect is shown in Reaction Formula 2:

[0031] Reaction 1:

[0032] Reaction formula 2.

[0033] In a specific implementation, the curing agent includes a compound shown in Formula 3:

[0034] Formula 3,

[0035] Wherein, R is selected from one or more of hydrogen atom, aliphatic hydrocarbon group, aromatic hydrocarbon group, R' is selected from one or more of aliphatic hydrocarbon group, aromatic hydrocarbon group, and L is selected from one or more of aliphatic hydrocarbon group, aromatic hydrocarbon group.

[0036] In some embodiments, the mass percentage of the curing agent in the resin composition is 0.5% to 10%, for example, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% or a range consisting of any two thereof, which is beneficial to the curing of the epoxidized rubber.

[0037] In some embodiments, the ketimine curing agent includes a dehydration condensation product of a ketone compound and a polyamine.

[0038] According to the inventors' research, ketone compounds are dehydrated and condensed with polyamines to be converted into corresponding ketimine curing agents (compounds as shown in Formula 3), thereby temporarily blocking the reactivity of the primary amino groups in the polyamines. The ketimine curing agents absorb water and decompose in a humid environment to release polyamines and ketone compounds with curing effects. The resin composition including the above-mentioned ketimine curing agent has both a long curing time and good water resistance and moisture resistance.

[0039] In addition, the aldimine curing agent includes a dehydration condensation product of an aldehyde compound and a polyamine.

[0040] According to the inventors' research, aldehyde compounds are dehydrated and condensed with polyamines to be converted into corresponding aldimine curing agents (compounds as shown in Formula 3), thereby temporarily blocking the reactivity of the primary amino groups in the polyamines. The aldimine curing agents absorb water and decompose in a humid environment to release polyamines and aldehyde compounds with curing effects. The resin composition including the above-mentioned aldimine curing agent has both a long curing time and good water resistance and moisture resistance.

[0041] In some embodiments, the ketone compound includes one or more of acetone, butanone, methyl isobutyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, and acetophenone.

[0042] In addition, the aldehyde compound includes one or more of benzaldehyde, phenylacetaldehyde, n-butyraldehyde, isobutyraldehyde, isovaleraldehyde, and 2,2-dimethyl-3-lauroyloxy-propionaldehyde.

[0043] Specifically, the polyvalent primary amine includes a cyclohexane ring and methylamino groups directly bonded to the cyclohexane ring, and the number of methylamino groups directly bonded to the cyclohexane ring is two or more.

[0044] In some embodiments, the polyamine includes one or more of 1,2-dimethylaminocyclohexane, 1,3-dimethylaminocyclohexane, 1,4-dimethylaminocyclohexane, 1,2-dimethylamino-4-methylcyclohexane, 1,3-dimethylamino-5-methylcyclohexane, 1,4-dimethylamino-2-methylcyclohexane, 1,2-dimethylamino-4-ethylcyclohexane, and 1,3-dimethylamino-5-ethylcyclohexane.

[0045] The ketimine curing agent in the present invention is formed by the dehydration condensation of the above-mentioned ketone compound and the above-mentioned polyamine, and the aldimine curing agent is formed by the dehydration condensation of the above-mentioned aldehyde compound and the above-mentioned polyamine. The polyamines constituting the ketimine curing agent and the aldimine curing agent may be the same or different.

[0046] In some embodiments, the epoxidized rubber (or epoxy resin) includes one or more of epoxidized polybutadiene (or epoxidized butadiene rubber), epoxidized styrene-butadiene rubber, epoxidized natural rubber, epoxidized synthetic polyisoprene, epoxidized isoprene-butadiene rubber, epoxidized carboxylated nitrile rubber, and epoxidized ethylene-propylene-diene monomer rubber. For example, the epoxidized ethylene-propylene-diene monomer rubber refers to an epoxidized rubber synthesized with ethylene and propylene as main monomers.

[0047] In a specific implementation, the epoxidized rubber includes epoxidized styrene-butadiene rubber, which is beneficial to improving the adhesion of the resin composition.

[0048] In addition, the epoxy equivalent of the epoxidized rubber is 100 to 5000 g / eq, for example, 100 g / eq, 200 g / eq, 300 g / eq, 500 g / eq, 1000 g / eq, 2000 g / eq, 3000 g / eq, 5000 g / eq, which is beneficial to improving the adhesion of the resin composition.

[0049] Specifically, the mass percentage of the epoxidized rubber in the resin composition is 1% to 20%, for example, 1%, 2%, 3%, 5%, 10%, 15%, 20% or a range consisting of any two thereof.

[0050] In some embodiments, the styrene-based thermoplastic elastomer (or styrene block copolymer resin) includes one or more of styrene-butadiene block copolymer elastomer (SBS), styrene-isoprene block copolymer elastomer (SIS), styrene-ethylene / butylene block copolymer elastomer (SEBS), and styrene-ethylene / propylene block copolymer elastomer (SEPS).

[0051] The styrene-based thermoplastic elastomer in the present invention is copolymerized with styrene and a hydrocarbon compound having an unsaturated double bond. The hydrocarbon compound having an unsaturated double bond includes one or more of butadiene, isoprene, ethylene, butylene, and propylene. For example, the styrene-ethylene / butylene block copolymer elastomer is copolymerized with styrene, ethylene, and butylene.

[0052] In a specific implementation, the mass percentage of the styrene-based thermoplastic elastomer in the resin composition is 5% to 30%, for example, 5%, 10%, 15%, 20%, 25%, 30% or a range consisting of any two thereof.

[0053] In some embodiments, the resin composition further includes a tackifier, which helps to improve the adhesion of the resin composition.

[0054] In some embodiments, the tackifier includes one or more of a petroleum resin tackifier, a terpene resin tackifier, a rosin resin tackifier, a coumarone resin tackifier, and a styrene resin tackifier, preferably a petroleum resin tackifier, which helps to improve the adhesion of the resin composition.

[0055] In a specific implementation, the mass percentage of the tackifier in the resin composition is 1% to 10%, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% or a range consisting of any two thereof.

[0056] In some embodiments, the resin composition further includes a solvent, which is beneficial for dissolving the styrene-based thermoplastic elastomer and improving the uniformity of the resin composition.

[0057] In some embodiments, the solvent includes one or more of acetate solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, and halogenated alkane solvents.

[0058] Among them, the aliphatic hydrocarbon solvent includes one or more of a first aliphatic hydrocarbon solvent and a second aliphatic hydrocarbon solvent. The boiling point of the first aliphatic hydrocarbon solvent is 80~110°C, for example, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C or a range composed of any two of them, which is beneficial to avoid too long drying time of the resin composition.

[0059] Specifically, the first aliphatic hydrocarbon solvent includes one or more of n-heptane (boiling point: 98.4° C.), cyclohexane (boiling point: 80.7° C.), and methylcyclohexane (boiling point: 101.1° C.).

[0060] The boiling point of the second aliphatic hydrocarbon solvent is 110-140°C, for example, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C or a range consisting of any two thereof, which is beneficial to prolonging the drying time of the resin composition and thereby prolonging the operable time of its curing process.

[0061] Specifically, the second aliphatic hydrocarbon solvent includes one or more of n-octane (boiling point of 125.7°C), cis-1,2-dimethylcyclohexane (boiling point of 129.7°C), cis-1,3-dimethylcyclohexane (boiling point of 120.1°C), cis-1,4-dimethylcyclohexane (boiling point of 124.3°C), trans-1,2-dimethylcyclohexane (boiling point of 123.4°C), trans-1,3-dimethylcyclohexane (boiling point of 124.5°C), trans-1,4-dimethylcyclohexane (boiling point of 119.4°C), and ethylcyclohexane (boiling point of 132°C).

[0062] In a specific implementation, the boiling point of the acetate solvent is less than or equal to 140°C, for example, less than or equal to 140°C, less than or equal to 130°C, less than or equal to 120°C, less than or equal to 110°C, less than or equal to 100°C, less than or equal to 90°C, or a range consisting of any two thereof, which is beneficial for dissolving the styrene-based thermoplastic elastomer and improving the uniformity of the resin composition.

[0063] Specifically, the acetate solvent includes one or more of n-butyl acetate (boiling point is 126.5°C), isobutyl acetate (boiling point is 118°C), tert-butyl acetate (boiling point is 97.8°C), isopropyl acetate (boiling point is 88.8°C), ethyl acetate (boiling point is 77°C), and n-propyl acetate (boiling point is 101.6°C).

[0064] Specifically, the aromatic hydrocarbon solvent includes one or more of benzene and toluene, and the halogenated alkane solvent includes one or more of dichloromethane and dichloroethane.

[0065] Illustratively, the solvent includes, by mass, 0 to 50 parts of methylcyclohexane, 0 to 50 parts of ethylcyclohexane, 0 to 50 parts of n-propyl acetate, and 0 to 50 parts of n-butyl acetate.

[0066] In some embodiments, the resin composition may further include additives, and the additives include one or more of a silane coupling agent, a leveling agent, a defoaming agent, a colorant, and an antioxidant.

[0067] Specifically, the silane coupling agent includes one or more of 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane.

[0068] In a specific implementation, the mass percentage of the silane coupling agent in the resin composition is 0.05% to 5%, for example, 0.05%, 0.1%, 0.2%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.2%, 1.4%, 1.5%, 2.0%, 2.5%, 3.0%, 4.0%, 5.0% or a range composed of any two thereof, preferably 0.5% to 2%.

[0069] Specifically, the leveling agent includes one or more of a silicone leveling agent, an acrylic leveling agent, a fluorine leveling agent, and a vinyl resin leveling agent. The mass percentage of the leveling agent in the resin composition is 0.01% to 5%, for example, 0.01%, 0.05%, 0.1%, 0.2%, 0.5%, 1%, 2%, 3%, 4%, 5% or a range consisting of any two of them.

[0070] Specifically, the defoaming agent includes one or more of a silicone defoaming agent, an acrylic defoaming agent, a fluorine defoaming agent, and a vinyl resin defoaming agent, and the mass percentage of the defoaming agent in the resin composition is 0.01% to 5%, for example, 0.01%, 0.05%, 0.1%, 0.2%, 0.5%, 1%, 2%, 3%, 4%, 5% or a range consisting of any two of them.

[0071] Specifically, the colorant includes one or more of inorganic pigments, organic pigments, and organic dyes, and the mass percentage of the colorant in the resin composition is 0.01% to 5%, for example, 0.01%, 0.05%, 0.1%, 0.2%, 0.5%, 1%, 2%, 3%, 4%, 5% or a range consisting of any two of them.

[0072] Specifically, the antioxidant includes one or more of hindered phenol antioxidants and phosphite antioxidants, and the weight percentage of the antioxidant in the resin composition is 0.01% to 5%, for example, 0.01%, 0.05%, 0.1%, 0.2%, 0.5%, 1%, 2%, 3%, 4%, 5% or a range consisting of any two of them.

[0073] The embodiment of the present invention further provides a method for preparing the above resin composition, comprising the following steps: mixing epoxidized rubber, styrene-based thermoplastic elastomer, and a curing agent to obtain a resin composition.

[0074] In some embodiments, the process of mixing the epoxidized rubber, the styrene-based thermoplastic elastomer, and the curing agent includes: mixing the epoxidized rubber, the styrene-based thermoplastic elastomer, the curing agent, the tackifier, and the solvent to obtain a resin composition.

[0075] In some embodiments, the process of mixing the epoxidized rubber, the styrene-based thermoplastic elastomer, and the curing agent includes: mixing the epoxidized rubber, the styrene-based thermoplastic elastomer, the curing agent, the tackifier, the solvent, and the additives to obtain a resin composition.

[0076] In a specific implementation, raw materials such as epoxidized rubber, styrene-based thermoplastic elastomer, curing agent, tackifier, solvent, etc. are put into a reaction kettle and stirred evenly at 60-90°C, for example, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, or a range composed of any two thereof, to obtain a resin composition.

[0077] In the present invention, the mass of the raw materials forming the resin composition before and after mixing is substantially unchanged, that is, the total mass of the raw materials forming the resin composition is substantially equal to the mass of the resin composition.

[0078] For example, when the raw materials forming the resin composition are epoxidized rubber, styrene-based thermoplastic elastomer, curing agent, tackifier, and solvent, the total mass of the epoxidized rubber, styrene-based thermoplastic elastomer, curing agent, tackifier, and solvent is substantially equal to the mass of the resin composition.

[0079] An embodiment of the present invention further provides a structural part, including an electronic component and a protective layer (or insulating layer) disposed on the surface of the electronic component, wherein the protective layer is formed by curing the above-mentioned resin composition or a resin composition prepared according to the preparation method of the above-mentioned resin composition.

[0080] The present invention is further described below through specific embodiments.

[0081] In the following examples and comparative examples, the raw materials or reagents used are:

[0082] (1) Epoxidized butadiene rubber: manufactured by Daicel Corporation, trade name EPOLEAD PB3600, epoxy equivalent weight 193 g / eq;

[0083] (2) Epoxidized styrene-butadiene rubber: manufactured by Daicel Corporation, trade name EPOFRIEND AT501, styrene content of 40 wt%, epoxy equivalent of 1055 g / eq;

[0084] (3) Ketimine curing agent: Ketimine LSW-501, manufactured by Dalian Liansheng New Materials Co., Ltd., is a dehydration condensation product of methyl isobutyl ketone and 1,3-dimethylaminocyclohexane, with an amine equivalent of 140 g / eq. The chemical formula is shown in Formula 4:

[0085] Formula 4;

[0086] (4) Aldimine curing agent: Aldimine LSW-501E, manufactured by Dalian Liansheng New Materials Co., Ltd., is a dehydration condensation product of isobutyraldehyde and 1,3-dimethylaminocyclohexane, with an amine equivalent of 125 g / eq, and a chemical formula as shown in Formula 5:

[0087] Formula 5;

[0088] (5) Aldimine curing agent: Aldimine LSW-501H, manufactured by Dalian Liansheng New Materials Co., Ltd., is a dehydration condensation product of benzaldehyde and 1,3-dimethylaminocyclohexane, with an amine equivalent of 160 g / eq, and a chemical formula as shown in Formula 6:

[0089] Formula 6;

[0090] (6) Styrene-butadiene block copolymer elastomer (SBS): manufactured by Kraton Corporation of the United States, trade name D1155, styrene content of 40 wt%;

[0091] (7) Styrene-isoprene block copolymer elastomer (SIS): manufactured by Kraton Corporation, USA, trade name D1161, styrene content of 15 wt%;

[0092] (8) Petroleum resin tackifier: manufactured by Japan Zeon Co., Ltd., trade name D100, aliphatic-aromatic copolymer petroleum resin tackifier.

[0093] Example 1

[0094] In parts by mass, 7.34 parts of epoxidized butadiene rubber, 2.66 parts of ketimine LSW-501, 15 parts of styrene-butadiene block copolymer elastomer (SBS), 5 parts of petroleum resin tackifier, 10 parts of methylcyclohexane, 50 parts of ethylcyclohexane, and 10 parts of n-butyl acetate were added to a reactor and mixed at 70° C. for 4 hours to obtain a resin composition.

[0095] Example 2

[0096] In parts by mass, 6.07 parts of epoxidized butadiene rubber, 3.93 parts of aldimine LSW-501E, 15 parts of styrene-butadiene block copolymer elastomer (SBS), 5 parts of petroleum resin tackifier, 10 parts of methylcyclohexane, 50 parts of ethylcyclohexane, and 10 parts of n-butyl acetate were added to a reactor and mixed at 70° C. for 4 h to obtain a resin composition.

[0097] Example 3

[0098] In parts by mass, 5.47 parts of epoxidized butadiene rubber, 4.53 parts of aldimine LSW-501H, 15 parts of styrene-butadiene block copolymer elastomer (SBS), 5 parts of petroleum resin tackifier, 10 parts of methylcyclohexane, 50 parts of ethylcyclohexane, and 10 parts of n-butyl acetate were added to a reactor and mixed at 70° C. for 4 h to obtain a resin composition.

[0099] Example 4

[0100] In parts by mass, 9.38 parts of epoxidized styrene-butadiene rubber, 0.62 parts of ketimine LSW-501, 15 parts of styrene-butadiene block copolymer elastomer (SBS), 5 parts of petroleum resin tackifier, 10 parts of methylcyclohexane, 50 parts of ethylcyclohexane, and 10 parts of n-butyl acetate were added to a reactor and mixed at 70° C. for 4 hours to obtain a resin composition.

[0101] Example 5

[0102] In parts by mass, 8.90 parts of epoxidized styrene-butadiene rubber, 1.10 parts of aldimine LSW-501E, 15 parts of styrene-butadiene block copolymer elastomer (SBS), 5 parts of petroleum resin tackifier, 10 parts of methylcyclohexane, 50 parts of ethylcyclohexane, and 10 parts of n-butyl acetate were added to a reactor and mixed at 70° C. for 4 hours to obtain a resin composition.

[0103] Example 6

[0104] In parts by mass, 8.70 parts of epoxidized styrene-butadiene rubber, 1.30 parts of aldimine LSW-501H, 15 parts of styrene-butadiene block copolymer elastomer (SBS), 5 parts of petroleum resin tackifier, 10 parts of methylcyclohexane, 50 parts of ethylcyclohexane, and 10 parts of n-butyl acetate were added to a reactor and mixed at 70° C. for 4 hours to obtain a resin composition.

[0105] Comparative Example 1

[0106] 25 parts by mass of styrene-butadiene block copolymer elastomer (SBS), 5 parts by mass of petroleum resin tackifier, 10 parts by mass of methylcyclohexane, 50 parts by mass of ethylcyclohexane, and 10 parts by mass of n-butyl acetate were added to a reaction kettle and mixed at 70° C. for 4 hours to obtain a resin composition.

[0107] Comparative Example 2

[0108] 25 parts by mass of styrene-isoprene block copolymer elastomer (SIS), 5 parts by mass of petroleum resin tackifier, 10 parts by mass of methylcyclohexane, 50 parts by mass of ethylcyclohexane, and 10 parts by mass of n-butyl acetate were added to a reaction kettle and mixed at 70° C. for 4 h to obtain a resin composition.

[0109] Table 1 summarizes the type of epoxidized rubber, epoxy equivalent and mass fraction of the epoxidized rubber, type and mass fraction of the styrene-based thermoplastic elastomer, and type and mass fraction of the curing agent in each of the Examples and Comparative Examples.

[0110] The performance of the resin compositions in each embodiment and comparative example was tested by the following process, and the specific results are shown in Table 2 and Table 3:

[0111] (1) Viscosity Evaluation: Viscosity The viscosity (unit: mPa·s) of the resin composition just prepared was measured using a Brookfield DVNext lamina viscometer at 25° C. and 10 revolutions per minute (RPM) using a CPA-52Z rotor.

[0112] (2) Dry to touch time: The resin compositions of the examples and comparative examples were applied to glass using a dispensing machine to form a coating film. After coating, the coating film was touched with a finger every 5 seconds to confirm whether the surface was sticky. The time when the surface was no longer sticky was taken as the dry to touch time. At this time, the thickness of the coating film (i.e., the dried coating film) was about 130 μm.

[0113] (3) Water absorption: The resin composition was dried at room temperature for 12 hours to form a cured product. The water absorption test was conducted according to the following "PCT24" method: The size of the sample (cured product) was 50 mm 3 mm (diameter Thickness), the test conditions are 121℃, 100%RH, 2 atm, 24 h; the water absorption rate is calculated as follows: the weight increase of the sample after "PCT24" treatment / the initial weight of the sample 100%.

[0114] (4) Wrinkles attached to glass: The resin compositions of each embodiment and comparative example were coated on glass to form a coating film, and dried at room temperature for 12 hours to obtain a dried sample. At this time, the thickness of the coating film (i.e., the dried coating film) was about 130 μm. The changes in the film surface were observed and recorded as the initial state (initial). The dried sample was placed in a PCT test chamber under the conditions of 121°C, 100% RH, and 2 atm, and the changes in the film surface after 1 day (24 h), 2 days (48 h), and 3 days (72 h) were observed and recorded. The evaluation criteria were: the film surface wrinkles were flat and no difference was recorded as level 0; the film surface was slightly orange peel with an area less than 1 / 3 of the total area, which was recorded as level 1; the film surface was slightly orange peel with an area ratio of 1 / 3 to 1, which was recorded as level 2; when the film surface orange peel with an area ratio of 1 / 3 to the total area was 1, the film surface was slightly orange peel; the film surface was severely orange peel with a level 3; the film surface was severely bubbling with a level 4.

[0115] (5) Wrinkles attached to polyimide film: The resin compositions of the embodiments and comparative examples were coated on polyimide films to form coatings, which were dried at room temperature for 12 hours to obtain dried samples. At this time, the thickness of the coating (i.e., the dried coating) was about 130 μm. The changes in the film surface were observed and recorded as the initial state (initial). The dried samples were placed in a PCT test chamber at 121 °C, 100% RH, and 2 atm. The changes in the membrane surface were observed and recorded after 1 day (24 h), 2 days (48 h), and 3 days (72 h). The evaluation criteria were as follows: if the membrane surface was smooth and had no difference in wrinkles, it was recorded as level 0; if the area of ​​slight orange peel on the membrane surface was less than 1 / 3 of the total area, it was recorded as level 1; if the ratio of the area of ​​slight orange peel on the membrane surface to the total area was 1 / 3~1, it was recorded as level 2; if the ratio of the area of ​​orange peel on the membrane surface to the total area was 1, the entire membrane surface had slight orange peel; if the entire membrane surface had severe orange peel, it was recorded as level 3; if the entire membrane surface had severe blistering, it was recorded as level 4.

[0116] (6) Insulation evaluation: The insulation is characterized by the resistance to ion migration (i.e., resistance value) of the resin composition. Referring to JEITA ED-4701 / 100, the resin compositions of each embodiment and comparative example were subjected to a high temperature and high humidity bias test. The test method is as follows: The prepared resin composition was coated on a polyimide tape substrate having a tin-plated (0.2 μm) 8 μm thick copper metal wiring (pattern width 4 μm, line width 12 μm, pattern spacing 16 μm), with a coating thickness of 100 μm; and dried and placed at room temperature for 12 hours to prepare a test piece. The resistance value of the test piece when a direct current voltage of 50 V (DC50 V) was applied was measured using an ion migration evaluation system (manufactured by ESPEC), and recorded as the initial resistance value. After the test piece was placed at 130°C and a humidity of 85% for 96 hours, the resistance value when a DC50 V voltage was applied was measured. At this time, if the resistance value remained at 1.00E+7 Ω or more, it was recorded as O, and if it remained below 1.00E+7 Ω, it was recorded as X.

[0117] (7) Heat resistance test: The pyrolysis temperature (temperature at which the weight is reduced by 10%, Td) of the cured product formed by the dried resin composition of each embodiment and comparative example (drying condition: drying and placing at room temperature for 12 hours) was measured using a differential thermal gravimetric simultaneous measuring device (TGA, manufactured by METTLER TOLEDO). 10 ), and the measurement was performed under a nitrogen flow of 50 mL / min and the temperature was increased from 30°C to 800°C at a heating rate of 10°C / min.

[0118] Table 1

[0119]

[0120] Table 2

[0121]

[0122] Table 3

[0123]

[0124] As shown in Table 2, compared with Comparative Examples 1 and 2, the resin compositions in Examples 1 to 6 include epoxidized rubber, styrene-based thermoplastic elastomer, and a curing agent, wherein the curing agent includes one or more of a ketimine curing agent and an aldimine curing agent. The resin compositions have lower water absorption, longer dry-to-touch time, and higher pyrolysis temperature Td. 10 and good insulation properties, therefore, the resin composition has good insulation properties, water resistance and heat resistance.

[0125] In addition, it can be seen from Table 3 that, compared with Comparative Examples 1 and 2, the coatings formed by the resin compositions in Examples 1 to 6 have better wrinkle conditions when attached to glass (PCT placed for 3 days) and wrinkle conditions when attached to polyimide films (PCT placed for 3 days), and the surfaces are relatively smooth. Therefore, when the resin composition is applied to a glass substrate or a polyimide substrate, it has good moisture resistance and water resistance.

[0126] In summary, the resin composition of Examples 1-6 includes epoxidized rubber, styrene-based thermoplastic elastomer, and a curing agent, wherein the curing agent includes one or more of a ketimine curing agent and an aldimine curing agent. The resin composition has insulating properties and has good water resistance and moisture resistance when applied to a glass substrate or a polyimide substrate.

[0127] Finally, it should be noted that those skilled in the art will readily conceive of other embodiments of the present invention after considering the specification and practicing the invention disclosed herein. The present invention is intended to cover any variations, uses or adaptations of the present invention, which follow the general principles of the present invention and include common knowledge or customary technical means in the art not disclosed by the present invention, are not limited to the precise structure described above, and may be modified and changed in various ways without departing from the scope thereof. The scope of the present invention is limited only by the appended claims.

Claims

1. A resin composition, characterized in that The invention comprises epoxidized rubber, styrene-based thermoplastic elastomer and a curing agent, wherein the curing agent comprises one or more of a ketimine curing agent and an aldimine curing agent.

2. The resin composition according to claim 1, characterized in that The mass percentage of the curing agent in the resin composition is 0.5% to 10%.

3. The resin composition according to claim 1, characterized in that The ketimine curing agent includes a dehydration condensation product of a ketone compound and a polyamine; And / or, the aldimine curing agent includes a dehydration condensation product of an aldehyde compound and a polyamine.

4. The resin composition according to claim 3, characterized in that The ketone compound includes one or more of acetone, butanone, methyl isobutyl ketone, methyl isoamyl ketone, methyl isopropyl ketone and acetophenone; And / or, the aldehyde compound includes one or more of benzaldehyde, phenylacetaldehyde, n-butyraldehyde, isobutyraldehyde, isovaleraldehyde, and 2,2-dimethyl-3-lauroyloxy-propionaldehyde; And / or, the polyamine includes one or more of 1,2-dimethylaminocyclohexane, 1,3-dimethylaminocyclohexane, 1,4-dimethylaminocyclohexane, 1,2-dimethylamino-4-methylcyclohexane, 1,3-dimethylamino-5-methylcyclohexane, 1,4-dimethylamino-2-methylcyclohexane, 1,2-dimethylamino-4-ethylcyclohexane, and 1,3-dimethylamino-5-ethylcyclohexane.

5. The resin composition according to claim 1, characterized in that The epoxidized rubber includes one or more of epoxidized polybutadiene, epoxidized styrene-butadiene rubber, epoxidized natural rubber, epoxidized synthetic polyisoprene, epoxidized isoprene-butadiene rubber, epoxidized carboxylated nitrile rubber, and epoxidized ethylene-propylene-diene monomer rubber; And / or, the epoxy equivalent of the epoxidized rubber is 100 to 5000 g / eq; And / or, the mass percentage of the epoxidized rubber in the resin composition is 1% to 20%.

6. The resin composition according to claim 1, characterized in that The styrene-based thermoplastic elastomer includes one or more of styrene-butadiene block copolymer elastomer, styrene-isoprene block copolymer elastomer, styrene-ethylene / butylene block copolymer elastomer, and styrene-ethylene / propylene block copolymer elastomer; And / or, the mass percentage of the styrene-based thermoplastic elastomer in the resin composition is 5% to 30%.

7. The resin composition according to claim 1, characterized in that The resin composition further comprises a tackifier; Preferably, the tackifier includes one or more of a petroleum resin tackifier, a terpene resin tackifier, a rosin resin tackifier, a coumarone resin tackifier, and a styrene resin tackifier; Preferably, the mass percentage of the tackifier in the resin composition is 1% to 10%.

8. The resin composition according to claim 1, characterized in that The resin composition further comprises a solvent, wherein the solvent comprises one or more of an acetate solvent, an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, and a halogenated alkane solvent, wherein the aliphatic hydrocarbon solvent comprises one or more of a first aliphatic hydrocarbon solvent and a second aliphatic hydrocarbon solvent, wherein the boiling point of the first aliphatic hydrocarbon solvent is 80-110° C., and the boiling point of the second aliphatic hydrocarbon solvent is 110-140° C.; Preferably, the mass percentage of the solvent in the resin composition is 40% to 80%.

9. A method for preparing the resin composition according to any one of claims 1 to 8, characterized in that: The following steps are involved: The epoxidized rubber, the styrene-based thermoplastic elastomer and the curing agent are mixed to obtain the resin composition; Preferably, the process of mixing the epoxidized rubber, the styrene-based thermoplastic elastomer and the curing agent comprises: mixing the epoxidized rubber, the styrene-based thermoplastic elastomer, the curing agent, a tackifier and a solvent to obtain the resin composition.

10. A structural member, characterized in that: The invention comprises an electronic component and a protective layer arranged on the surface of the electronic component, wherein the protective layer is formed by curing the resin composition according to any one of claims 1 to 8 or the resin composition prepared by the method for preparing the resin composition according to claim 9.

Images