Reaction type ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad plate, composition and preparation method thereof

Abstract

The invention discloses a reaction type ultraviolet shielding high-toughness flame-retardant epoxy resin solution for a copper-clad plate, a composition and a preparation method of the reaction type ultraviolet shielding high-toughness flame-retardant epoxy resin solution, and is characterized in that the reaction type ultraviolet shielding high-toughness flame-retardant epoxy resin solution for the copper-clad plate is prepared from 1, 1, 2, 3, 3-tetramethyl-1, 3, 3-tetramethyl-1 The epoxy resin is prepared by performing chemical reaction on 1, 2, 2-tetra (p-hydroxyphenyl) ethane tetraglycidyl ether epoxy resin, high-bromine epoxy resin, ethyl triphenyl phosphine acetate and diphenylmethane-4, 4 '-diisocyanate and then adding butanone. The composition is prepared by mixing a reaction type ultraviolet shielding high-toughness flame-retardant epoxy resin solution for the copper-clad plate, E51 bisphenol A epoxy resin, linear phenolic resin, ODA type benzoxazine resin, 2-ethyl-4-methylimidazole and butanone. The resin for the copper-clad plate, provided by the invention, has the advantages of reactive ultraviolet shielding, high heat resistance, high toughness and excellent flame retardant property, and the prepared copper-clad plate has excellent comprehensive performance and strong practicability.

Description

Technical Field

[0001] The present invention belongs to the technical field of synthesis modification and application of organic compound epoxy resin, and relates to a reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates, a composition and a preparation method thereof. The reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution and composition for copper-clad laminates of the present invention (prepared) are particularly suitable for the preparation of copper-clad laminates for printed circuit boards. Background Art

[0002] Copper clad laminate is the basic material of the electronics industry, mainly used for processing and manufacturing printed circuit boards (PCBs), and is widely used in various electronic products such as computers, new energy vehicles, mobile communications, and home appliances. Existing copper clad laminate resins are basically produced by using various common epoxy resins, brominated epoxy resins, halogen-free flame-retardant epoxy resins, heat-resistant epoxy resins, phosphorus-containing phenolic resins, benzoxazine resins, etc., with curing agents and solvents. With the development of electronic products towards miniaturization, multi-function, high-frequency, high-speed and high-reliability, printed circuit boards have developed from single-layer to double-sided and multi-layer. In the production process of double-sided printed circuit boards and multi-layer boards, due to the promotion and application of photosensitive solder resists and the need for double-sided exposure, during the exposure process, ultraviolet light will have a mutual influence on the images on both sides of the board and generate ghosting, thereby causing the scrapping of the printed circuit board. Therefore, it is necessary to add a resin with ultraviolet shielding to the board to avoid ghosting during exposure.

[0003] At present, copper clad laminate manufacturers generally use low-bromine epoxy to add tetrafunctional epoxy resin to prepare epoxy resin with UV shielding function. However, it is not easy to achieve good compatibility with low-bromine epoxy resin due to the addition of tetrafunctional epoxy, and the toughness is also poor and Tg is also low.

[0004] In the prior art, CN101735176A discloses "a method for synthesizing a tetrafunctional epoxy resin and the epoxy resin obtained therefrom". The further application of this resin in the copper clad laminate industry is to add a flame retardant epoxy resin, or further add a toughening epoxy resin to the mixture to meet the requirements of the copper clad laminate industry for flame retardancy and a certain toughness. However, it is a physical addition type, and the uneven mixing and the migration of different types of resins during pressing affect the uniformity of the entire board, and the performance cannot meet the requirements. Summary of the invention

[0005] The purpose of the present invention is to overcome the deficiencies in the above-mentioned prior art and provide a reactive UV-shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates, a composition and a preparation method thereof. Thus, a reactive UV-shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates with excellent comprehensive performance, a composition and a preparation method thereof are provided.

[0006] The invention discloses a reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates. The reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates is characterized in that the reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates is prepared by chemically reacting 1,1,2,2-tetra(p-hydroxyphenyl)ethane tetraglycidyl ether epoxy resin, high-bromine epoxy resin, ethyl triphenylphosphine acetate and diphenylmethane-4,4'-diisocyanate, and then adding butanone to dilute the solution.

[0007] In the context of the present invention: the reactive ultraviolet shielding high-toughness flame-retardant epoxy resin for copper-clad laminate has a chemical structure fragment formula as shown below:

[0008]

[0009] In the content of the present invention: the mass percentage content of the solid content in the reactive UV shielding high-toughness flame-retardant epoxy resin solution is 75±1% (ie: 74% to 76%), the viscosity is 2000 to 4000 mpas, and the number average molecular weight is 800 to 2000.

[0010] In the context of the present invention: the 1,1,2,2-tetra(p-hydroxyphenyl)ethane tetraglycidyl ether epoxy resin has a chemical structural formula as shown below:

[0011]

[0012] The product brand and production provider of the 1,1,2,2-tetrakis (p-hydroxyphenyl) ethane tetraglycidyl ether epoxy resin are: TPGEE TGE Shandong Jiaying Chemical Technology Co., Ltd.

[0013] In the context of the present invention: the high-bromine epoxy resin has a chemical structural formula as shown below:

[0014]

[0015] The product brand and production provider of the high-bromine epoxy resin are: NPEB-400, Kunshan Nanya.

[0016] The diphenylmethane-4,4'-diisocyanate has a chemical structural formula as shown below:

[0017]

[0018] The ethyl triphenylphosphine acetate has a simplified chemical structure as shown below:

[0019]

[0020] In the content of the present invention: the preparation method of the reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates comprises the following steps:

[0021] a. Add 40-50 parts by weight of 1,1,2,2-tetrakis(p-hydroxyphenyl)ethane tetraglycidyl ether epoxy resin and 50-60 parts by weight of high-bromine epoxy resin into a reactor (or reactor), heat to 135°C, evacuate for 1 hour, and the vacuum gauge pressure is less than 15kPa;

[0022] b. Add 0.04-0.1 parts by mass of ethyl triphenylphosphine acetate to the reactor, then slowly drop 20-30 parts by mass of diphenylmethane-4,4'-diisocyanate into the reactor, stir, heat to 170-180°C, and react for 4-6 hours;

[0023] c. Finally, 40 to 50 parts by weight of butanone is added to the reaction kettle and stirred evenly to obtain a reactive UV-shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates.

[0024] In the preparation method of the above-mentioned reactive UV-shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates: the reactive UV-shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates prepared in step c has a viscosity of 2000-4000 mpas and a number average molecular weight of 800-2000.

[0025] In the preparation method of the reactive UV-shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates, the mass percentage of solid content in the reactive UV-shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates prepared in step c is preferably 75±1%.

[0026] Another content of the present invention is: a reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates, which is characterized in that it includes the following components: 90 to 110 parts by mass of a reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates, 20 to 30 parts by mass of E51 bisphenol A epoxy resin, 30 to 40 parts by mass of linear phenolic resin, 15 to 20 parts by mass of ODA-type benzoxazine resin, 0.2 to 1.0 parts by mass of 2-ethyl-4-methylimidazole and 40 to 60 parts by mass of butanone.

[0027] The reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates, E51 bisphenol A epoxy resin, linear phenolic resin, ODA type benzoxazine resin, 2-ethyl-4-methylimidazole and butanone are stirred and mixed uniformly to prepare a reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates.

[0028] In another aspect of the present invention: the chemical structure formula of the ODA type benzoxazine resin is:

[0029]

[0030] The product brand and production provider of the ODA type benzoxazine resin are: DFE148, Sichuan Dongcai Technology Group Co., Ltd.

[0031] The production and providing enterprise, product grade and production and providing enterprise of the E51 bisphenol A epoxy resin are: DY-128, Shandong Deyuan Epoxy Technology Co., Ltd.

[0032] The structural fragment formula of the linear phenolic resin is:

[0033]

[0034] The product brand and production provider of the linear phenolic resin are: RD-126, Shandong Laiwu Runda New Materials Co., Ltd.

[0035] In another aspect of the present invention: the chemical structural formula of the 2-ethyl-4-methylimidazole is:

[0036]

[0037] The prepared reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates is used to prepare copper-clad laminates. The specific preparation method is as follows: 90 to 110 parts by weight of reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates, 20 to 30 parts by weight of E51 bisphenol A epoxy resin, 30 to 40 parts by weight of linear phenolic resin, 15 to 20 parts by weight of ODA type benzoxazine resin, 0.2 to 1.0 parts by weight of 2-ethyl-4-methylimidazole and 40 to 60 parts by weight of butanone are mixed to prepare a reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates (referred to as glue solution); 7 layers (which can be any number of layers from 1 to 500 layers) of 7628 glass fiber cloth are dipped in the glue solution, the solvent is dried, and then hot-pressed at 150°C / 0.5h+170°C / 0.5h+180°C / 2.0h to obtain the copper-clad laminate. The preparation process of copper clad laminate is prior art.

[0038] Compared with the prior art, the present invention has the following characteristics and beneficial effects:

[0039] (1) The present invention uses 1,1,2,2-tetra(p-hydroxyphenyl)ethane tetraglycidyl ether with ultraviolet shielding, high-bromine epoxy resin with flame retardancy and diphenylmethane-4,4'-diisocyanate to react under the action of ethyl triphenylphosphine acetate catalyst to generate an oxazolidinone structure with high heat resistance and extend the length of the epoxy main chain. The prepared products (reactive ultraviolet shielding high-toughness flame retardant epoxy resin for copper clad laminates, reactive ultraviolet shielding high-toughness flame retardant epoxy resin solution for copper clad laminates and reactive ultraviolet shielding high-toughness flame retardant epoxy resin solution composition for copper clad laminates) have the characteristics of ultraviolet shielding, excellent flame retardancy, high heat resistance, excellent toughness, etc.; because 1,1,2,2-tetra(p-hydroxyphenyl)ethane tetraglycidyl ether is reacted on the main chain structure of the epoxy resin, the problem of poor compatibility is solved;

[0040] (2) The resin (i.e., reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminate) prepared by the present invention has a Tg of ≥160°C (high heat resistance) and an impact strength of ≥50KJ / m 2 (High toughness), used for the preparation of copper clad laminates. The copper clad laminates produced have good toughness, no cracking or powdering when drilling, UV transmittance <0.5% (UV shielding), flame retardancy UL94-V0 and other excellent comprehensive properties;

[0041] (3) The product of the present invention has a simple preparation process, is easy to operate, and has strong practicability. DETAILED DESCRIPTION

[0042] The embodiments given below are intended to further illustrate the present invention, but should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made to the present invention by technicians in this field based on the above-mentioned contents of the present invention still fall within the scope of protection of the present invention.

[0043] In the following embodiments, the specific unit of "parts by mass" is "kilogram (kg)".

[0044] Embodiment 1-1~1-8:

[0045] The preparation method of the reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates comprises the following steps:

[0046] a. Add 40-50 parts by weight of 1,1,2,2-tetrakis(p-hydroxyphenyl)ethane tetraglycidyl ether epoxy resin and 50-60 parts by weight of high-bromine epoxy resin into a reactor (or reactor), heat to 135°C, evacuate for 1 hour, and the vacuum gauge pressure is less than 15kPa;

[0047] b. Add 0.04-0.1 parts by mass of ethyl triphenylphosphine acetate to the reactor, then slowly drop 20-30 parts by mass of diphenylmethane-4,4'-diisocyanate into the reactor, stir, heat to 170-180°C, and react for 4-6 hours;

[0048] c. Finally, add 40-50 parts by mass of butanone into the reaction kettle and stir evenly to obtain a reactive UV shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates, with a viscosity of 2000-4000 mpas and a number average molecular weight of 800-2000.

[0049] In Examples 1-1 to 1-8:

[0050] The reactive UV shielding high-toughness flame-retardant epoxy resin has a chemical structure fragment formula as shown below:

[0051]

[0052] The 1,1,2,2-tetra(p-hydroxyphenyl)ethane tetraglycidyl ether epoxy resin has a chemical structural formula as shown below:

[0053]

[0054] The product brand and production provider of the 1,1,2,2-tetrakis (p-hydroxyphenyl) ethane tetraglycidyl ether epoxy resin are: TPGEE TGE Shandong Jiaying Chemical Technology Co., Ltd.

[0055] The high-bromine epoxy resin has a chemical structural formula as shown below:

[0056]

[0057] The product brand and production provider of the high-bromine epoxy resin are: NPEB-400, Kunshan Nanya.

[0058] The diphenylmethane-4,4'-diisocyanate has a chemical structural formula as shown below:

[0059]

[0060] The ethyl triphenylphosphine acetate has a chemical structural formula as shown below:

[0061]

[0062] Examples 1-1 to 1-8 use different dosages and process conditions to react to prepare reactive UV-shielding high-toughness flame-retardant epoxy resin solutions for copper-clad laminates. The specific dosages of the raw materials of each component and the chemical reaction process conditions are shown in Table 1:

[0063] Table 1: Formula quantity (unit: kg) and process conditions for preparing reactive UV shielding high toughness flame retardant epoxy resin solution for copper clad laminate:

[0064]

[0065]

[0066] After testing, the performance parameters of the reactive UV-shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates obtained in Examples 1-1 to 1-8 are shown in Table 2 below:

[0067] Table 2:

[0068]

[0069] Note: "Solid content (%)" in Table 2 is the mass percentage content of the solid content in the reactive UV-shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates.

[0070] Embodiments 2-1 to 2-8:

[0071] A reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates, comprising 90 to 110 parts by mass of a reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates, 20 to 30 parts by mass of an E51 bisphenol A epoxy resin, 30 to 40 parts by mass of a linear phenolic resin, 15 to 20 parts by mass of an ODA-type benzoxazine resin, 0.2 to 1.0 parts by mass of 2-ethyl-4-methylimidazole and 40 to 60 parts by mass of butanone;

[0072] That is, a reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates, E51 bisphenol A epoxy resin, linear phenolic resin, ODA type benzoxazine resin, 2-ethyl-4-methylimidazole and butanone are stirred and mixed uniformly to prepare a reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates;

[0073] The reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates is a reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates prepared in one of the above embodiments 1-1 to 1-8;

[0074] The product brand and production provider of the E51 bisphenol A epoxy resin are: DY-128, Shandong Deyuan Epoxy Technology Co., Ltd.

[0075] The structural fragment formula of the linear phenolic resin is:

[0076]

[0077] The product brand and production provider of the linear phenolic resin are: RD-126, Shandong Laiwu Runda New Materials Co., Ltd.

[0078] The structural formula of the ODA type benzoxazine resin is:

[0079]

[0080] The product brand and production provider of the ODA type benzoxazine resin are: DFE148, Sichuan Dongcai Technology Group Co., Ltd.

[0081] The structural formula of the 2-ethyl-4-methylimidazole is:

[0082]

[0083] Examples 2-1 to 2-8 use different dosages and process conditions to react to prepare reactive UV-shielding high-toughness flame-retardant epoxy resin solution compositions for copper-clad laminates. The specific dosages of the raw materials of each component and the chemical reaction process conditions are shown in Table 3 below.

[0084] Table 3: Formula of reactive UV shielding high toughness flame retardant epoxy resin solution composition for copper clad laminate (unit: mass parts, all kg):

[0085]

[0086] The reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates prepared in Examples 2-1 to 2-8 is used to prepare copper-clad laminates. The specific preparation method is: 90 to 110 parts by weight of reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates, 20 to 30 parts by weight of E51 bisphenol A epoxy resin, and 30 to 40 parts by weight of Linear phenolic resin, 15-20 parts by mass of ODA type benzoxazine resin, 0.2-1.0 parts by mass of 2-ethyl-4-methylimidazole and 40-60 parts by mass of butanone are mixed to form a reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution composition (referred to as glue solution) for copper clad laminates; then 7 layers of 7628 glass fiber cloth are dipped in the glue solution, the solvent is dried, and then hot-pressed at 150°C / 0.5h+170°C / 0.5h+180°C / 2.0h to obtain a copper clad laminate. The preparation process of the copper clad laminate is prior art.

[0087] The performance results of the copper-clad laminates prepared by using the reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates of Examples 2-1 to 2-8 are specifically shown in Table 4:

[0088] Table 4: Performance results of copper-clad laminates prepared using the high-toughness and high-reactivity epoxy resin solution compositions for copper-clad laminates of Examples 2-1 to 2-8:

[0089]

[0090] Note: "Example No." "2-1" in Table 4 refers to the high-toughness and high-reactivity epoxy resin solution composition for copper-clad laminates of Example 2-1, which corresponds in sequence.

[0091] Embodiment 3:

[0092] The preparation method of a reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates comprises the following steps: adding 40 parts by mass of 1,1,2,2-tetra(p-hydroxyphenyl)ethane tetraglycidyl ether epoxy resin and 50 parts by mass of high-bromine epoxy to a reactor, heating to 135°C, evacuating for 1h, and the vacuum gauge pressure is less than 15kpa; adding 0.04 parts by mass of ethyl triphenylphosphine acetate to the reactor, and then slowly dropping 20 parts by mass of diphenylmethane-4,4'-diisocyanate, stirring, heating to 170°C, and reacting for 6 hours; finally adding 40 parts by mass of butanone, stirring evenly, and obtaining a reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates. The viscosity of the solution is 2800mpas, and the solution is a yellow-brown liquid.

[0093] Embodiment 4:

[0094] The preparation method of a reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates comprises the following steps: adding 50 parts by mass of 1,1,2,2-tetra(p-hydroxyphenyl)ethane tetraglycidyl ether epoxy resin and 60 parts by mass of high-bromine epoxy to a reactor, heating to 135°C, evacuating for 1h, and the vacuum gauge pressure is less than 15kpa; adding 0.10 parts by mass of ethyl triphenylphosphine acetate to the reactor, and then slowly dropping 30 parts by mass of diphenylmethane-4,4'-diisocyanate, stirring, heating to 180°C, and reacting for 4 hours; finally adding 50 parts by mass of butanone, stirring evenly, and obtaining a reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates. The viscosity of the solution is 3200mpas, and the solution is a yellow-brown liquid.

[0095] Embodiment 5:

[0096] The preparation method of a reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates comprises the following steps: adding 45 parts by mass of 1,1,2,2-tetra(p-hydroxyphenyl)ethane tetraglycidyl ether epoxy resin and 55 parts by mass of high-bromine epoxy to a reactor, heating to 135°C, evacuating for 1h, and the vacuum gauge pressure is less than 15kpa; adding 0.07 parts by mass of ethyl triphenylphosphine acetate to the reactor, and then slowly dropping 25 parts by mass of diphenylmethane-4,4'-diisocyanate, stirring, heating to 175°C, and reacting for 5 hours; finally adding 45 parts by mass of butanone, stirring evenly, and obtaining a reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates. The viscosity of the solution is 3000mpas, and the solution is a yellow-brown liquid.

[0097] Embodiment 6:

[0098] The preparation method of a reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates comprises the following steps: adding 42 parts by mass of 1,1,2,2-tetra(p-hydroxyphenyl)ethane tetraglycidyl ether epoxy resin and 53 parts by mass of high-bromine epoxy to a reactor, heating to 135°C, evacuating for 1h, and the vacuum gauge pressure is less than 15kpa; adding 0.06 parts by mass of ethyl triphenylphosphine acetate to the reactor, slowly dropping 23 parts by mass of diphenylmethane-4,4'-diisocyanate, stirring, heating to 173°C, and reacting for 5.5 hours; finally adding 42 parts by mass of butanone, stirring evenly, and obtaining a reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates. The viscosity of the solution is 2600mpas, and the solution is a yellow-brown liquid.

[0099] Embodiment 7:

[0100] The preparation method of a reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates comprises the following steps: adding 42 parts by mass of 1,1,2,2-tetra(p-hydroxyphenyl)ethane tetraglycidyl ether epoxy resin and 58 parts by mass of high-bromine epoxy to a reactor, heating to 135°C, evacuating for 1h, and the vacuum gauge pressure is less than 15kpa; adding 0.09 parts by mass of ethyl triphenylphosphine acetate to a reactor, and then slowly dropping 27 parts by mass of diphenylmethane-4,4'-diisocyanate, stirring, heating to 176°C, and reacting for 4.5 hours; finally adding 47 parts by mass of butanone, stirring evenly, and obtaining a reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates. The viscosity of the solution is 3500mpas, and the solution is a yellow-brown liquid.

[0101] It can be seen from Examples 1-1 to 1-8 and Examples 3-7 that 1,1,2,2-tetra(p-hydroxyphenyl)ethane tetraglycidyl ether epoxy resin, high bromide epoxy, and diphenylmethane-4,4'-diisocyanate are used to generate a diphenylmethane-4,4'-diisocyanate-modified epoxy resin solution having a highly heat-resistant oxazolidinone structure under the action of high temperature and the catalyst ethyl triphenylphosphine acetate, thereby providing a reactive UV shielding, high toughness, high heat resistance, and excellent flame retardant isocyanate-modified epoxy resin for copper clad laminates with excellent comprehensive performance.

[0102] Embodiment 8:

[0103] A reactive ultraviolet-shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates comprises 90 parts by mass of a reactive ultraviolet-shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates, 20 parts by mass of E51 bisphenol A epoxy resin, 30 parts by mass of linear phenolic resin, 15 parts by mass of ODA-type benzoxazine resin, 0.2 parts by mass of 2-ethyl-4-methylimidazole and 40 parts by mass of butanone. The reactive ultraviolet-shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates is prepared by uniformly mixing and stirring the above components.

[0104] The prepared reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates is used to prepare copper-clad laminates. The method is: 7 layers of 7628 glass fiber cloth are impregnated with the reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates, and then cured by hot pressing plate according to the existing technical method to obtain the copper-clad laminate. The test results show that the Tg is 169°C and the impact strength is 56KJ / m 2 The copper clad laminate has good toughness and does not crack or drop powder when drilling. The UV transmittance is 0.43% and the flame retardancy is UL94-V0.

[0105] Embodiment 9:

[0106] A reactive ultraviolet-shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates comprises 110 parts by mass of a reactive ultraviolet-shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates, 30 parts by mass of E51 bisphenol A epoxy resin, 40 parts by mass of linear phenolic resin, 20 parts by mass of ODA-type benzoxazine resin, 1.0 parts by mass of 2-ethyl-4-methylimidazole and 60 parts by mass of butanone. The reactive ultraviolet-shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates is prepared by uniformly mixing and stirring the above components.

[0107] The prepared reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates is used to prepare copper-clad laminates. The method is: 7 layers of 7628 glass fiber cloth are impregnated with the reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates, and then cured by hot pressing plate according to the existing technical method to obtain the copper-clad laminate. The test results show that the Tg is 166°C and the impact strength is 58KJ / m 2 The copper clad laminate has good toughness and does not crack or drop powder when drilling. The UV transmittance is 0.46% and the flame retardancy is UL94-V0.

[0108] Embodiment 10:

[0109] A reactive ultraviolet-shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates comprises 100 parts by mass of a reactive ultraviolet-shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates, 25 parts by mass of E51 bisphenol A epoxy resin, 35 parts by mass of linear phenolic resin, 18 parts by mass of ODA-type benzoxazine resin, 0.6 parts by mass of 2-ethyl-4-methylimidazole and 50 parts by mass of butanone. The reactive ultraviolet-shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates is prepared by uniformly mixing and stirring the above components.

[0110] The prepared reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates is used to prepare copper-clad laminates. The method is: 7 layers of 7628 glass fiber cloth are impregnated with the reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates, and then cured by hot pressing plate according to the existing technical method to obtain the copper-clad laminate. The test results show that the Tg is 164°C and the impact strength is 53KJ / m 2 The copper clad laminate has good toughness and does not crack or drop powder when drilling. The UV transmittance is 0.33% and the flame retardancy is UL94-V0.

[0111] Embodiment 11:

[0112] A reactive ultraviolet-shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates comprises 95 parts by mass of a reactive ultraviolet-shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates, 23 parts by mass of E51 bisphenol A epoxy resin, 33 parts by mass of linear phenolic resin, 16 parts by mass of ODA-type benzoxazine resin, 0.4 parts by mass of 2-ethyl-4-methylimidazole and 45 parts by mass of butanone. The reactive ultraviolet-shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates is prepared by uniformly mixing and stirring the above components.

[0113] The prepared reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates is used to prepare copper-clad laminates. The method is: 7 layers of 7628 glass fiber cloth are impregnated with the reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates, and then cured by hot pressing plate according to the existing technical method to obtain the copper-clad laminate. The test results show that the Tg is 169°C and the impact strength is 61KJ / m 2 The copper clad laminate has good toughness and does not crack or drop powder when drilling. The UV transmittance is 0.40% and the flame retardancy is UL94-V0.

[0114] Embodiment 12:

[0115] A reactive ultraviolet-shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates comprises 105 parts by mass of a reactive ultraviolet-shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates, 28 parts by mass of E51 bisphenol A epoxy resin, 37 parts by mass of linear phenolic resin, 19 parts by mass of ODA-type benzoxazine resin, 0.8 parts by mass of 2-ethyl-4-methylimidazole and 55 parts by mass of butanone. The reactive ultraviolet-shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates is prepared by uniformly mixing and stirring the above components.

[0116] The prepared reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates is used to prepare copper-clad laminates. The method is: 7 layers of 7628 glass fiber cloth are impregnated with the reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates, and then cured by hot pressing plate according to the existing technical method to obtain the copper-clad laminate. The test results show that the Tg is 168°C and the impact strength is 57KJ / m 2 The copper clad laminate has good toughness and does not crack or drop powder when drilling. The UV transmittance is 0.39% and the flame retardancy is UL94-V0.

[0117] Embodiment 13:

[0118] A reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates is prepared by chemically reacting 1,1,2,2-tetra(p-hydroxyphenyl)ethane tetraglycidyl ether epoxy resin, high-bromine epoxy resin, ethyl triphenylphosphine acetate and diphenylmethane-4,4'-diisocyanate, and then adding butanone to dilute the solution.

[0119] The reactive ultraviolet shielding high-toughness flame-retardant epoxy resin for copper-clad laminate has a simplified chemical structure fragment formula as shown below:

[0120]

[0121] Furthermore, the mass percentage content of the solid content in the reactive UV-shielding high-toughness flame-retardant epoxy resin solution described in Example 13 is controlled within the range of 75±1% (i.e., 74% to 76%), its viscosity is within the range of 2000 to 4000 mpas, and its number average molecular weight is between 800 and 2000.

[0122] In Example 13: the 1,1,2,2-tetra(p-hydroxyphenyl)ethane tetraglycidyl ether epoxy resin has the following chemical structural formula:

[0123]

[0124] In Example 13: The high-bromine epoxy resin has a chemical structural formula as shown below:

[0125]

[0126] Embodiment 14:

[0127] The preparation method of the reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates comprises the following steps:

[0128] a. Add 40 parts by mass of 1,1,2,2-tetrakis(p-hydroxyphenyl)ethane tetraglycidyl ether epoxy resin and 50 parts by mass of high-bromine epoxy resin into a reactor (or reactor), heat to 135°C, evacuate for 1 hour, and the vacuum gauge pressure is less than 15kPa;

[0129] b. Add 0.04 parts by mass of ethyl triphenylphosphine acetate to the reactor, then slowly drop 20 parts by mass of diphenylmethane-4,4'-diisocyanate into the reactor, stir, heat to 170°C, and react for 6 hours;

[0130] c. Finally, 40 parts by mass of butanone was added into the reaction kettle and stirred evenly to obtain a reactive UV-shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates.

[0131] Embodiment 15:

[0132] The preparation method of the reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates comprises the following steps:

[0133] a. Add 50 parts by mass of 1,1,2,2-tetrakis(p-hydroxyphenyl)ethane tetraglycidyl ether epoxy resin and 60 parts by mass of high-bromine epoxy resin into a reactor (or reactor), heat to 135°C, evacuate for 1 hour, and the vacuum gauge pressure is less than 15kPa;

[0134] b. Add 0.1 parts by mass of ethyl triphenylphosphine acetate to the reactor, then slowly drop 30 parts by mass of diphenylmethane-4,4'-diisocyanate into the reactor, stir, heat to 180°C, and react for 4 hours;

[0135] c. Finally, 50 parts by mass of butanone was added into the reaction kettle and stirred evenly to obtain a reactive UV-shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates.

[0136] Embodiment 16:

[0137] The preparation method of the reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates comprises the following steps:

[0138] a. Add 45 parts by mass of 1,1,2,2-tetrakis(p-hydroxyphenyl)ethane tetraglycidyl ether epoxy resin and 55 parts by mass of high-bromine epoxy resin into a reactor (or reactor), heat to 135°C, evacuate for 1 hour, and the vacuum gauge pressure is less than 15kPa;

[0139] b. Add 0.07 parts by mass of ethyl triphenylphosphine acetate to the reactor, then slowly drop 25 parts by mass of diphenylmethane-4,4'-diisocyanate into the reactor, stir, heat to 175°C, and react for 5 hours;

[0140] c. Finally, 45 parts by mass of butanone was added into the reaction kettle and stirred evenly to obtain a reactive UV-shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates.

[0141] Embodiment 17:

[0142] The reactive UV-shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates is prepared by stirring and mixing 90 parts by mass of a reactive UV-shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates, 20 parts by mass of E51 bisphenol A epoxy resin, 30 parts by mass of linear phenolic resin, 15 parts by mass of ODA-type benzoxazine resin, 0.2 parts by mass of 2-ethyl-4-methylimidazole and 40 parts by mass of butanone.

[0143] Embodiment 18:

[0144] The reactive UV-shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates is prepared by stirring and mixing 110 parts by mass of a reactive UV-shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates, 30 parts by mass of E51 bisphenol A epoxy resin, 40 parts by mass of linear phenolic resin, 20 parts by mass of ODA-type benzoxazine resin, 1.0 parts by mass of 2-ethyl-4-methylimidazole and 60 parts by mass of butanone.

[0145] Embodiment 19:

[0146] The reactive UV-shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates is prepared by stirring and mixing 100 parts by mass of a reactive UV-shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates, 25 parts by mass of E51 bisphenol A epoxy resin, 35 parts by mass of linear phenolic resin, 18 parts by mass of ODA-type benzoxazine resin, 0.6 parts by mass of 2-ethyl-4-methylimidazole and 50 parts by mass of butanone.

[0147] The solid amount mentioned in the present invention and the examples is defined as follows: the mass percentage of non-volatile matter in the total mass of 1g sample after baking in an oven at 160°C for 1 hour, and the solid amount finally determined by adding butanone is calculated based on the mass of non-volatile matter;

[0148] That is, the definition of a high-toughness and high-reactivity epoxy resin solution for copper-clad laminates with a solid content of 75±1% is: after 1g of the sample is baked in an oven at 160°C for 1 hour, the mass percentage of non-volatile matter in the total mass is 75±1%.

[0149] In the content of the present invention and the above-mentioned embodiments: the "mass percentage content of solid content is 75±1%", that is: in the reactive UV-shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates, the mass percentage content of solid content is 75±1% (that is: one within the range of 74% to 76%). The definition of "solid content" is: the mass percentage of non-volatile matter in 1g of sample after baking in an oven at 160°C for 1 hour, and the solid content is finally determined by calculating the mass of the solvent added based on the mass of the non-volatile matter. For example: the mass percentage content of solid content in the reactive UV-shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates is 75%, which means: after 1g of sample is baked in an oven at 160°C for 1 hour, the mass percentage of non-volatile matter in 1g of sample (the sum of non-volatile matter and volatile solvent) is 75%

[0150] In the above embodiments: the percentages used, unless otherwise specified, are all mass (weight) percentages or percentages known to those skilled in the art; the proportions used, unless otherwise specified, are all mass (weight) proportions; and the weights may be in grams or kilograms.

[0151] In the above embodiments, the process parameters (temperature, time, etc.) in each step and the numerical values ​​of the amounts of each component are ranges, and any point can be applied.

[0152] The technical contents not specifically described in the present invention and the above embodiments are the same as the prior art, and the raw materials are all commercially available products.

[0153] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technical personnel in this field can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. Reactive UV shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates, characterized by: The reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminate is prepared by chemically reacting 1,1,2,2-tetra(p-hydroxyphenyl)ethane tetraglycidyl ether epoxy resin, high-bromine epoxy resin, ethyl triphenylphosphine acetate and diphenylmethane-4,4'-diisocyanate, and then adding butanone for dilution.

2. The reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminate according to claim 1, characterized in that: The reactive ultraviolet shielding high-toughness flame-retardant epoxy resin for copper-clad laminate has a simplified chemical structure fragment formula as shown below:

3. The reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates according to claim 1 or 2, characterized in that: The solid content in the reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution is 75±1% by weight, the viscosity is 2000-4000 mpas, and the number average molecular weight is 800-2000.

4. The reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates according to claim 1 or 2, characterized in that: The 1,1,2,2-tetra(p-hydroxyphenyl)ethane tetraglycidyl ether epoxy resin has a chemical structural formula as shown below:

5. The reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates according to claim 1 or 2, characterized in that: The high-bromine epoxy resin has a chemical structural formula as shown below:

6. The reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminate according to claim 1, characterized in that: The method for preparing the reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates comprises the following steps: a. Add 40-50 parts by weight of 1,1,2,2-tetrakis(p-hydroxyphenyl)ethane tetraglycidyl ether epoxy resin and 50-60 parts by weight of high-bromine epoxy resin into a reactor, heat to 135°C, evacuate for 1 hour, and the vacuum gauge pressure is less than 15 kPa; b. Add 0.04-0.1 parts by mass of ethyl triphenylphosphine acetate to the reactor, then slowly drop 20-30 parts by mass of diphenylmethane-4,4'-diisocyanate into the reactor, stir, heat to 170-180°C, and react for 4-6 hours; c. Finally, 40 to 50 parts by weight of butanone is added to the reaction kettle and stirred evenly to obtain a reactive UV-shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates.

7. The reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates according to claim 6, characterized in that: The reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates prepared in step c has a viscosity of 2000-4000 mpas and a number average molecular weight of 800-2000.

8. The reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates according to claim 6, characterized in that: The weight percentage of solid content in the reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates prepared in step c is 75±1%.

9. A reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates, characterized in that The invention comprises the following components: 90 to 110 parts by weight of reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution for copper-clad laminates, 20 to 30 parts by weight of E51 bisphenol A epoxy resin, 30 to 40 parts by weight of linear phenolic resin, 15 to 20 parts by weight of ODA type benzoxazine resin, 0.2 to 1.0 parts by weight of 2-ethyl-4-methylimidazole and 40 to 60 parts by weight of butanone.

10. The reactive ultraviolet shielding high-toughness flame-retardant epoxy resin solution composition for copper-clad laminates according to claim 7, characterized in that: The chemical structure formula of the ODA type benzoxazine resin is:

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