TW202248339A - Resin composition of phosphorus-containing benzene bisphenol polymer as well as preparation method and application of resin composition - Google Patents

Abstract

The invention provides a resin composition of a phosphorus-containing benzene bisphenol polymer as well as a preparation method and application of the resin composition, and relates to the technical field of high polymer materials. The resin composition comprises the following raw materials in parts by weight: 100 parts of epoxy resin, 40-80 parts of a phosphorus-benzene bisphenol polymer, 100-300 parts of cyanate ester resin and 28-32 parts of a hardening agent. The structure of the phosphorus-benzene bisphenol polymer is shown as a formula I or a formula II, and the phosphorus-benzene bisphenol polymer is obtained by reacting phenylphosphonic dichloride or phenyl dichlorophosphate with a tetramethyl bisphenol compound. The resin composition disclosed by the invention is simple in formula, and the laminated plate prepared from the resin composition has the advantages of high glass transfer temperature, low water absorption, good dip soldering resistance, good flame retardancy and the like.

Description

Resin composition containing phosphorus benzene bisphenol polymer and its preparation method and application

The invention relates to the technical field of polymer materials, in particular to a resin composition containing phosphorus benzene bisphenol polymer, a preparation method and application thereof.

The printed circuit board is the circuit substrate of the electronic device. The printed circuit board carries other electronic components and electrically connects these components to provide a stable circuit working environment. A common printed circuit board substrate is copper clad laminate (CCL), which is mainly composed of resin, reinforcing material and copper foil. Common resins such as epoxy resin, phenolic resin, polyurethane formaldehyde, cyanate ester, bismaleimide, hydrocarbon resin and Teflon, etc.; commonly used reinforcing materials such as glass fiber cloth, glass fiber mat, insulation paper etc.

Generally speaking, printed circuit boards can be made by impregnating a reinforcing material such as glass fabric in resin, and curing the glass fabric impregnated with resin to a semi-hardened state (ie, B-stage, B-stage), Obtain a prepreg (prepreg); laminate a certain number of prepregs, and laminate a metal foil on at least one outer side of the laminated prepreg to provide a laminate, and perform a heat-pressing operation on the laminate (ie, C-stage, C -stage) to obtain a metal-clad laminate; etch the metal foil on the surface of the metal-clad laminate to form a specific circuit pattern.

Printed circuit boards must reach a certain level in terms of flame retardancy, heat resistance, dimensional stability, chemical stability, processability, toughness and mechanical strength. Generally speaking, the printed circuit board prepared by using epoxy resin can have the above characteristics, so epoxy resin is the most commonly used resin in the industry.

Brominated resins or phosphorus-containing flame retardants such as DOPO are often added to epoxy resins to improve flame resistance. Such as DOPO derivatives used in printed circuit boards, its polyphenolic hydroxyl or polyamino derivatives can be used as a curing agent for polymers. However, the use of related materials requires a large amount of use, it is difficult to control the uniformity of the reaction, and it will also affect the heat resistance or moisture absorption of the board. In addition, the compatibility of ingredients with resin system solvents is especially important.

Phosphate ester flame retardant is also a widely used additive flame retardant, which is prepared by reacting alcohol or phenol with phosphorus trichloride and then hydrolyzing it, such as tricresyl phosphate, triphenyl phosphate, and tricumyl phosphate , tributyl phosphate, trioctyl phosphate, cresyl diphenyl phosphate, etc. There are many types of related phosphates, but the heat resistance is poor, and the compatibility with polymers is not ideal. Further, there are also novel phosphate flame retardants with complex structures improved on this basis, such as: tris(1-oxo-1-phospha-2,6,7-trioxabicyclo[2,2 , 2] octane-4-methylene) phosphate (Trimer), phosphorus content up to 21.1%; 1-oxo-4-hydroxymethyl-2,6,7-trioxa-1-phosphabicyclo[ 2, 2, 2] octane (PEPA), the phosphorus content of PEPA is 17.2%, the thermal stability is very good, and it has good compatibility with the polymer. N, N-p-phenylenediamine (2-hydroxyl) tetraethyl dibenzyl phosphonate, dimethyl methyl phosphonate (DMMP), the phosphorus content is as high as 25%. The above phosphate ester flame retardants have good flame retardancy, but they are still additive flame retardants.

In addition, the phosphorus content of bisphenol A-bis(diphenyl phosphate) (BDP for short) can reach more than 8%. Although these materials have a good flame retardant effect, they often cause debinding of the added materials. Delamination, poor heat resistance and other problems.

Too much addition of additive-type flame retardants can easily cause materials to float out and stick between laminates. During the electroplating process, it is easy to contaminate the electroplating solution, aging the electroplating solution, and there are many restrictions on use. It is also necessary to consider the compatibility properties of related resin compositions.

Based on this, it is necessary to address the above problems and provide a resin composition containing phosphobenzene bisphenol polymer, wherein the phosphobenzene bisphenol polymer has the functions of flame retardant and hardener, so that the formulation of the resin composition is simplified, and the flame retardant The dosage of the agent is low, and the laminated board prepared from the resin composition has excellent flame resistance and good physical and chemical properties.

The resin composition containing the phosphorus benzene bisphenol polymer provided by the invention comprises the following raw materials of weight part:

Epoxy resin 100 parts,

Phosphobenzene bisphenol polymer 40~80 parts,

Cyanate resin 100~300 parts,

Hardener 28~32 parts;

式I

式II The structure of the phosphobenzene bisphenol polymer is shown in formula I or formula II:

Formula I

Formula II

、

、

中的一種。 Wherein, n=2~5, R is selected from: CH ₃ CCH ₃ ,

,

,

One of.

In the above resin composition, the phosphobenzene bisphenol polymer functions as both a flame retardant and a hardener, which simplifies the formulation of the resin composition, reduces the amount of flame retardant, and obtains excellent performance by screening the types and proportions of raw materials. The epoxy resin composition, and the laminate made from the resin composition have excellent flame resistance and good physical and chemical properties.

The phosphobenzene bisphenol polymer in the present invention has a degree of polymerization n=2~5 and a phosphorus content of more than 5%. It has good solubility in benzenes, ketones, amides, pyridine, etc., and is easy to add to resins. Prepared in a solvent, the electronic plastic produced has good flame retardancy and heat resistance, and the produced plate has the advantages of high tear strength, high glass transition temperature, and suitable hardness of the electronic plate.

The experimental data show that the degree of polymerization n of the phosphobenzene bisphenol polymer is preferably 2~5, if n is too low (<2), the phosphorus content of the phosphobenzene bisphenol polymer is high, and the tear strength of the laminated board prepared is relatively low. Low; if n is too high (>5), the phosphorous content is low, and the flame retardant effect of the laminated board produced will be worse (only V1 grade), the thermal stability of the board will be worse, the solder resistance will be worse, and the flatness will be worse. , There will also be a phenomenon of degumming and delamination.

式III

式IV In one of the embodiments, the preparation method of the phosphobenzene bisphenol polymer is carried out according to the synthetic route shown in formula III or formula IV:

Formula III

Formula IV

Mix phenylphosphonic acid dichloride or phenyl dichlorophosphate and tetramethyl bisphenol compound, add toluene and co-solvent, and reflux reaction to obtain the compound shown in formula I or formula II.

、

、

。 In one of the embodiments, the tetramethylbisphenol compound is selected from: tetramethylbisphenol A,

,

,

.

In one embodiment, the co-solvent is selected from one or both of pyridine and 4-dimethylaminopyridine.

In one embodiment, the molar ratio of the phenylphosphonyl dichloride or phenyl dichlorophosphate to the tetramethylbisphenol compound is 1: (1~2).

In one embodiment, the reflux reaction temperature is 120-180° C., and the reaction time is 10-20 hours.

In one embodiment, after the reflux reaction is completed, a purification step is further included: washing the product with tetrahydrofuran or water, and distilling off the solvent to obtain a purified target product.

In one embodiment, the epoxy resin is selected from one or both of bisphenol A novolac epoxy resin and bisphenol F novolac epoxy resin.

In one embodiment, the cyanate resin is selected from one or more of bisphenol A cyanate, bisphenol F cyanate, and cycloaliphatic aromatic cyanate. The cycloaliphatic chain aromatic cyanate can be selected from the cycloaliphatic aromatic cyanate produced by Dow Chemical.

In one embodiment, the hardening agent is selected from one or both of diamino-diphenylsulfone and amino-triazine phenol-formaldehyde resins. The above-mentioned hardener can react with the functional groups in the epoxy resin molecules to form an interpenetrating network epoxy composite material.

In one embodiment, the resin composition further includes 120-180 parts of solvent and 25-35 parts of functional additives.

In one embodiment, the solvent is selected from: toluene, γ-butyrolactone, methyl ethyl ketone, cyclohexanone, methyl ethyl ketone, acetone, xylene, methyl isobutyl ketone, N,N-dimethylformaldehyde One or more of amide, N,N-dimethylacetamide, and N-methylpyrrolidone.

In one embodiment, the functional additive is selected from one or more of fillers, hardening accelerators, dispersants, and tougheners.

In one of the embodiments, the hardening accelerator is selected from: 2-methylimidazole (2-Methyl-Imidazole, 2MI), 2-ethyl-4-methylimidazole (2-Ethyl-4-Methyl-Imidazole , 2E4MI) and one or more of 2-phenylimidazole (2-Phenyl-Imidazole, 2PI).

In one embodiment, the filler is selected from one or more of silica, glass powder, talc powder, kaolin, kaolin, mica, alumina, and zirconia.

The present invention also provides a prepreg, which is prepared from the raw materials of the above-mentioned resin composition containing the phosphorus-containing bisphenol polymer.

The present invention also provides an application of the above resin composition or prepreg containing phosphorus benzene bisphenol polymer in the preparation of laminated boards.

Compared with the prior art, the present invention has the following beneficial effects:

In the resin composition of the present invention, the phosphobenzene bisphenol polymer has the functions of both a flame retardant and a hardener, so that the formulation of the resin composition is simplified, and the consumption of the flame retardant is low. Excellent performance epoxy resin composition, the laminate made of this resin composition has good physical and chemical properties, such as high glass transition temperature (Tg), low water absorption, good dip soldering resistance, good flame retardancy, etc.

In order to facilitate the understanding of the present invention, preferred embodiments will be given below to describe the present invention more fully. However, the present invention can be embodied in many different forms and is not limited to the embodiments described herein. On the contrary, these embodiments are provided to make the understanding of the disclosure of the present invention more thorough and comprehensive.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the technical field of the invention. The terms used herein in the description of the present invention are for the purpose of describing specific embodiments only, and are not intended to limit the present invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

In the following examples and comparative examples, unless otherwise specified, the raw materials are all commercially available or prepared by conventional methods.

Example 1

1. Preparation of phosphobenzene bisphenol polymer

式V Set up a reaction bottle, install a thermometer and a reflux tube, and condense with 0 °C water. Add 2.84 g of tetramethylbisphenol A, 10 ml of toluene, and 10 ml of pyridine into the bottle, stir to dissolve, and then add in batches 0.49 g of phenylphosphonic acid dichloride, fed with nitrogen, heated and stirred at 140 °C for reaction, after 16 hours of reaction, stopped the reaction and added THF (tetrahydrofuran) to wash the crude product, and then distilled under reduced pressure to obtain the structure as formula V The product A1 shown has a yield of more than 80%. The molecular mass detected by MASS is 2316.7, n=5, and the phosphorus content is 6.68%. The results of proton nuclear magnetic resonance spectrum (NMR spectrometer of Varian Company, model Mercury-VX200 MHz) are shown in Fig. 1 .

Formula V

2. Preparation of resin composition

Weigh each raw material according to the ratio of raw materials in Table 1, put each raw material in a stirrer, and stir at room temperature for 2-4 hours to obtain resin composition C1.

3. Preparation of laminates

Coat resin composition C1 on 7628 glass fiber cloth with a roll coater, the impregnation amount of resin and glass fiber cloth is 43%, then place it in a dryer, heat and dry at 180 °C for 2~5 min, and make The semi-hardened prepreg is produced, and then eight pieces of prepreg are laminated, and a 1 oz copper foil is laminated on each of the outermost layers on both sides. This was then hot-pressed to obtain a copper foil-coated laminate D1. Among them, the hot pressing conditions are: heating up to 200 °C at a heating rate of 2.0 °C/min, and hot pressing at 200 °C with a total pressure of 25 kg/cm2 (initial pressure of 12 kg/cm2) for 90 min.

Example 2

1. Preparation of phosphobenzene bisphenol polymer

，得到結構如式VI所示的產物A2，產率為86%，MASS檢測分子質量為1405，n=3，含磷量為5.33%。

式VI It is basically the same as the preparation method of phosphobenzene bisphenol polymer in Example 1, the difference is that 2.84 g tetramethylbisphenol A is replaced by 3.24 g

, the product A2 with the structure shown in formula VI was obtained, the yield was 86%, the molecular mass detected by MASS was 1405, n=3, and the phosphorus content was 5.33%.

Formula VI

2. Preparation of resin composition

Weigh each raw material according to the ratio of raw materials in Table 1, put each raw material in a stirrer, and stir at room temperature for 2-4 hours to obtain resin composition C2.

3. Preparation of laminates

The resin composition was replaced by resin composition C2, and the others were the same as in Example 1 to obtain a laminate D2.

Example 3

1. Preparation of phosphobenzene bisphenol polymer

式VII The preparation method of the phosphobenzene bisphenol polymer in Example 1 is basically the same, the difference is that 0.49 g of phenylphosphonic acid dichloride is replaced by 0.53 g of phenyl dichlorophosphate to obtain a product A3 with a structure as shown in formula VII, producing The rate was 89%, the molecular mass detected by MASS was 1357.4, n=3, and the phosphorus content was 5.8%. The results of proton nuclear magnetic resonance spectroscopy (NMR spectrometer of Varian Company, model Mercury-VX200 MHz) are shown in Fig. 2 .

Formula VII

2. Preparation of resin composition

Weigh each raw material according to the ratio of raw materials in Table 1, put each raw material in a stirrer, and stir at room temperature for 2-4 hours to obtain resin composition C3.

3. Preparation of laminates

The resin composition was replaced by resin composition C3, and the others were the same as in Example 1 to obtain a laminate D3.

Example 4

1. Preparation of phosphobenzene bisphenol polymer

，得到結構如式VIII所示的產物A4，產率為83%，MASS檢測分子質量為2058，n=3，含磷量為5.64%。

式VIII The preparation method of phosphobenzene bisphenol polymer is basically the same as in Example 3, the difference is that 2.84 g tetramethyl bisphenol A is replaced by 3.24 g

, the product A4 with the structure shown in formula VIII was obtained, the yield was 83%, the molecular mass detected by MASS was 2058, n=3, and the phosphorus content was 5.64%.

Formula VIII

2. Preparation of resin composition

Weigh each raw material according to the ratio of raw materials in Table 1, put each raw material in a stirrer, and stir at room temperature for 2-4 hours to obtain resin composition C4.

3. Preparation of laminates

The resin composition was replaced by resin composition C4, and the others were the same as in Example 1 to obtain a laminate D4.

Example 5

1. Preparation of phosphobenzene bisphenol polymer

The preparation method of phosphobenzene bisphenol polymer is the same as embodiment 1.

3. Preparation of resin composition

Weigh each raw material according to the ratio of raw materials in Table 1, put each raw material in a stirrer, stir at room temperature for 2-4 h, mix well, and obtain resin composition C5.

4. Preparation of laminates

The resin composition was replaced by resin composition C5, and the others were the same as in Example 1 to obtain a laminate D5.

Example 6

1. Preparation of phosphobenzene bisphenol polymer

The preparation method of phosphobenzene bisphenol polymer is the same as embodiment 1.

3. Preparation of resin composition

Weigh each raw material according to the ratio of raw materials in Table 1, put each raw material in a stirrer, stir at room temperature for 2-4 hours, mix well, and obtain resin composition C6.

4. Preparation of laminates

The resin composition was replaced by resin composition C6, and the others were the same as in Example 1 to obtain a laminate D6.

Example 7

1. Preparation of phosphobenzene bisphenol polymer

The preparation method of phosphobenzene bisphenol polymer is the same as embodiment 1.

3. Preparation of resin composition

Weigh each raw material according to the ratio of raw materials in Table 1, put each raw material in a stirrer, stir at room temperature for 2-4 h, mix well, and obtain resin composition C7.

4. Preparation of laminates

The resin composition was replaced by resin composition C7, and the others were the same as in Example 1 to obtain a laminate D7.

Example 8

1. Preparation of phosphobenzene bisphenol polymer

The preparation method of phosphobenzene bisphenol polymer is the same as embodiment 1.

3. Preparation of resin composition

Weigh each raw material according to the ratio of raw materials in Table 1, put each raw material in a stirrer, stir at room temperature for 2-4 hours, mix well, and obtain resin composition C8.

4. Preparation of laminates

The resin composition was replaced by resin composition C8, and the others were the same as in Example 1 to obtain a laminate D8.

Example 9

1. Preparation of phosphobenzene bisphenol polymer

The preparation method of phosphobenzene bisphenol polymer is the same as embodiment 1.

3. Preparation of resin composition

Weigh each raw material according to the ratio of raw materials in Table 1, put each raw material in a stirrer, stir at room temperature for 2-4 h, mix well, and obtain resin composition C9.

4. Preparation of laminates

The resin composition was replaced by resin composition C9, and the others were the same as in Example 1 to obtain a laminate D9.

Comparative example 1

1. Preparation of phosphobenzene bisphenol polymer

The preparation method of phosphobenzene bisphenol polymer is the same as embodiment 1.

3. Preparation of resin composition

Weigh each raw material according to the ratio of raw materials in Table 1, put each raw material in a stirrer, stir at room temperature for 2-4 hours, mix well, and obtain resin composition E1.

4. Preparation of laminates

The resin composition was replaced by resin composition E1, and the others were the same as in Example 1 to obtain laminate F1.

Comparative example 2

1. Preparation of phosphobenzene bisphenol polymer

The preparation method of phosphobenzene bisphenol polymer is the same as embodiment 1.

3. Preparation of resin composition

Weigh each raw material according to the ratio of raw materials in Table 1, put each raw material in a stirrer, stir at room temperature for 2-4 hours, mix well, and obtain resin composition E2.

4. Preparation of laminates

The resin composition was replaced by the resin composition E2, and the others were the same as in Example 1 to obtain the laminate F2.

Comparative example 3

1. Preparation of phosphobenzene bisphenol polymer

The preparation method of phosphobenzene bisphenol polymer is the same as embodiment 1.

3. Preparation of resin composition

Weigh each raw material according to the ratio of raw materials in Table 1, put each raw material in a stirrer, stir at room temperature for 2-4 hours, mix well, and obtain resin composition E3.

4. Preparation of laminates

The resin composition was replaced by the resin composition E3, and the others were the same as in Example 1 to obtain a laminate F3.

Comparative example 4

1. Preparation of phosphobenzene bisphenol polymer

The preparation method of phosphobenzene bisphenol polymer is the same as embodiment 1.

3. Preparation of resin composition

Weigh each raw material according to the ratio of raw materials in Table 1, put each raw material in a stirrer, stir at room temperature for 2-4 hours, mix well, and obtain resin composition E4.

4. Preparation of laminates

The resin composition was replaced by resin composition E4, and the other was the same as in Example 1 to obtain laminate F4.

Comparative example 5

1. Preparation of phosphobenzene bisphenol polymer

The preparation method of phosphobenzene bisphenol polymer is the same as embodiment 1.

3. Preparation of resin composition

Weigh each raw material according to the ratio of raw materials in Table 1, put each raw material in a stirrer, stir at room temperature for 2-4 hours, mix well, and obtain resin composition E5.

4. Preparation of laminates

The resin composition was replaced by the resin composition E5, and the others were the same as in Example 1 to obtain a laminate F5.

Experimental example 1

Carry out performance test to each laminated board in embodiment and contrast, test method is as follows:

(1) Glass transition temperature test: The glass transition temperature (Tg) was measured using a dynamic mechanical analyzer (DMA). The test specification for the glass transition temperature is the IPC-TM-650.2.4.25C and 24C detection methods of the Institute for Interconnecting and Packaging Electronic Circuits (IPC).

(2) Dielectric constant and dissipation factor test: Calculate the dielectric constant (dielectric constant, Dk) and dissipation factor (dissipation factor, Df) at a working frequency of 5 GHz according to the ASTM D150 specification.

(3) Water absorption test: carry out the pressure cooker test (PCT) test, place the laminate in a pressure vessel, and test it at 121 ℃, saturated humidity (100% R.H.) and 1.2 atmospheric pressure for 2 hours. High humidity resistance of laminates.

(4) Thermal expansion coefficient and Z-axis direction expansion rate test: Tested with a thermal expansion analyzer model TA 2940 of TA instrument company, the test condition is a heating rate of 5 degrees per minute from 50 ℃ to 260 ℃, and the test sample is 3×3 mm ² The coefficient of thermal expansion in the thickness direction (Z-axis direction) and the expansion rate in the z-axis direction of the laminate sample of different sizes.

(5) Thermal decomposition temperature test: use a thermogravimetric analyzer (TGA) to measure the temperature when the mass is reduced by 5% compared with the initial mass, which is the thermal decomposition temperature.

(6) Toughness test: Place the laminate flat on the plane fixture, contact the surface of the laminate vertically with a cross-shaped metal fixture, and then apply vertical pressure, then remove the cross fixture, and observe the shape of the cross on the laminate Check the surface of the laminate, if there is no white crease, it is judged as good, if there is a little white line, it is normal, and if there is crack or break, it is bad.

(7) Tear strength test: Tear strength refers to the adhesion of copper foil to the substrate, usually the copper foil per inch (25.4mm) width is torn vertically from the board surface, with the required force The size to express the strength of adhesion. MIL-P-55110E stipulates that the pass standard for substrates with 1 oz copper foil is 8 lb/in.

(8) Flammability test: Using UL94V, vertical combustion test method, fix the printed circuit board in a vertical position, burn it with a Bunsen burner, and compare its spontaneous extinguishment and combustion-supporting characteristics.

The ratio of raw materials of the resin composition and the performance of the laminate in the examples are shown in Table 1, and the ratio of raw materials and the performance of the laminate of the resin composition in the comparative example are shown in Table 2. [Table 1] Raw material ratio of resin composition and laminate properties (parts by weight) in the embodiment Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 resin composition C1 C2 C3 C4 C5 C6 C7 C8 C9 epoxy resin 100 100 100 100 100 100 100 100 100 A1 50 / / / 20 60 50 50 50 A2 / 50 / / / / / / / A3 / / 50 / / / / / / A4 / / / 50 / / / / / Cyanate resin 200 200 200 200 200 200 100 300 200 diaminodiphenylsulfone 30 30 30 30 30 30 30 30 30 2E4MI 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Silica filler 30 30 30 30 30 30 30 30 / Silane coupling agent 1 1 1 1 1 1 1 1 / toluene 150 150 150 150 150 150 150 150 150 Laminate Properties D1 D2 D3 D4 D5 D6 D7 D8 D9 DSC Tg ( ^o C ) 226.7 228.1 224.2 231.2 227.4 225.3 221.5 232.5 226.1 Dk (5GHz) 4.08 4.11 4.13 4.17 4.2 4.05 4.21 4.01 4.13 Df (5GHz) 0.0053 0.0056 0.0056 0.0057 0.0054. 0.0052 0.0057 0.0051 0.0053 Water absorption (%) PCT2 hours 0.27 0.25 0.28 0.29 0.27 0.29 0.28 0.22 0.30 Coefficient of Thermal Expansion (ppm/ ^oC ) 24.21 23.9 26.31 29.08 43.09 24.15 33.35 22.1 45.21 Z-axis expansion (%) 1.76 1.72 1.95 1.83 2.14 1.73 1.81 1.68 2.72 Thermal decomposition temperature ( ^oC ) 399.9 402.1 399.9 403.5 407.5 395.4 392.3 406.5 401.5 toughness good good good good generally good good generally good Tear Strength (1oz) (lb/in) 8.6 8.9 8.7 9.0 9.0 8.3 8.2 9.3 8.5 Solder dip resistance(288 ^oC )(min) >10 >10 >10 >10 >10 >10 >10 >10 >10 UL94 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 [Table 2] Resin composition raw material ratio and laminate performance (parts by weight) in the comparative example Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 resin composition E1 E2 E3 E4 E5 epoxy resin 100 100 100 100 100 A1 10 80 50 50 / A2 / / / / / BDP / / / / 50 Cyanate resin 200 200 50 400 200 Diaminodiphenylsulfone hardener 30 30 30 30 30 2E4MI 0.5 0.5 0.5 0.5 0.5 Silica filler 30 30 30 30 30 Silane coupling agent 1 1 1 1 1 toluene 150 150 150 150 150 Laminate properties F1 F2 F3 F4 F5 DSC Tg ( ^o C ) 228.1 225.1 219.4 236.1 224.1 Dk(5GHz) 4.2 4.04 4.31 3.98 4.06 Df(5GHz) 0.0053 0.0052 0.0059 0.0050 0.0051 Water absorption (%) PCT2 hours 0.26 0.31 0.35 0.19 0.29 Coefficient of Thermal Expansion (ppm/ ^oC ) 48.21 23.95 49.55 20.1 25.31 Z-axis expansion (%) 2.32 1.72 2.45 1.62 1.92 Thermal decomposition temperature ( ^oC ) 408.1 393.9 362.1 410.5 387.1 toughness inferior good good inferior good Tear Strength (1oz) (lb/in) 9.1 7.9 7.2 9.3 8.5 Solder dip resistance(288 ^oC )(min) >10 <10 <10 >10 >10 UL94 NG V-0 V-0 V-0 V-0

In Table 1 and Table 2, the epoxy resin adopts the bisphenol A novolac type epoxy resin EPICLON N-865 manufactured by DIC Co., Ltd., and BDP is bisphenol A-bis(diphenyl phosphate) (Taiwan Liuhe Chemical Industry Co., Ltd. , CAS No.: 5945-33-5), the cyanate resin adopts bisphenol A type cyanate resin (Yangzhou Tianqi CE01PS), and the silane coupling agent is KBM-974H (Shin-Etsu Chemical).

It can be seen from Table 1 and Table 2 that the laminates D1-D9 prepared using the epoxy resins of Examples 1-9 of the present invention as raw materials have excellent heat resistance, dimensional stability and other properties. The laminates of the comparative example have poor toughness (such as F1, F4), or poor flame retardancy (such as F1), or poor dip soldering resistance (such as F2, F3), or low thermal decomposition temperature (such as F5).

Comparing the laminates F1, D5, D1, D6 and F2, within a certain range, with the increase of the amount of phosphobenzene bisphenol polymer, the Dk and Df of the laminates decrease, the dimensional stability becomes better, and the toughness increases; In this range, the toughness of the laminate becomes worse (such as F1); above this range, the water absorption of the laminate increases, the heat resistance decreases, and the tear strength decreases (such as F2).

Compared with laminates F3, D7, D1, D8 and F4, within a certain range, as the amount of cyanate ester increases, Dk and Df decrease, dimensional stability improves, heat resistance increases, tear strength increases, and water absorption decreases ; Below this range, the dimensional stability becomes poor (such as F3); above this range, the toughness of the laminate becomes poor (such as F4).

Comparing laminates D1, D2, D3, D4, D5 and F5, compared to using BDP as a flame retardant, using the phosphobenzene bisphenol polymer of the present invention as a flame retardant, the laminates have better heat resistance and tear resistance The strength is also higher.

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

The above-mentioned embodiments only express several implementation modes of the present invention, and the descriptions thereof are relatively specific and detailed, but should not be construed as limiting the patent scope of the invention. It should be pointed out that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent for the present invention should be based on the appended claims.

Figure 1 is the hydrogen nuclear magnetic resonance spectrum of phosphobenzene bisphenol polymer A1. Figure 2 is the hydrogen nuclear magnetic resonance spectrum of the phosphobenzene bisphenol polymer A3.

Claims (10)

A resin composition containing phosphobenzene bisphenol polymer, wherein, including the following raw materials in parts by weight: 100 parts of epoxy resin, 40-80 parts of phosphobenzene bisphenol polymer, 100-300 parts of cyanate resin, hardener 28～32 parts; The structure of described phosphobenzene bisphenol polymer is as shown in formula I or formula II:

Formula I

Formula II wherein, n=2~5, R is selected from: CH ₃ CCH ₃ ,

,

,

One of. The resin composition as claimed in item 1, wherein the preparation method of the phosphobenzene bisphenol polymer is carried out according to the synthetic route shown in formula III or formula IV:

Formula III

Formula IV Mix phenylphosphonic acid dichloride or phenyl dichlorophosphate and tetramethylbisphenol compound, add toluene and co-solvent, and reflux reaction to obtain the compound shown in formula I or formula II. The resin composition as claimed in item 2, wherein, the tetramethylbisphenol compound is selected from: tetramethylbisphenol A,

,

,

; The co-solvent is selected from one or both of pyridine and 4-dimethylaminopyridine; the molar ratio of the phenylphosphonic dichloride or phenyl dichlorophosphate to tetramethylbisphenol compound is 1: (1 ~2). The resin composition according to claim 2, wherein the reflux reaction temperature is 120-180° C., and the reaction time is 10-20 hours. The resin composition as claimed in item 1, wherein, the epoxy resin is selected from: one or both of bisphenol A novolak epoxy resins and bisphenol F novolac epoxy resins; the cyanate ester resin Selected from: one or more of bisphenol A cyanate, bisphenol F cyanate, and cycloaliphatic aromatic cyanate. The resin composition according to claim 1, wherein the hardener is selected from one or both of diamino-diphenylsulfone and amino-triazine phenolic resins. The resin composition according to any one of claims 1 to 6, further comprising 120-180 parts of solvent and 25-35 parts of functional additives. The resin composition as claimed in item 7, wherein the solvent is selected from: toluene, γ-butyrolactone, methyl ethyl ketone, cyclohexanone, butanone, acetone, xylene, methyl isobutyl ketone, N, One or more of N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; the functional additives are selected from: fillers, hardening accelerators, dispersants, One or more than two types of tougheners. A prepreg, wherein it is prepared from the raw material of the resin composition containing the phosphorous benzene bisphenol polymer described in any one of claims 1 to 8. Application of a resin composition containing a phosphorous benzene bisphenol polymer as described in any one of claims 1 to 8 or a prepreg as described in claim 9 in the preparation of laminated boards.

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