CN113844129A - Preparation method of halogen-free copper-clad plate with low dielectric loss and high heat resistance - Google Patents

Preparation method of halogen-free copper-clad plate with low dielectric loss and high heat resistance Download PDF

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CN113844129A
CN113844129A CN202111066750.5A CN202111066750A CN113844129A CN 113844129 A CN113844129 A CN 113844129A CN 202111066750 A CN202111066750 A CN 202111066750A CN 113844129 A CN113844129 A CN 113844129A
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resin
parts
copper
clad plate
preparation
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李凌云
刘政
杨永亮
郑宝林
栾好帅
姜晓亮
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SHANDONG JINBAO ELECTRONICS CO Ltd
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SHANDONG JINBAO ELECTRONICS CO Ltd
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    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
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    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2457/00—Electrical equipment
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    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
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Abstract

The invention belongs to the technical field of copper-clad plate production, and relates to a preparation method of a halogen-free copper-clad plate with low dielectric loss and high heat resistance. In the resin glue solution, biphenyl groups are introduced into an epoxy resin framework, so that the heat resistance of the resin glue solution can be improved, the free volume is reduced, the toughness is improved, the water absorption is reduced, and the stress generated in the high-temperature lead-free welding process of the manufactured PCB is reduced. The BT modified PPO resin not only retains the original excellent heat resistance and low metal ion migration resistance of the BT resin, but also has good dimensional stability, and greatly improves the dielectric property and the mechanical processing property of the BT resin. The copper-clad plate prepared by the invention has the advantages that the T288 can not be delaminated within 120min, the Tg is as high as 230 ℃, and the Df is less than 0.006, so that the high-frequency high-speed circuit board is suitable for the high-layer design of the high-frequency high-speed circuit board, and the packaging efficiency and the reliability of the PCB are greatly improved.

Description

Preparation method of halogen-free copper-clad plate with low dielectric loss and high heat resistance
Technical Field
The invention belongs to the technical field of copper-clad plate production, and particularly relates to a preparation method of a halogen-free copper-clad plate with low dielectric loss and high heat resistance.
Background
Although European Union (WEEE) and RoHS instructions do not definitely forbid the fire retardant containing bromine, the copper-clad plate containing bromine can release a large amount of toxic gas (brominated type) during combustion or electric appliance fire, and the smoke quantity is large; when the PCB is subjected to hot air leveling and element welding, the board is influenced by high temperature (>200 ℃) and can release trace hydrogen bromide; whether toxic gases are also produced is also under evaluation. Some electronic and electrical complete machinery factories in japan and europe have extended the forbidden range to all halogen-containing flame retardants. No matter the predicted data or the actual sales data, the halogen-free copper-clad plate is shown to be in a rapid growth period.
With the wide popularization of 5G communication technology, electronic products are changing day by day, faster data transmission speed is needed, higher system operation frequency is also needed, meanwhile, lead-free welding requires materials to endure higher temperature, higher requirements are provided for printed circuit boards, and the epoxy phenolic resin system commonly applied to copper-clad plates originally has very large dielectric loss, so that the application of the epoxy phenolic resin system in the high-frequency and high-speed field is limited. Various high-performance resin materials such as BT resin, PPE, SMA, PI, PTFE and the like are developed in many advanced foreign countries to meet the development requirements of electronic communication technologies, and the reasonable application of the resins has important significance in the research and development of copper-clad plates.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a halogen-free copper-clad plate with low dielectric loss and high heat resistance.
The specific technical scheme is as follows:
a preparation method of a halogen-free, low-dielectric-loss and high-heat-resistance copper-clad plate comprises the following steps:
(1) mixing 20-40 parts of biphenyl epoxy resin, 60-90 parts of BT modified PPO resin, 10-40 parts of phosphorus-containing flame retardant, 1-20 parts of crosslinking curing agent and curing accelerator, 0.1-1 part of dispersant, 40-100 parts of solvent and 10-50 parts of filling material according to parts by weight, emulsifying and stirring uniformly;
(2) after the low dielectric electronic grade glass fiber cloth is soaked in the resin prepared in the step (1), the resin is processed by a sizing machine at the temperature of 100-200 ℃ to prepare a prepreg;
(3) stacking a plurality of prepregs prepared in the step (2) together, and covering a copper foil on each of two sides to obtain a plate; and (3) correspondingly superposing the plate and the stainless steel plate up and down, sending the plate and the stainless steel plate into a vacuum press, and carrying out hot pressing at the temperature of 250 ℃ and 70-150kgf/cm for 300min to obtain the halogen-free low-dielectric-loss high-heat-resistance copper clad plate.
On the basis of the technical scheme, the invention can be further improved as follows:
in the step (1), the biphenyl type resin is an epoxy resin with a biphenyl (biphenyl) structure-containing phenolic resin as a main chain, the aromatic ring occupation ratio of the resin is high, and the resin also has high fluidity, excellent solubility and low viscosity in toluene and butanone, and can be dissolved in a solvent in advance to prepare a solution. The biphenyl resin structure is as follows:
Figure BDA0003258730590000021
wherein the BT modified PPO resin is prepared by mixing PPO resin and BT resin according to the weight ratio of 9: 1, the BT resin is a B-stage prepolymer obtained by copolymerizing Arocy B-10 and 4, 4' -diaminodiphenylmethane bismaleimide, and is also dissolved in a solvent in advance;
the phosphorus-containing flame retardant is at least one of a phosphazene compound or resorcinol bis [ di (2, 6-dimethylphenyl) phosphate, wherein the phosphorus content of the phosphazene compound is 13 wt%, the phosphazene compound is an inorganic compound with P, N alternating double bonds arranged as a main chain structure, the inorganic compound exists in a ring or linear structure, a phenoxy group is connected to a phosphorus atom, and the introduction of the phenoxy group enables the phosphazene compound to be a product combining the inorganic compound and an organic compound, so that the phosphorus-containing flame retardant is a good halogen-free environment-friendly flame retardant. The structural formula is as follows:
Figure BDA0003258730590000031
wherein the resorcinol bis [ bis (2, 6-dimethylphenyl) phosphate is a polycondensation type phosphate flame retardant with a phosphorus content of 10.5 wt%.
Wherein the crosslinking curing and curing accelerator is at least one of 2-ethyl zinc octoate, 2-methyl 4-ethyl imidazole or silane coupling agent KH-560, and trace amount of curing agent or curing accelerator can be added to 10% solution to ensure accurate feeding.
Wherein the dispersant is a BYK W-903 type wetting dispersant, and the solvent is one or more than two of toluene, acetone or butanone and xylene.
Wherein the filling material is one or more than two of high-purity superfine spherical nano amorphous silicon micro powder and aluminum hydroxide, the content of SiO2 in the silicon micro powder reaches 99.9 percent, the average particle size is 3-5 mu m, the maximum particle size is not more than 20 mu m, and finally the filling material is added.
Preferably, in the step (2), the gelling time of the prepreg is controlled to be 80-100 seconds;
preferably, in the step (3), the number of prepregs can be adjusted according to different thickness requirements, the plate and the stainless steel plate are correspondingly overlapped up and down, then a high heat-resistant felt is paved, the plate and the stainless steel plate are sent into a vacuum press, and the plate and the stainless steel plate are hot-pressed for 180min at the temperature of 250 ℃ and 70-150kgf/cm, so that the halogen-free copper-clad plate with low dielectric loss and high heat resistance is prepared.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention impregnates the E-GLASS fiber cloth of low dielectric type into the special resin glue solution, biphenyl type (biphenyl) epoxy resin in the resin glue solution introduces biphenyl group into the epoxy resin framework, on one hand, the heat resistance of the resin glue solution can be improved, and on the other hand, the free volume can be reduced, so that the toughness is improved, and the water absorption is reduced. In addition, the biphenyl structure in the epoxy resin increases the molecular weight between crosslinking functional groups (epoxy groups), reduces the elastic modulus in a hot state, has the characteristic of high toughness, and reduces the stress generated in the high-temperature lead-free welding process of the PCB manufactured by the biphenyl structure.
(2) The BT modified PPO resin not only retains the original excellent heat resistance and low metal ion migration resistance of the BT resin, but also has good dimensional stability, greatly improves the dielectric property, reduces the dielectric loss and the dielectric constant, and greatly improves the machining property.
(3) The phosphorus-containing flame retardant used in the invention has a unique self-extinguishing function, has a higher thermal decomposition temperature and a flame-retardant effect, can reach UL-94VO level flame-retardant performance, and has a flame-retardant performance greatly superior to that of the traditional flame-retardant system. And smoke and toxic gas are few, so that the flame-retardant material is an environment-friendly flame-retardant material and can meet the requirements of the European Union RollS instruction and WEEE instruction.
(4) The spherical silicon added into the glue solution has small particle size and good dispersibility, so that the PCB has lower molding shrinkage and good dimensional stability. The glass fiber cloth used for impregnation is also low dielectric E-glass fiber cloth. The copper-clad plate prepared by the invention has the advantages that the T288 can not be delaminated within 120min, the Tg is up to 225 ℃, and the Df is less than 0.006, so that the high-frequency high-speed circuit board is suitable for the high-layer design of the high-frequency high-speed circuit board, and the packaging efficiency and the reliability of the PCB are greatly improved.
Detailed Description
The principles and features of this invention are described below in conjunction with examples, which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
(1) Preparing resin glue solution: according to the weight portion, 22 portions of biphenyl epoxy resin, 85 portions of BT modified PPO resin (Arocy B-10 and 4, 4' -diaminodiphenylmethane bismaleimide B-stage prepolymer and PPO resin are blended in a mass ratio of 1: 9), 20 portions of phosphorus-containing flame retardant phosphazene compound (the phosphorus content is 13% wt), 0.5 portion of curing accelerator 2-ethyl zinc octoate, 0.01 portion of 2-methyl 4-ethyl imidazole, 0.4 portion of dispersant BYK W-903, 100 portions of solvent butanone, 80 portions of filling material high-purity superfine spherical nano amorphous silicon micro powder and 20 portions of aluminum hydroxide are mixed, emulsified and stirred uniformly;
(2) and (2) dipping the low-dielectric electronic-grade glass fiber cloth in the resin glue solution prepared in the step (1), and preparing a prepreg through a gluing machine at 170 ℃.
(3) Taking 6 prepregs obtained in the step (2) to be overlaid together, and covering 18-micrometer copper foils on two sides of each prepreg to obtain a plate; the plate and the stainless steel plate are overlapped up and down correspondingly, a high heat-resistant felt is paved, and the plate is sent into a vacuum press to be processed at the temperature of 170 ℃ and 250 ℃ and the kgf/cm of 1202And (4) carrying out hot pressing for 180min under the condition to obtain the halogen-free copper-clad plate with low dielectric loss and high Tg.
Comparative example 1
(1) Preparing resin glue solution: according to the weight parts, 40 parts of PPE resin (dihydroxy-terminated polyphenyl ether oligomer), 140 parts of dicyclopentadiene epoxy resin, 10 parts of DDS resin, 0.3 part of 2-methyl 4-ethylimidazole as a crosslinking curing agent, 0.5 part of BYK W-903 as a dispersing agent, 100 parts of solvent acetone, 20 parts of tetrabromobisphenol A as a flame retardant and 40 parts of high-purity superfine spherical nano amorphous silicon micro powder as a filling material are mixed, emulsified and stirred uniformly;
(2) and (2) dipping the low-dielectric electronic-grade glass fiber cloth in the resin glue solution prepared in the step (1), and preparing a prepreg through a gluing machine at 170 ℃.
(3) Taking 6 prepregs obtained in the step (2) to be overlaid together, and covering 18-micrometer copper foils on two sides of each prepreg to obtain a plate; the plate and the stainless steel plate are overlapped up and down correspondingly, a high heat-resistant felt is paved, and the plate is sent into a vacuum press to be processed at the temperature of 170 ℃ and 250 ℃ and the kgf/cm of 1202And (4) carrying out hot pressing for 180min under the condition to obtain the halogen-free copper-clad plate with low dielectric loss and high Tg.
Example 2
(1) Preparing resin glue solution: according to the weight parts, 35 parts of biphenyl epoxy resin, 75 parts of BT modified PPO resin (a B-stage prepolymer of Arocy B-10 and 4, 4' -diaminodiphenylmethane bismaleimide and PPO resin are blended in a mass ratio of 1: 9), 10 parts of phosphorus-containing flame retardant resorcinol bis [ bis (2, 6-dimethylphenyl) phosphate (the phosphorus content is 10.5 wt%), 10 parts of phosphazene compound (the phosphorus content is 13 wt%), 0.5 part of curing accelerator 2-zinc ethyloctoate, 0.01 part of 2-methyl 4-ethylimidazole, 0.5 part of dispersant BYK W-903, 100 parts of solvent butanone and 100 parts of filling material high-purity spherical nano amorphous silicon micro powder are mixed, and are emulsified and stirred uniformly;
(2) and (2) dipping the low-dielectric electronic-grade glass fiber cloth in the resin glue solution prepared in the step (1), and preparing a prepreg through a gluing machine at 170 ℃.
(3) Taking 6 prepregs obtained in the step (2) to be overlaid together, and covering 18-micrometer copper foils on two sides of each prepreg to obtain a plate; the plate and the stainless steel plate are overlapped up and down correspondingly, a high heat-resistant felt is paved, and the plate is sent into a vacuum press to be processed at the temperature of 170 ℃ and 250 ℃ and the kgf/cm of 1202And hot pressing for 180min under the condition to obtain the copper-clad plate with low dielectric loss and high Tg.
(2) And (2) dipping the low-dielectric electronic-grade glass fiber cloth in the resin glue solution prepared in the step (1), and preparing a prepreg through a gluing machine at 180 ℃.
(3) Taking 6 prepregs obtained in the step (2) to be overlaid together, and covering 18-micrometer copper foils on two sides of each prepreg to obtain a plate; laminating the plate and stainless steel plate, spreading high heat-resistant felt, and vacuum pressing at 165-235 deg.C and 70-150kgf/cm2And (4) carrying out hot pressing for 200min under the condition to obtain the halogen-free copper-clad plate with low dielectric loss and high Tg.
Example 3
(1) Preparing resin glue solution: according to the weight portion, 60 portions of biphenyl epoxy resin butanone solution (50 percent by weight), 140 portions of BT modified PPO resin solution (Arocy B-10 and 4, 4' -diaminodiphenylmethane bismaleimide B-stage prepolymer and PPO resin are mixed according to the mass ratio of 1: 9 and dissolved in butanone, 50 percent by weight), 18 portions of phosphazene compound (phosphorus content is 13 percent by weight), 0.5 portion of curing accelerator 2-ethyl zinc octoate, 0.01 portion of 2-methyl 4-ethyl imidazole, 0.5 portion of dispersant BYK W-903, 10 portions of solvent toluene and 100 portions of filling material high-purity superfine spherical nano amorphous silicon powder are mixed, emulsified and stirred uniformly;
(2) and (2) dipping the low-dielectric electronic-grade glass fiber cloth in the resin glue solution prepared in the step (1), and preparing a prepreg through a gluing machine at 180 ℃.
(3) Taking 4 prepregs prepared in the step (2) to be overlapped together, and covering 18-micrometer copper foils on two sides of each prepreg to obtain a plate; the plate and the stainless steel plate are overlapped up and down correspondingly, a high heat-resistant felt is paved, and the plate is sent into a vacuum press to be processed at the temperature of 170 ℃ and 235 ℃ and the pressure of 130kgf/cm2And hot pressing for 200min under the condition to obtain the copper-clad plate with low dielectric loss and high Tg.
The results of comparing the properties of the samples obtained in examples 1 to 3 with those of comparative example 1 are shown in Table 1.
TABLE 1 comparison of the Properties of the samples obtained in examples 1-3 with comparative example 1
Figure BDA0003258730590000071
As can be seen from Table 1, compared with comparative example 1, the copper-clad plates prepared in examples 1 to 3 of the scheme of the invention have excellent flame retardance, dielectric loss, Tg and T288 test effects, and the halogen-free copper-clad plate prepared by the invention is proved to have lower dielectric loss, higher heat resistance and better flame retardance. The copper-clad plate prepared by the invention has the advantages that the T288 can not be delaminated within 120min, the Tg is as high as 230 ℃, and the Df is less than 0.006, so that the high-frequency high-speed circuit board is suitable for the high-layer design of the high-frequency high-speed circuit board, and the packaging efficiency and the reliability of the PCB are greatly improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. A preparation method of a halogen-free, low-dielectric-loss and high-heat-resistance copper-clad plate is characterized by comprising the following steps:
(1) preparing glue solution: mixing 20-40 parts of biphenyl epoxy resin, 60-90 parts of BT modified PPO resin, 10-40 parts of phosphorus-containing flame retardant, 1-20 parts of crosslinking curing agent and curing accelerator, 0.1-1 part of dispersant, 40-100 parts of solvent and 10-50 parts of filling material according to parts by weight, emulsifying and stirring uniformly;
(2) after the low dielectric electronic grade glass fiber cloth is soaked in the resin prepared in the step (1), the resin is processed by a sizing machine at the temperature of 100-200 ℃ to prepare a prepreg;
(3) stacking a plurality of prepregs prepared in the step (2) together, and covering a copper foil on each of two sides to obtain a plate; the plate and the stainless steel plate are overlapped up and down correspondingly, and then sent into a vacuum press, and the temperature is controlled at 100 ℃ and 250 ℃ and 70-150kgf/cm2And hot pressing for 150-.
2. The method according to claim 1, wherein the biphenyl type resin is an epoxy resin having a phenolic resin with a biphenyl (biphenyl) structure as a main chain, and has high fluidity, excellent solubility and low viscosity in toluene and butanone, and the biphenyl type epoxy resin has a structure of:
Figure FDA0003258730580000011
3. the preparation method of claim 1, wherein the BT modified PPO resin is prepared by mixing PPO resin and BT resin according to the weight ratio of 9: 1, and the BT resin is a B-stage prepolymer obtained by copolymerizing Arocy B-10 and 4, 4' -diaminodiphenylmethane bismaleimide.
4. The preparation method according to claim 1, wherein the phosphorus-containing flame retardant is at least one of a phosphazene compound and resorcinol bis [ bis (2, 6-dimethylphenyl) phosphate.
5. The method of claim 4, wherein the phosphazene compound contains 13 wt% phosphorus and has the following structural formula:
Figure FDA0003258730580000021
6. the method of claim 4, wherein the resorcinol bis [ bis (2, 6-dimethylphenyl) phosphate is a polycondensation type phosphate flame retardant having a phosphorus content of 10.5 wt%.
7. The method according to claim 1, wherein the crosslinking curing and curing accelerator is at least one of zinc 2-ethyloctoate, 2-methyl-4-ethylimidazole or silane coupling agent KH-560.
8. The method according to claim 1, wherein the dispersant is a BYK W-903 type wetting dispersant.
9. The method according to claim 1, wherein the solvent is at least one of toluene, acetone, butanone and xylene.
10. The preparation method according to claim 1, wherein the filler is selected from the group consisting of high-purity ultra-fine spherical nano amorphous silica micropowder and aluminum hydroxideAt least one of (1), SiO in the fine silica powder2The content is 99.9%, the average particle size is 3-5 μm, and the maximum particle size is not more than 20 μm.
CN202111066750.5A 2021-09-13 2021-09-13 Preparation method of halogen-free copper-clad plate with low dielectric loss and high heat resistance Pending CN113844129A (en)

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CN114953646A (en) * 2022-06-09 2022-08-30 山东金宝电子股份有限公司 Preparation method of copper-clad plate for mini LED backboard and copper-clad plate
CN116512702A (en) * 2023-05-06 2023-08-01 江苏耀鸿电子有限公司 High-frequency high-speed PPO resin-based copper-clad plate and preparation process thereof

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US7547849B2 (en) * 2005-06-15 2009-06-16 E.I. Du Pont De Nemours And Company Compositions useful in electronic circuitry type applications, patternable using amplified light, and methods and compositions relating thereto
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CN114953646A (en) * 2022-06-09 2022-08-30 山东金宝电子股份有限公司 Preparation method of copper-clad plate for mini LED backboard and copper-clad plate
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