阅读说明：本技术 一种无卤高Tg阻燃耐热覆铜箔环氧玻纤布基层压板及其制备方法 (Halogen-free high-Tg flame-retardant heat-resistant copper foil-clad epoxy fiberglass cloth-based laminated board and preparation method thereof ) 是由 李洪彬 于 2019-09-04 设计创作，主要内容包括：本发明提供了一种无卤高Tg阻燃耐热覆铜箔环氧玻纤布基层压板及其制备方法,其中制备方法主要包括步骤101,填料分散：按重量份取18～22份含磷环氧树脂和48～52份酚醛环氧树脂,往其中加入18～22份PMA,混合搅拌,边搅拌边加入18～22份填料后加速搅拌,形成分散填料；所述填料为氢氧化铝和/或二氧化硅,其中氢氧化铝和二氧化硅混合比例为1：1；步骤102,树脂入槽：将48～52份酚醛环氧树脂和18～22份高耐热性环氧树脂树脂和步骤101获得的分散填料混合后得到混合料；步骤103,加入固化剂；步骤104,停机测S/G；步骤2,含浸；步骤3,堆叠；步骤4,组合；步骤5,压合,步骤6,裁剪。本发明具有Tg大于170℃(DSC)、优异的耐热性能(T-288>60min)、低Z轴膨胀系数、低吸水率、具有耐CAF功能。(The invention provides a halogen-free high-Tg flame-retardant heat-resistant copper foil-clad epoxy fiberglass cloth-based laminated board and a preparation method thereof, wherein the preparation method mainly comprises the following steps of 101, filler dispersion: taking 18-22 parts by weight of phosphorus-containing epoxy resin and 48-52 parts by weight of novolac epoxy resin, adding 18-22 parts by weight of PMA, mixing and stirring, adding 18-22 parts by weight of filler while stirring, and then accelerating stirring to form dispersed filler; the filler is aluminum hydroxide and/or silicon dioxide, wherein the mixing ratio of the aluminum hydroxide to the silicon dioxide is 1: 1; step 102, resin entering: mixing 48-52 parts of novolac epoxy resin, 18-22 parts of high-heat-resistance epoxy resin and the dispersed filler obtained in the step 101 to obtain a mixture; 103, adding a curing agent; step 104, stopping the machine and measuring the S/G; step 2, impregnation; step 3, stacking; step 4, combining; and 5, pressing, and 6, cutting. The invention has Tg greater than 170 ℃ (DSC), excellent heat resistance (T-288>60min), low Z-axis expansion coefficient, low water absorption and CAF resistance.)

1. the preparation method of the halogen-free high-Tg flame-retardant heat-resistant copper-clad foil epoxy fiberglass cloth-based laminated board is characterized by comprising the following steps of:

Step 1, preparing ingredients;

Wherein, the preparation of the ingredients comprises the following steps:

Step 101, filler dispersion: taking 18-22 parts by weight of phosphorus-containing epoxy resin and 48-52 parts by weight of novolac epoxy resin, adding 18-22 parts by weight of PMA, mixing and stirring, adding 18-22 parts by weight of filler while stirring, and then accelerating stirring to form dispersed filler;

The filler is aluminum hydroxide and/or silicon dioxide, wherein the mixing ratio of the aluminum hydroxide to the silicon dioxide is 1: 1;

Step 102, resin entering: mixing 48-52 parts of novolac epoxy resin, 18-22 parts of high-heat-resistance epoxy resin and the dispersed filler obtained in the step 101 to obtain a mixture;

Step 103, adding a curing agent: adding 18-22 parts of phenolic resin, 48-52 parts of benzoxazine resin, 58-62 parts of phosphorus-containing flame retardant curing agent and 0.45-0.55 part of catalyst dimethylimidazole into the mixture obtained in the step 102, and continuously stirring to enable the mixture and the mixture to fully generate a curing reaction to form glue;

Step 104, stopping and measuring S/G: extracting a sample from the ingredients formed in the step 103, measuring the S/G value of the sample, and if the measured S/G range is in a 280-320S interval, enabling the ingredients to be qualified and entering the next step;

Step 2, impregnation: soaking glass fiber cloth into the ingredients prepared in the step 1, and drying to obtain a semi-solid sheet;

And 3, stacking: stacking at least one prepreg to a certain preset thickness so as to meet the requirements of different thicknesses;

and 4, combining: covering a single-sided or double-sided copper foil on the prepreg stacked in the step 3, combining the prepreg with a die, and then sending the combined prepreg into a hot press;

Step 5, pressing: melting the resin in the prepreg at high temperature, and expelling bubbles under high pressure to gradually harden the resin and bond the resin with the copper foil to form a substrate;

step 6, checking: and cutting off the edge materials of the laminated substrate, and then checking the appearance, the thickness and the like to obtain a finished product.

2. The method for preparing a flame-retardant heat-resistant copper foil-coated epoxy glass fiber cloth base laminated board according to claim 1, wherein in the step 101, after the addition of the silicon dioxide is completed, the rotating speed is not lower than 1000 r/Min.

3. the preparation method of the halogen-free high-Tg flame-retardant heat-resistant copper clad foil epoxy fiberglass cloth-based laminate according to claim 1 or 2, characterized in that in the step 101, after the addition of the silicon dioxide is completed, the stirring time is not less than 4.5H.

4. The method for preparing the halogen-free high-Tg flame-retardant heat-resistant copper clad foil epoxy fiberglass cloth-based laminate according to claim 1, wherein in the step 103, the stirring is continuously carried out for not less than 5H.

5. the preparation method of the halogen-free high-Tg flame-retardant heat-resistant copper clad foil epoxy fiberglass cloth-based laminate according to claim 1, wherein in the step 2, the specific steps of immersing the fiberglass cloth into the ingredients prepared in the step 1 are as follows: driving the electronic-grade glass fiber cloth on a cloth rack of an impregnation machine, controlling the glass fiber cloth to advance by tension, enabling the glass cloth to pass through an impregnation groove full of glue, enabling the glass cloth soaked with the glue to enter an oven, volatilizing redundant solvent and carrying out further reaction on resin and a curing agent; and drying to obtain the semi-fixing sheet.

6. the method for preparing the halogen-free high-Tg flame-retardant heat-resistant copper clad laminate based on epoxy fiberglass cloth as claimed in claim 1, wherein the mold in the step 4 is a mold-steel plate.

7. The method for preparing the flame-retardant heat-resistant copper foil-coated epoxy fiberglass cloth-based laminated board as claimed in claim 1, wherein in the step 5, during the pressing process, the temperature is controlled to be 1.2-1.8 ℃/min, the pressure is 3.0Mpa, and the vacuum is 730 mmhg.

8. The method for preparing the flame-retardant and heat-resistant copper foil-coated epoxy fiberglass cloth-based laminated board as claimed in claim 1, wherein in the step 104,

if the S/G is longer, adding 0.01-0.1 part of catalyst for accelerating the reaction;

if the S/G is shorter, additionally preparing a new ingredient with long S/G length according to the steps 101-103, uniformly mixing the new ingredient with the original ingredient, and then detecting the S/G, wherein in the preparation process of the new ingredient, the addition amount of the bisphenol A type bromine epoxy resin is increased by 10-20%.

9. the method for preparing the flame-retardant and heat-resistant copper foil-coated epoxy fiberglass cloth-based laminated board as claimed in claim 1, wherein the temperature is controlled to be between 25 and 50 ℃ during the curing process of step 103.

10. the flame-retardant heat-resistant copper-clad epoxy fiberglass cloth-based laminated board prepared by the preparation method of claims 1-9.

Technical Field

The invention relates to the technical field of electronic materials, in particular to a halogen-free high-Tg flame-retardant heat-resistant copper foil-clad epoxy fiberglass cloth-based laminated board and a preparation method thereof.

background

copper Clad Laminate (CCL) is a product which is prepared by using wood pulp paper or glass fiber cloth as a reinforcing material, soaking the reinforcing material with resin, coating Copper foil on one side or two sides, and carrying out hot pressing. The copper-clad plate is a basic material in the electronic industry, is mainly used for processing and manufacturing Printed Circuit Boards (PCBs), and is widely applied to electronic products such as televisions, radios, computers, mobile communication and the like.

the copper-clad plates available in the market can be mainly classified into the following types from the viewpoint of base materials: paper substrates, glass fiber cloth substrates, synthetic fiber cloth substrates, nonwoven fabric substrates, composite substrates, and others.

the preparation process flow of the glass fiber cloth substrate is as follows approximately: cutting → pre-stacking → combining → pressing → disassembling → cutting → packaging → warehousing → delivering.

the traditional high-heat-resistance high-Tg copper-clad plate suitable for the lead-free process adopts halogen (Br and other elements) as a flame retardant, but the substance can generate a carcinogenic substance-dioxin under the condition of incomplete combustion, so that the environment is influenced to a certain extent, and the environment is not protected.

On the other hand, the traditional common Tg sheet material adopts amine compounds as curing agents which react with epoxy resin, and the copper-clad plate has the defects of low Tg and unsuitability for a lead-free tin spraying process with environmental protection requirements.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provide a halogen-free high-Tg flame-retardant heat-resistant copper foil-clad epoxy glass fiber cloth-based laminated board and a preparation method thereof.

in order to solve the technical problems, the invention adopts the following technical scheme:

A preparation method of a halogen-free high-Tg flame-retardant heat-resistant copper-clad foil epoxy fiberglass cloth-based laminated board comprises the following steps:

Step 1, preparing ingredients;

Wherein, the preparation of the ingredients comprises the following steps:

Step 101, filler dispersion: taking 18-22 parts by weight of phosphorus-containing epoxy resin and 48-52 parts by weight of novolac epoxy resin, adding 18-22 parts by weight of PMA (propylene glycol monomethyl ether acetate), mixing and stirring, adding 18-22 parts by weight of filler while stirring, and then accelerating stirring to form dispersed filler;

the filler is aluminum hydroxide and/or silicon dioxide, wherein the mixing ratio of the aluminum hydroxide to the silicon dioxide is 1: 1;

step 102, resin entering: mixing 48-52 parts of novolac epoxy resin, 18-22 parts of high-heat-resistance epoxy resin and the dispersed filler obtained in the step 101 to obtain a mixture;

step 103, adding a curing agent: adding 18-22 parts of phenolic resin, 48-52 parts of benzoxazine resin, 58-62 parts of phosphorus-containing flame retardant curing agent and 0.45-0.55 part of catalyst dimethylimidazole into the mixture obtained in the step 102, and continuously stirring to enable the mixture and the mixture to fully generate a curing reaction to form glue;

step 104, stopping and measuring S/G: extracting a sample from the ingredients formed in the step 103, measuring the S/G (gel time) value of the sample, and if the measured S/G range is in a range of 280-320S, entering the next step if the ingredients are qualified;

Step 2, impregnation: soaking glass fiber cloth into the ingredients prepared in the step 1, and drying to obtain a semi-solid sheet;

and 3, stacking: stacking at least one prepreg to a certain preset thickness so as to meet the requirements of different thicknesses;

And 4, combining: covering a single-sided or double-sided copper foil on the prepreg stacked in the step 3, combining the prepreg with a die, and then sending the combined prepreg into a hot press;

Step 5, pressing: melting the resin in the prepreg at high temperature, and expelling bubbles under high pressure to gradually harden the resin and bond the resin with the copper foil to form a substrate;

Step 6, checking: and cutting off the edge materials of the laminated substrate, and then checking the appearance, the thickness and the like to obtain a finished product.

preferably, in the step 101, after the addition of the silica and the aluminum hydroxide is completed, the rotation speed is not lower than 1000 r/Min.

preferably, in the step 101, after the addition of the silica and the aluminum hydroxide is completed, the stirring time is not less than 4.5H.

Preferably, in the step 103, the stirring is continuously carried out for not less than 5H.

preferably, in the step 2, the specific steps of immersing the glass fiber cloth into the furnish prepared in the step 1 are as follows: driving the electronic-grade glass fiber cloth on a cloth rack of an impregnation machine, controlling the glass fiber cloth to advance by tension, enabling the glass cloth to pass through an impregnation groove full of glue, enabling the glass cloth soaked with the glue to enter an oven, volatilizing redundant solvent and carrying out further reaction on resin and a curing agent; and drying to obtain the semi-fixing sheet.

Preferably, the mold in the step 4 is a steel plate.

Preferably, in the pressing process in the step 5, the temperature is increased to 1.2-1.8 ℃/min, the pressure is 3.0Mpa, and the vacuum is 730 mmhg.

preferably, in the step 104, the step of,

If the S/G is longer, adding 0.01-0.1 part of catalyst for accelerating the reaction;

if the S/G is shorter, additionally preparing a new ingredient with long S/G length according to the steps 101-103, uniformly mixing the new ingredient with the original ingredient, and then detecting the S/G, wherein in the preparation process of the new ingredient, the addition amount of the bisphenol A type bromine epoxy resin is increased by 10-20%.

Preferably, the temperature is controlled between 25 ℃ and 50 ℃ during the step 103 of curing.

the flame-retardant heat-resistant copper-clad foil epoxy fiberglass cloth-based laminated board prepared by the preparation method.

has the advantages that:

The invention has the beneficial effects of environmental protection and harmlessness. Specifically, the invention adopts another phosphorus-containing epoxy resin as a flame retardant, can meet the flame-retardant requirement and also meets the environmental protection requirement; in addition, the invention adopts a unique phenolic aldehyde curing technology and a benzoxazine resin curing technology, enhances the crosslinking density with the epoxy resin, thereby improving the Tg of the board and being suitable for the lead-free tin spraying process of the PCB.

In addition, the substrate developed by the invention has Tg higher than 170 ℃ (DSC), excellent heat resistance (T-288>60min), low Z-axis expansion coefficient, low water absorption and CAF (by-product after copper foil metal electric reaction corrosion) resistance, and the required curing temperature and time can be obviously reduced and shortened compared with other halogen-free boards, thereby improving the PCB processing efficiency.

Drawings

FIG. 1 shows a flow chart of the preparation in the example of the present invention.

In order to more clearly illustrate the detailed description of the invention or the technical solutions in the prior art, the drawings that are needed in the detailed description of the invention or the prior art will be briefly described below. Throughout the drawings, like elements or portions are generally identified by like reference numerals. In the drawings, elements or portions are not necessarily drawn to scale.

Detailed Description

The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

it should be noted that all the directional indicators (such as upper, lower, left, right, front and rear … …) in the embodiment of the present invention are only used to explain the relative position relationship between the components, the movement situation, etc. in a specific posture (as shown in the drawing), and if the specific posture is changed, the directional indicator is changed accordingly.

In addition, the descriptions related to "first", "second", etc. in the present invention are only for descriptive purposes and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.

The embodiment of the invention relates to a preparation method of a halogen-free high-Tg flame-retardant heat-resistant copper foil-clad epoxy fiberglass cloth-based laminated board.