TWI381017B - Composition and Manufacturing Method of Halogen - free Printed Circuit Board with Low Dielectric Loss - Google Patents

Description

Halogen-free printed circuit board material composition and manufacturing method with low dielectric loss

The present invention relates to a printed circuit board material composition and manufacturing method, and more particularly to a halogen-free printed circuit board material composition and manufacturing method having low dielectric loss, which has no low dielectric loss. Halogen printed circuit board material composition and manufacturing method, in addition to enabling the printed circuit board substrate material to pass the UL 94V-0 flame retardancy test, and can be combined with a resin with low dielectric loss characteristics and inorganic powder to reduce the material Dielectric constant and dielectric loss make halogen-free printed circuit board material with low dielectric loss, low dielectric loss, heat resistance, low expansion, and meet the market requirements of lead-free solder. ,Environmental requirements.

For the conventionally known FR-4 copper foil substrate material, the flame retardant element is mainly bromine. However, since the substrate material containing bromine as a flame retardant element is burned, there is a large amount of black smoke, and The malodor is released and the harmful substances are released. Therefore, in order to comply with environmental regulations, the demand for halogen-free copper foil substrate materials has also increased. At the same time, in the signal transmission of the circuit, the system industry also constantly requires a faster transmission time of the signal, and at the same time, a clearer signal can be obtained, and because the line width and the line spacing of the printed circuit board are increasingly highly dense, The requirements for substrate materials are also more stringent, so as to ensure that the printed circuit board substrate can still operate normally under the stricter high temperature, high humidity and high voltage environment. Therefore, a halogen-free printed circuit board substrate with low dielectric loss characteristics has been developed. Materials, and in the manufacturing process, can be fabricated using lead-free solder printed circuit board material manufacturing methods.

For the general prior art, for example, the invention publication of the Republic of China Patent Publication No. I290160 "halogen-free flame-retardant epoxy resin composition, non-halogen combination type multi-layer board with flame retardant epoxy resin composition , prepreg, copper-clad laminate, printed wiring board, resin film with copper foil, resin film with carrier, combined laminated board, and combined multi-layer board", Announcement No. I289571 "Halogen-free Phosphorus-free, non-flammable thermosetting polymer material composition, although it is a halogen-free laminate material formulation, these patents only have "halogen-free" function, but do not have low dielectric constant, and low dielectric Electrical loss characteristics; in addition, in the US patent US7273900, although it has a low dielectric constant and low dielectric loss characteristics, the patent uses a bromine-containing and phosphorus-containing flame retardant as an additive type, and is not combined with In the material structure of the substrate, there is a problem that the environment in which the flame retardant is precipitated is polluted.

Therefore, for the conventional technology, if it is desired to satisfy the halogen-free function, it cannot have a low dielectric constant and a low dielectric loss characteristic; however, if a low dielectric constant and a low dielectric loss characteristic are required, There is a problem of polluting the environment. Therefore, it is not possible to simply combine the above-mentioned conventional patents to achieve a halogen-free function, and a demand having a low dielectric constant and a low dielectric loss characteristic, but other technical means must be sought to solve the problem.

Therefore, how can a printed circuit board and a manufacturing method thereof be obtained such that the material composition is halogen-free and has low dielectric loss characteristics, heat resistance, and low expansion property, and at the same time It is also a problem to be solved by meeting the requirements of the market and environmental protection through the requirements of lead-free solder.

The main object of the present invention is to provide a halogen-free printed circuit board material composition and manufacturing method with low dielectric loss, which is applied to a printed circuit board substrate material manufacturing environment, and has a low dielectric loss halogen-free printed circuit. The material of the board is halogen-free and has low dielectric loss characteristics, heat resistance and low expansion. At the same time, it can meet market and environmental requirements through the requirements of lead-free solder.

Another object of the present invention is to provide a halogen-free printed circuit board material composition and a manufacturing method with low dielectric loss, and the halogen-free printed circuit board material composition with low dielectric loss mainly comprises a phosphorus-containing phenolic resin. The cross-linking agent can not only pass the flame retardancy test of UL 94V-0 on the printed circuit board substrate material, but also combine the phosphorus energy with the material to become a material structure without doubt of precipitation, and can be matched with a low-medium The inorganic powder of the electrical loss characteristic is used to reduce the dielectric loss of the material.

According to the above object, the present invention provides a halogen-free printed circuit board material composition and manufacturing method with low dielectric loss, which is applied to a printed circuit board substrate material manufacturing environment, and has low dielectric loss of the present invention. The halogen printed circuit board material consists mainly of a phosphorus-containing phenolic resin as a crosslinking agent, in addition to allowing the printed circuit board substrate material to pass the UL 94V-0 flame retardancy test, and the phosphorus energy can be combined with the material to form a material structure. The material does not have the doubt of precipitation, and can match the resin with low dielectric loss characteristics and the inorganic powder to reduce the dielectric constant and dielectric loss of the material. At the same time, it can meet the requirements of market and environmental protection through the requirements of lead-free solder.

In order to make the person skilled in the art understand the purpose, features and effects of the present invention, the present invention will be described in detail by the following specific embodiments and the accompanying drawings.

The invention relates to a halogen-free printed circuit board material composition and a manufacturing method with low dielectric loss, and the halogen-free printed circuit board material composition with low dielectric loss mainly comprises: 1. Epoxy resin: epoxy resin used It is a halogen-free epoxy resin, including: phenolic epoxy resin (Phenol novolak epoxy, cresol novolak epoxy, bisphenol A novolak type epoxy), bisphenol epoxy resin (biphenol epoxy, bisphenol A type epoxy, bisphenol F Type epoxy,bisphenol M type epoxy),cyclopentadiene type epoxy,isocyanate modified Epoxy

2. Phosphorus-containing crosslinking agent: the phosphorus-containing crosslinking agent used is a reactive phosphorus-containing bisphenol A type crosslinking agent, wherein the phosphorus-containing crosslinking agent has a phosphorus content of 1 to 20%, and the molecule thereof The structure is as shown in Figure 1. Figure 1 is a molecular structure diagram showing the halogen-free low dielectric loss of the present invention. The molecular structure of the phosphorus-containing crosslinker in the composition of the printed circuit board material. In Fig. 1, the molecular structure of the phosphorus-containing crosslinking agent having a phosphorus content of 1 to 20% is shown, wherein R1, R2, and R3 may be phosphorus-containing compounds (DOPO, 9, 10-dihydro-9- Oxa-10-phosphaphanthrene 10-oxide), or an alkyl group of C1 to C10, or an aldehyde group of C1 to C10, or an alcohol group of C1 to C10 or an independent hydrogen group.

3. Crosslinking agent: The crosslinking agent used is a dicyandiamide or a phenol hardener.

4. Low dielectric loss inorganic powder: using inorganic powder with low dielectric loss, including: crystalline crystal silica, fuse type silica, aluminum hydroxide (Al(OH) 3), aluminum oxide (Al2O3), magnesium hydroxide (Mg (OH) 2), magnesium oxide (MgO), bismuth oxide (BeO), boron nitride (BN), tantalum nitride ((Si3N4) and other inorganic Powder.

5. Dispersant: The dispersant is a silane coupling agent (Silane), including an amino-silane and an epoxy-silane.

6. Diluent: Acetone, methyl ethyl ketone (MEK), cyclohexanol, 1-methoxy-2-propanol (PM), 1-methoxy-2-propanol methyl ester can be used. (PMA), dimethylformamide (DMF).

7. Catalyst: The catalyst used includes: a tertiary amine, such as, 2MI (2-methyl-imidazole), 2E4MI (2-ethyl-4-methyl-imidazole), 2PI (2-Phenyl-imidazole), BDMA (Benyl dimethylamine), BF3.MEA, and the like.

Wherein, the epoxy resin is crosslinked with a hardener to form a stable network structure, which has good solder heat resistance and anti-foaming property, and the epoxy resin of the selected epoxy resin has an Epoxy Equivalent Weight (Epoxy Equivalent Weight, EEW) is 200~1500, and the usage is 100 parts. In this case, if the epoxy equivalent is higher than 1500, the wetting state between the resin and the glass fiber bundle may be deteriorated, and if it is lower than 200, the flow gel may be excessively large. Herein, the hydrolyzed chlorine content must be less than 500 ppm, and if it is more than 500 ppm, the progress of the hardening reaction is affected.

The phosphorus-containing crosslinking agent is formed by forming a flame-retardant layer to slowly burn when exposed to a flame or a high temperature, and crosslinking with a hardener to form a stable network structure and forming a varnish. After being impregnated into the woven glass cloth, a flame retardant laminate is formed to have good solder heat resistance and foam resistance. The optimum phosphorus content in the formed sheet ranges from 2 to 6%, so the phosphorus-containing crosslinking agent is selected. The phosphorus content is 2 to 12% by weight, and the amount used is 10 to 100 parts. When the amount used is less than 10 parts, the molded plate has no flame retardant effect; if it exceeds 100 parts, the wetting state between the resin and the glass fiber bundle may be deteriorated, and the hardening reaction may be affected.

The crosslinking agent is a dicyandiamide or a phenol hardener, and the purpose thereof is to reinforce the deficiency of the degree of bonding of the phosphorus-containing crosslinking agent, Didicyandiamide, which has a molecular weight of 83, has two first-order amines, one second-grade amine, and one tertiary amine in its molecular structure. It does not react at room temperature and requires a temperature of 170 ° C. The above reaction will occur, so it can be stored for a long time, and its usage is 0.5~3.5 parts. If it is less than 0.5 part, there is no reinforcing effect. If it is higher than 3.5 parts, there will be a phenomenon of precipitation. The phenol hardener has an OH equivalent of 80 to 140, and has at least one active hydrogen reactive group in its molecular structure, and the amount thereof is 10 to 60 parts, and if it is less than 10 parts, there is no reinforcing effect. If it is higher than 60 parts, there will be a phenomenon that the glue is too large.

The catalyst is a tertiary amine, for example, 2MI, 2E4MI, 2PI, BDMA, etc., and the tertiary amine is characterized by lowering the reaction temperature. If a tertiary amine is not used, the hardening reaction starts at about 170 ° C, if used. The tertiary amine has a hardening reaction occurring at about 120 ° C, and the amount used is 0.01 to 3.0 parts. If the amount used is too high, the reactivity is too fast, which will affect the storage time. If the amount is too small, the effect is not effective.

The low dielectric loss inorganic powder additive has a particle diameter of 1 to 100 um, and includes: crystalline silica, fuse silica, and aluminum hydroxide (Al(OH) 3 ), aluminum oxide (Al2O3), magnesium hydroxide (Mg(OH)2), magnesium oxide (MgO) yttrium oxide (BeO), boron nitride (BN), tantalum nitride (Si3N4) and other inorganic powder, The amount of use is 10~100 parts. If the amount is too high, the raw glue is too thick, which affects the wetting of the glass cloth. If the amount is too small, it has no effect.

The dispersing agent is used for the purpose of uniformly dispersing the inorganic additive in the epoxy resin. The dispersing agent used in the formulation is a decane coupling agent, including an ainino-silane or an epoxy decane. Epoxy-silane to improve inorganic The combination stability between the object and the woven glass cloth achieves the purpose of uniform dispersion, and the coupling agent has no heavy metal, so it does not adversely affect the human body, and the usage amount is 0.1 to 5.0 parts, if the usage amount is too high Then speed up the reaction and affect the storage time. If the dosage is too small, it will have no effect.

The diluent is selected according to the principle that it does not remain in the material after being impregnated on the glass cloth and dried at 60 to 190 ° C, for example, acetone (Acetone), methyl ethyl ketone (MEK), methyl Butanone (MIBK), cyclohexanol, 1-methoxy-2-propanol (PM), 1-methoxy-2-propanol methyl ester (PMA), dimethylformamide DMF).

Figure 2 is a schematic diagram showing some embodiments of the material composition of the halogen-free printed circuit board having low dielectric loss of the present invention. As shown in Fig. 2, in the first embodiment, the epoxy resin is 100 parts of CNE-200, 30 parts of phosphorus-containing crosslinking agent, and the hardening agent is 2.0 parts of dicyandiamide, low dielectric loss inorganic powder. 50 parts, 0.2 parts of catalyst, 0.5 part of dispersing agent, 40 parts of diluent; in the second embodiment, the epoxy resin is 100 parts of Epon 828, 40 parts of phosphorus-containing crosslinking agent, and the hardening agent is dicyandiamide 2.0. 50 parts of low dielectric loss inorganic powder, 0.1 part of catalyst, 0.5 part of dispersant, 40 parts of diluent; in the third embodiment, the epoxy resin is 100 parts of Epon 828 and 40 parts of phosphorus-containing crosslinking agent. The hardener is 30 parts of phenol (PHL-6635), 50 parts of low dielectric loss inorganic powder, 0.3 parts of catalyst, 0.5 part of dispersant, and 40 parts of diluent. In the fourth embodiment, the epoxy resin is Epon 828 with 100 The fraction is 35 parts of a phosphorus-containing crosslinking agent, and the hardening agent is 2.2 parts of dicyandiamide, 50 parts of low dielectric loss inorganic powder, 0.25 parts of a catalyst, 0.5 part of a dispersing agent, and 40 parts of a diluent.

Figure 3 is a flow chart showing the flow steps of a method of fabricating a material composition of a halogen-free printed circuit board having low dielectric loss of the present invention. As shown in FIG. 3, first, in step 11, the amount of epoxy resin, phosphorus-containing crosslinking agent, hardener, low dielectric loss inorganic powder, catalyst, dispersant, and diluent, and type of use are selected. Herein, the selection manner may be, for example, the first embodiment, the second embodiment, the third embodiment, the fourth embodiment, the quantity and the type of use, and the process proceeds to step 12.

In step 12, the preparation was stirred at room temperature for 120 minutes and then proceeded to step 13.

In step 13, the varnish is immersed on a glass cloth of 7628 on a drum type impregnator, and the process proceeds to step 14.

In step 14, the plurality of impregnated glass cloths are pressed at a thickness of 7628 ^* 5 (0.039 mil) on both sides of the outermost layer with each of the 10z copper foils, and the process proceeds to step 15.

In step 15, the substrate after pressing is subjected to characteristic detection.

For the characteristic detection of the pressed substrate, for example, the lead-free solder test is performed with 5 copper-containing substrates, and the size is 290 ^* 210 mm after actually passing Lead free IR reflow 3 times (conditions are as shown in the following figure). Observe whether the copper-containing substrate has a blasting phenomenon.

For electrical detection, the impregnated glass cloth was pressed at a thickness of 2116*1 (0.005 mil) on both sides of the outermost layer with a 1 oz copper foil, and the pressed substrate was subjected to characteristic detection.

Here, the glass transition temperature is measured by a Thermal Mechanical Analyzer (TMA), a thermomechanical analyzer, and the Z-axis expansion coefficient can be simultaneously measured. The test specification for the glass transfer temperature is the IPC-TM-650.2.4.24C test method of The Institute for Interconnecting and Packaging Electronic Circuits (IPC). The test specification for the Z-axis expansion coefficient is the detection method of IPC-TM-650.2.4.41.

The test specification for heat resistance is the detection method of IPC-TN-650.2.4.24.1.

In the thermal shock test, the test piece was placed in a high-humidity environment of 2 atm, 121 ° C for 1 hour, and then placed in a tin furnace at 288 ° C for 20 seconds, then pulled up, and the immersion was repeated. The action is 5 times.

The test for the electrical test was tested with the HP4291 instrument.

Figure 4 is a schematic view showing the substrate characteristics of some embodiments of the material composition of the halogen-free printed circuit board having low dielectric loss of the present invention as illustrated in Figure 2. As shown in Fig. 4, the comparison of the substrate characteristics of Examples 1 to 4 and the comparison of the substrate characteristics of the control RF-4 and Examples 1 to 4 were carried out. As shown in FIG. 4, the characteristic detection items of the substrates of the first to fourth embodiments are the glass transition temperature - TMA (° C.), the Z-axis expansion coefficient (25 to 260 ° C) (%), and the heat resistance T-260. (min), thermal shock test, lead-free solder test, dielectric constant (1 M/GHz), and dielectric loss (1 M/GHz).

From the first embodiment, the second embodiment, the third embodiment, and the fourth embodiment, it can be seen that the use of a phosphorus-containing crosslinking agent and a low dielectric loss inorganic powder can result in a halogen-free printed circuit board material composition with low dielectric loss. And can pass the requirements of the lead-free solder process.

The above are only the preferred embodiments of the present invention, and are not intended to limit the scope of the present invention; all other equivalent changes or modifications which are not departing from the spirit of the present invention should be included in the following patents. Within the scope.

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1 is a molecular structure diagram for illustrating the molecular structure of a phosphorus-containing crosslinking agent in the material composition of the halogen-free printed circuit board having low dielectric loss of the present invention; FIG. 2 is a schematic view showing Illustrating the low dielectric loss of the present invention Some embodiments of the composition of the halogen-free printed circuit board material; FIG. 3 is a flow chart showing the flow steps of the manufacturing method for the material composition of the halogen-free printed circuit board having low dielectric loss of the present invention; and The figure is a schematic diagram showing the substrate characteristics of some embodiments of the halogen-free printed circuit board material composition of the present invention having low dielectric loss as illustrated in FIG.

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Claims (16)

A halogen-free printed circuit board material composition with low dielectric loss is applied to a printed circuit board substrate material manufacturing environment, and the halogen-free printed circuit board material composition with low dielectric loss mainly comprises: epoxy resin, the ring The oxygen resin is a halogen-free epoxy resin; the phosphorus-containing crosslinking agent is a reactive phosphorus-containing bisphenol A type crosslinking agent; a crosslinking agent; a low dielectric loss inorganic powder; a dispersing agent; a diluent; and a catalyst, wherein the molecular structure of the phosphorus-containing crosslinking agent is Among them, R1, R2, R3 are selected from methyl (methyl), phosphorus-containing compounds (DOPO, 9, 10-dihydro-9-oxa-10-phosphaphanthrene 10-oxide), C1 ~ C10 alkyl, C1 ~ An aldehyde group of C10, an alcohol group of C1 to C10, an independent hydrogen group, etc., and n is a positive integer. A halogen-free printed circuit board material composition with low dielectric loss is applied to a printed circuit board substrate material manufacturing environment, and the halogen-free printed circuit board material composition with low dielectric loss mainly comprises: epoxy resin, the ring The oxy-resin is a halogen-free epoxy resin having an epoxy equivalent of 200 to 1500 and a usage amount of 100 parts; and a phosphorus-containing crosslinking agent, the phosphorus-containing crosslinking agent is a reactive phosphorus-containing double a phenol A type crosslinking agent, the phosphorus content of the phosphorus-containing crosslinking agent is 1 to 20%; a crosslinking agent, the crosslinking agent is a dicyandiamide or a phenol hardener; a low dielectric a lossy inorganic powder, the low dielectric loss inorganic powder is an inorganic powder having a low dielectric loss; a dispersant, which is a silane coupling agent (Silane); a diluent; and a catalyst, wherein the phosphorus-containing cross-linking The molecular structure of the agent is Among them, R1, R2, R3 are selected from methyl (methyl), phosphorus-containing compounds (DOPO, 9, 10-dihydro-9-oxa-10-phosphaphanthrene 10-oxide), C1 ~ C10 alkyl, C1 ~ An aldehyde group of C10, an alcohol group of C1 to C10, an independent hydrogen group, etc., and n is a positive integer. The halogen-free printed circuit board material composition with low dielectric loss as described in claim 1 or 2, wherein the epoxy resin is selected from the group consisting of phenolphthalein epoxy resin (Phenol). Novolak epoxy, cresol novolak epoxy, bisphenol A novolak type epoxy), biphenol epoxy (bisphenol A type epoxy, bisphenol F type epoxy, bisphenol M type epoxy), cyclopentadiene type epoxy, urethane epoxy resin Isocyanate modified Epoxy) and so on. The halogen-free printed circuit board material composition having low dielectric loss as described in claim 1 or 2, wherein the phosphorus-containing crosslinking agent has a phosphorus content of 1 to 20% by weight and a usage amount of 10 ~100 copies. The halogen-free printed circuit board material composition having low dielectric loss according to claim 1 or 2, wherein the crosslinking agent is dicyandiamide and the amount of dicyandiamide used is 0.5~ 3.5 servings. The halogen-free printed circuit board material composition having low dielectric loss according to claim 1 or 2, wherein the crosslinking agent is a phenol hardener, and the OH equivalent is 80-140. The molecular structure contains at least one active hydrogen reactive group in an amount of 10 to 60 parts. The low-dielectric loss-free halogen-free printed circuit board material composition as described in claim 1 or 2, wherein the low dielectric loss inorganic powder has a low dielectric Electrically depleted inorganic powder with a particle size of 1~100um, selected from crystalline crystal silica, fuse silica, aluminum hydroxide (Al(OH)3), and trioxide Inorganic powders such as aluminum (Al2O3), magnesium hydroxide (Mg(OH)2), magnesium oxide (MgO), beryllium oxide (BeO), boron nitride (BN), tantalum nitride (Si3N4), etc., used in an amount of 10 ~100 copies. The halogen-free printed circuit board material composition having low dielectric loss as described in claim 1 or 2, wherein the dispersant is a decane coupling agent selected from an amino decane coupling agent (amino) in which no heavy metal is present. -silane), epoxy-silane, etc., used in an amount of 0.1 to 5.0 parts. The halogen-free printed circuit board material composition having low dielectric loss as described in claim 1 or 2, wherein the diluent is selected from the group consisting of acetone (Acetone), methyl ethyl ketone (MEK), and cyclohexanone ( Cyclohexanol), 1-methoxy-2-propanol (PM), 1-methoxy-2-propanol methyl ester (PMA), dimethylformamide (DMF), and the like. The halogen-free printed circuit board material composition having low dielectric loss as described in claim 1 or 2, wherein the catalyst is a tertiary amine. The halogen-free printed circuit board material composition having low dielectric loss according to claim 1 or 2, wherein the epoxy resin is 100 parts, and the phosphorus-containing crosslinking agent is 30 parts, the hardening The agent was 2.0 parts of dicyandiamide, 50 parts of the low dielectric loss inorganic powder, 0.2 parts of the catalyst, 0.5 part of the dispersant, and 40 parts of the diluent. The halogen-free printed circuit board material composition having low dielectric loss according to claim 1 or 2, wherein the epoxy resin is 100 parts, and the phosphorus is contained 40 parts of a crosslinking agent, which is 2.0 parts of dicyandiamide, 50 parts of the low dielectric loss inorganic powder, 0.1 part of the catalyst, 0.5 part of the dispersing agent, and 40 parts of the diluent. The halogen-free printed circuit board material composition having low dielectric loss according to claim 1 or 2, wherein the epoxy resin is 100 parts, and the phosphorus-containing crosslinking agent is 40 parts, the hardening The agent was 30 parts of phenols, 50 parts of the low dielectric loss inorganic powder, 0.3 parts of the catalyst, 0.5 parts of the dispersant, and 40 parts of the diluent. The halogen-free printed circuit board material composition having low dielectric loss according to claim 1 or 2, wherein the epoxy resin is 100 parts, and the phosphorus-containing crosslinking agent is 35 parts. The agent was 2.2 parts of dicyandiamide, 50 parts of the low dielectric loss inorganic powder, 0.25 parts of the catalyst, 0.5 parts of the dispersant, and 40 parts of the diluent. A manufacturing method of a halogen-free printed circuit board material composition with low dielectric loss is applied to a printed circuit board substrate material manufacturing environment, and the manufacturing method comprises the following procedure: preparation according to the first or second item of the patent application scope The halogen-free printed circuit board material having a low dielectric loss is composed of the varnish adjusted and stirred at room temperature for 120 minutes; the varnish is impregnated on the glass cloth; and the impregnated glass cloth and copper are The foil is pressed. Halogen-free printing with low dielectric loss as described in claim 15 The manufacturing method of the material composition of the circuit board, wherein the step of pressing the impregnated glass cloth and the copper foil is performed by pressing the impregnated glass cloth on the outermost surface with each copper foil. .