TWI588161B - Low-k material and precursor thereof - Google Patents

Description

Low dielectric constant material and its precursor

The present disclosure relates to low dielectric constant materials, and more particularly to the composition of their precursors.

As electronic information products are gradually moving toward higher frequency and higher speed, the use of insulating materials with low dielectric constant (Dk) and low dielectric loss (Df) in printed circuit board substrates has received increasing attention.

Polytetrafluoroethylene (PTFE) has many unique properties such as high temperature resistance, chemical resistance, release property, low water absorption and insulation, especially low dielectric constant (Dk) and dielectric loss (Df). ), the application of high frequency copper clad laminates has been around for many years. Generally, the application of PTFE-clad laminates can be divided into two types, one is to impregnate the fiberglass cloth in the PTFE emulsion, and the other is to mix the PTFE emulsion with the inorganic ceramic powder.

In addition to PTFE, polyphenylene ether, BT resin, and cyanate resin are also commonly used as adhesion materials for low dielectric constant (Dk) and low dielectric loss (Df) copper clad laminates. However, the copper clad laminate made of the above material has a dielectric constant higher than that of the copper clad laminate made of PTFE. In addition, varnish compositions such as polyphenylene ether resin, bismaleimide (BMI) and triazine (BT, Bismaleimide Triazine) polymer resin, cyanate resin, polyamidoximine and its derivatives In materials, or epoxy systems, PTFE is added to reduce dielectric constant and dielectric loss. However, the above resins are oily systems and are generally not compatible with PTFE emulsions, so only PTFE micropowder can be added for the purpose. however Generally, a small-sized PTFE fine powder (having an average particle diameter of about 4 to 10 μm) is easily dispersed uniformly in a general organic polymer, but its low molecular weight (about 100,000 or less) increases the dielectric constant and dielectric loss. As for the high molecular weight PTFE micropowder (molecular weight higher than 2 million), the average particle size range is too large (between 30 and 500 μm) and is not easily dispersed uniformly in a general oily resin system, and is easily agglomerated and unevenly distributed in the resin. Inconsistent electrical performance.

In summary, there is a need for new low dielectric constant materials and their precursors to improve the compatibility of high molecular weight PTFE micropowders with varnish compositions.

The precursor of the low dielectric constant material provided by the embodiment includes: (a) a varnish composition; 5-30 parts by weight of (b) a composite fine powder of polytetrafluoroethylene and polyoxyalkylene; and 0.05- 3 parts by weight of (c) a surfactant, wherein (a) the varnish composition comprises: (a1) 100 parts by weight of a polyphenylene ether resin, 20 to 30 parts by weight of triallyl isocyanurate, and 0.01 To 0.03 parts by weight of the initiator; (a2) 100 parts by weight of the polyphenylene ether resin, 20 to 30 parts by weight of the rubber, 20 to 30 parts by weight of triallyl isocyanurate, and 0.01 to 0.03 parts by weight Or (a3) 100 parts by weight of a copolymer of polyamidoximine and bismaleimide.

The precursor of the low dielectric constant material provided by the embodiment includes: (a) a varnish composition; 5-30 parts by weight of (b) a composite fine powder of tetrafluoroethylene and polyoxyalkylene; and 0.05-3 Parts by weight of (c) interface polyactive agent. If (b) polytetrafluoroethylene If the ratio of the composite fine powder of the alkene and the polyoxyalkylene is too low, the dielectric constant cannot be lowered. If (b) the ratio of the composite fine powder of polytetrafluoroethylene to polyoxyalkylene is too high, the adhesive strength of the prepreg after press-bonding is too low. If the proportion of the (c) surfactant is too low, the polytetrafluoroethylene and polyoxyalkylene composite powders do not disperse well. If the proportion of (c) surfactant is too high, it affects the dielectric loss properties of the laminated laminate. The surfactant used in the present disclosure has a main function of lowering the surface tension of the resin composition of the present invention and helping the composite fine powder of polytetrafluoroethylene and polyoxymethane to be uniformly dispersed in the resin composition. Surfactants are usually non-ionic fluorine-based surfactants, such as DuPont Capstone FS3100, Japan AGC Qingmei Chemical's fluorine-based surfactant S-386, S-611, and non-ionic lanthanide surfactants, such as Momentive's CoatOSil * 1211, a non-ionic fluorine-based surfactant is preferred.

In one embodiment, the (a) varnish composition comprises (a1) 100 parts by weight of a polyphenylene ether resin, 20 to 30 parts by weight of triallyl isocyanurate (TAIC), and 0.01 to 0.03 parts by weight. An initiator; (a2) 100 parts by weight of a polyphenylene ether resin, 20 to 30 parts by weight of rubber, 20 to 30 parts by weight of TAIC, and 0.01 to 0.03 parts by weight of an initiator; or 100 parts by weight of (a3) poly Copolymer of amidoximine and bismaleimide. If the ratio of TAIC is too low, the glass transition temperature (Tg) of the laminate formed by press-bonding is not high enough and the heat resistance is poor. If the proportion of TAIC is too high, the dielectric properties of the laminated laminate are reduced. In one embodiment, the polyphenylene ether resin is a polyphenylene ether resin having a terminal methacryloxy group (such as SA-9000 sold by Sabic Co., Ltd.) and a polyphenylene ether resin having a terminal vinyl benzyl ether (such as Mitsubishi Gas). OPE-2st) sold by chemistry, or a combination of the above. In an embodiment, the rubber comprises polybutadiene, styrene-butadiene-styrene block polymer (SBS), short chain polymethylstyrene, or a combination thereof. If the proportion of rubber is too low, it affects the dielectric properties of the laminate formed by press-bonding. If the proportion of rubber is too high, This will reduce the Tg of the laminated laminate. In one embodiment, the initiator may be an azo such as 2,2'-azobis(2,4-dimethyl-n-valeronitrile). ), dimethyl 2,2'-azobis(2-methylpropionate), 2,2-azobisisobutyronitrile (2,2) -azobis isobutyronitrile), 2,2-azobis(2-methylisobutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile) (1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis[N-2-propyl-2-methylpropanamide] (2,2'-azobis[N -(2-propenyl)-2-methyl propionamide]), 1-[(cyano-1-methylethyl)-azo]carbamamine (1-[(cyano-1-methylethyl)azo]formamide , 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azo double (N-cyclohexyl-2-methylpropionamide), or other suitable azo initiators; peroxides include benzamidine Benzyl peroxide, 1,1-bis(tert-butyl peroxy)cyclohexane, 2, 5-bis(t-butylperoxy)-2,5-dimethylcyclohexane (2,5-bis(tert-butylperoxy)-2,5-dimethylcyclohexane), 2,5-double (third Butylperoxy)-2,5-bis(tert-butylperoxy-2,5-dimethyl-3-cyclo-hexyne), di-tert-butyl peroxide Di-t-butyl peroxide, bis(1-(tert-butylperoxy)-1-methy-ethyl)benzene ), tert-butyl hydroperoxide, tert-butyl peroxide, tert-butyl benzoic acid (tert-butyl) Peroxybenzoate), Cumene hydroperoxide, cyclohexanone peroxide, dicumyl peroxide, lauroyl peroxide, or other suitable peroxide. The above-mentioned initiators may be used in combination or in combination, depending on the needs. If the ratio of the initiator is too low, the crosslinking density of the reactants is lowered, and the Tg of the laminate formed by press-bonding is lowered. If the ratio of the initiator is too high, the reaction rate is too fast and it is difficult to handle.

In one embodiment, in (a3) a copolymer of polyamidoximine and bismaleimide, the polyamidoximine is polymerized from diphenylmethane diisocyanate (MDI) and trimellitic anhydride (TMA). Made. The bismaleimide may be 4,4'-bismaleimide diphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, or the above The combination. The weight ratio of polyamidimide to bismaleimide is between 70:100 and 70:50. If the proportion of the bismaleimide is too low, the formed laminate is easily layered between layers, the laminate has low mechanical strength, and the laminate is easily deformed. If the proportion of bismaleimide is too high, after the composition is allowed to stand for a long time, some of the bismaleimide will precipitate, which will affect the storage stability of the composition, and the crosslink density will be too high. The resulting laminate is too brittle.

In a composite fine powder of polytetrafluoroethylene (PTFE) and polyoxyalkylene provided by an embodiment, the weight ratio of PTFE to polyoxyalkylene is between 95:5 and 90:10. If the ratio of PTFE is too low, the relative amount of polyoxymethane is too large, resulting in a high dielectric constant and dielectric loss of the composite powder of polytetrafluoroethylene (PTFE) and polyoxyalkylene, lowering the dielectric constant and dielectric. The effect of loss. If the ratio of PTFE is too high, the composite material formed by PTFE and polyoxyalkylene is not hard enough to smoothly use the method of jet pulverization, and the particle size is effectively reduced to an average particle diameter of 2-10 μm. is too big, At the same time, it also causes poor dispersibility, which affects the formability and adhesion of the laminate, and the appearance of the prepreg is also poor. The weight average molecular weight of PTFE can range from 2 million to 5 million. The composite fine powder of the above PTFE and polyoxyalkylene may have an average particle diameter (D50) of between 2 μm and 10 μm. If the average particle size of the composite fine powder is too large, the appearance of the prepreg is poor, and uneven and granular PTFE is present on the surface of the cured sheet.

In an embodiment of the present disclosure, a composite fine powder of PTFE and polyoxyalkylene is prepared by uniformly mixing 100 parts by weight of PTFE with 10 to 40 parts by weight of decane. The PTFE may be wetted by adding a suitable solvent depending on the mixing, and the solvent is not particularly limited as long as it can wet the PTFE, such as an alcohol such as methanol, ethanol, isopropanol, or a benzene such as toluene or xylene.

In other embodiments, 60-80% of the decane may be further replaced with a cerium sol to further improve the heat resistance of the composite. If the amount of the cerium sol added is too high, the reaction rate of decane in PTFE is affected, and decane is easily gelled during the hydrolysis condensation reaction. The decane can penetrate between the pores of the PTFE and undergo a hydrolysis condensation reaction (in situ polymerization) to form a network structure of polyoxyalkylene to prevent further aggregation of the PTFE to achieve the effect of dispersing the PTFE. On the other hand, polyoxyalkylene can coat the surface of PTFE to harden PTFE, making it easy to pulverize. If the amount of decane used is too high, the amount of polyoxane in the composite fine powder formed is too large, and the properties of PTFE are lost. If the amount of decane is too low, decane cannot coat PTFE, resulting in poor dispersion of PTFE, and also causes the PTFE coated polysiloxane to be less brittle, and it is impossible to prepare fine powder by a general jet pulverization method.

Then, 0.1 to 0.0001% by weight of the total weight of PTFE and decane is added to the above mixture, and then uniformly mixed, and then water is added to make decane in PTFE. The polymerization is carried out in situ to form a polyoxyalkylene. The catalyst is not particularly limited as long as it can catalyze the hydrolysis of decane, such as sulfuric acid, hydrochloric acid, formic acid, acetic acid, citric acid, amines, potassium hydroxide, or sodium hydroxide. If the amount of the catalyst is too high, the hydrolysis condensation reaction rate is too fast, the reaction is not easy to control, and the decane gel is likely to cause particles. If the amount of the catalyst is too low, the hydrolysis condensation reaction rate is too slow and the reaction time is too long. The molar ratio of water to decane is between 0.5:1 and 3:1. If the amount of water is too high, the reaction phase will be separated; if the amount of water is too small, the hydrolysis of decane will be insufficient, and excessive decane will remain, which will affect the product effect.

In an embodiment of the present disclosure, the temperature of the in-situ polymerization reaction is between room temperature (about 25 ° C) and 45 ° C, and the reaction time is between 4 hours and 16 hours. If the temperature of the in-situ polymerization reaction is too high and/or the reaction time is too long, the hydrolysis condensation reaction is not easily controlled. If the temperature of the in-situ polymerization reaction is too low and/or the reaction time is too short, the decane cannot sufficiently carry out the hydrolysis condensation reaction.

In an embodiment of the invention, the PTFE is preferably a PTFE prepared by suspension polymerization or dispersion polymerization of a tetrafluoroethylene (TFE) monomer, and has a weight average molecular weight of between 2 million and 5 million, preferably having no Viscous. The above PTFE may be a suspension polymerization, and since the suspension polymerization does not use a fluorine-containing surfactant, it does not contain PFOA. The above PTFE may further comprise a small amount of a comonomer modifier such as a perfluoroolefin, particularly a hexafluoropropylene (HFP) or a perfluoro(alkyl vinyl) ether, which improves the film forming ability during baking (sintering). The alkyl group has 1 to 5 carbon atoms, preferably perfluoro(propyl vinyl) ether (PPVE) and perfluoro(methyl vinyl) ether (PMVE). The above modifier is used in an amount insufficient to impart melt processability to PTFE, and the above copolymer is referred to as modified PTFE. Typical modifiers are used in amounts of less than 3% by weight, preferably less than 1% by weight. The type of polytetrafluoroethylene is powdery or agglomerated, and the particle size is about 20 to 260 μm. It is worth noting that the above PTFE Completely free of perfluorooctanoic acid (PFOA).

In one embodiment, the decane is R ¹ _m R ² _n Si(OR ³ ) _4-mn , R ⁴ _j R ⁵ _k SiCl _4-jk , or a combination thereof, wherein m, n, j, k are each 0 Or a positive integer, an integer of m + n = 0 to 2, and an integer of j + k = 0 to 3. R ¹ , R ² , R ⁴ , and R ⁵ are each selected from H, C _1-6 alkyl (such as methyl, ethyl, propyl, or butyl), C _3-6 cycloalkyl (such as Cyclopentyl or cyclohexyl), C _2-6 alkenyl (such as vinyl or propenyl), aryl (such as phenyl), halogenated C _1-6 hydrocarbyl (such as chloromethyl or γ-chloropropyl) ), an amine group (such as γ-aminopropyl), a methacryloxy group (such as γ-methacryloxypropyl or γ-glycidoxypropyl), an epoxy group (such as 3, 4-epoxycyclohexane ethyl), fluorenyl (such as γ-mercaptopropyl), thio, ureido (such as γ-ureidopropyl), or isocyanato (such as γ-isocyanatopropyl) ). R ³ is a C _1-3 alkyl group such as methyl, ethyl or propyl. In one embodiment of the present invention, the decane may be methyltrimethoxydecane, methyltriethoxydecane, phenyltrimethoxydecane, phenyltriethoxydecane, vinyltrimethoxydecane, orthoquinone. Ethyl acetate, polyethyl phthalate (TEOS-40), methyl n-decanoate, γ-aminopropyltriethoxydecane, N-(γ-aminoethyl)-γ-aminopropyltrimethoxy Decane, 3-(2,3-epoxypropoxy)propyltrimethoxydecane, 2-(3,4-epoxycyclohexane)ethyltrimethoxydecane, 3-(methacryloxyl) ) propyl trimethoxy decane, γ-mercaptopropyl trimethoxy decane, γ-ureidopropyl triethoxy decane, γ-isocyanatopropyl triethoxy decane, tetrachloro decane, methyl three Chlorodecane, phenyltrichlorodecane, methylphenyldichlorodecane, vinyltrichloromethane, or a combination thereof. In one embodiment of the invention, the decane is preferably phenyltrimethoxydecane, vinyltrimethoxydecane, n-decanoic acid ethyl ester, 3-(2,3-epoxypropoxy)propyltrimethoxydecane. , 3-(methacryloxy)propyltrimethoxydecane, or a combination thereof.

Next, a mixture of polyoxyalkylene and polytetrafluoroethylene is dried. For example, the water mixture can be warmed up until no moisture is released, and then filtered at 100 mesh. The cloth was filtered to obtain a wet powder. The wet powder is then dried at 200 ° C to 300 ° C for 2 hours to 4 hours to obtain a dry powder. The main purpose of drying is to remove water and solvent. Another purpose is to reduce the sterol group (Si-OH) of polyoxyalkylene to avoid excessive sterol groups, affecting dielectric constant and dielectric. loss. The weigh content can be obtained by weighing the dry powder. The formula is as follows: polyoxymethane % = [(dry powder weight - polytetrafluoroethylene weight) / dry powder weight] × 100%.

Finally, the physical pulverized dry powder, such as jet pulverization, can obtain a composite fine powder of PTFE and polyoxyalkylene, the average particle diameter (D50) is between 2.0 μm and 10 μm, and the weight ratio of PTFE to polyoxyalkylene is between 95. : between 5 and 90:10. The weight average molecular weight of the PTFE in the composite fine powder is substantially the same as the weight average molecular weight of the PTFE initially used. The above physical pulverization method such as jet pulverization and classification method only pulverizes the composite material without cracking the PTFE therein.

In one embodiment, 30 parts by weight of a flame retardant may be added to the precursor of the dielectric material, wherein the flame retardant is not particularly limited, and the flame retardant requirement may be met, for example, a bromine-based flame retardant such as decabromo. Diphenylethane or the like, or a phosphorus-nitrogen flame retardant such as a cyclic phenoxyphosphazene compound.

In an embodiment of the present invention, 0.5-1 part by weight of a decane coupling agent and 20-40 parts by weight of cerium oxide may be further added to the precursor of the dielectric material. The above decane coupling agent may be (3-glycidoxypropyl)trimethoxydecane, (3-glycidoxypropyl)triethoxydecane, 3-(methacryloxy)propyltrimethyl Oxydecane, or a combination thereof. The decane coupling agent bridges the "molecular bridge" between the interface between the inorganic substance and the organic substance, and connects the two materials with different properties to improve the performance of the composite and increase the bonding strength. Different decane coupling agents are required for different resin systems. Taking a polyphenylene ether system as an example, 3-(methacryloxy)propyltrimethoxydecane can be preferably used as a decane coupling agent. Adding to the dielectric material The addition of cerium oxide such as molten cerium oxide contributes to lowering the coefficient of thermal expansion of the cured resin and reducing the cost.

The low dielectric constant material has a dielectric constant between 3.4 and 3.8 and a dielectric loss between 0.002 and 0.015. Compared with the direct use of PTFE micropowder and varnish composition precursor, the low dielectric constant material formed by the composite powder of PTFE and polyoxyalkylene and the varnish composition has a lower dielectric constant and dielectric. loss.

The above and other objects, features, and advantages of the present invention will become more apparent and understood.

Example

The names and sources of the drugs used in the present invention are listed below, but are not limited to the listed drugs:

PTFE powder:

CGM 031B, purchased from Zhonghao Chenguang Chemical Research Institute Co., Ltd., with an average particle size between 70μm and 90μm.

CGM 031C, purchased from Zhonghao Chenguang Chemical Research Institute Co., Ltd., with an average particle size between 130μm and 260μm.

CGM 16 (F), purchased from Zhonghao Chenguang Chemical Research Institute Co., Ltd., with an average particle size of 25 μm.

Antimony compound:

Phenyltrimethoxydecane: XL70 from Wacker.

(3-Glycidoxypropyl)trimethoxydecane: Z 6040 available from Dow Corning.

3-(Methethyloxy)propyltrimethoxydecane: Dynasylan MEMO from Evonic.

Ethyl decanoate: TES 28 from Wacker.

Cerium oxide sol: Levasil CT20 DH from Aksu.

Diphenylmethane diisocyanate: purchased from Japan Nippon polyurethane Industry Co. Ltd Millionate MT.

Trimellitic anhydride (TMA): purchased from Taiwan Hengzhou Trading Company.

N-methylpyrrolidone (NMP): purchased from BASF.

Dimethylacetamide (DMAC): purchased from DuPont.

4,4'-Bismaleimide Diphenylmethane: BMI-1000 available from Daiwakasei Industry Co., LTD., Japan.

Polyphenylene ether resin having a methacryloxy group at the end: SA-9000 available from Sabic.

Triallylisocyanurate (TAIC): purchased from Hunan Xiangxiang Chemical Co., Ltd., China.

Polybutadiene rubber: Ricon 153 from Cray Valley.

Styrene-butadiene-styrene block polymer (SBS): D1155 from Kraton.

Short chain polymethylstyrene: F115 available from Eastman.

Brominated flame retardant: Saytex 8010 from Albemarle.

Molten type cerium oxide: Megasil 525 available from Tobike, Taiwan.

Initiator: Di-t-butyl peroxide purchased from Guangzhou Yufeng Chemical Co., Ltd., China.

Surfactant: Fluorinated surfactant S386 from AGC Qingmei Chemical of Japan.

Glass cloth: purchased from Taiwan Glass Group's glass fiber cloth 2116.

The following Examples 1 to 4 are preparation methods of a composite fine powder of polytetrafluoroethylene and a ruthenium-containing compound.

Example 1

Add 1000g of PTFE powder (CGM 031B) to the reaction vessel, add appropriate amount of methanol, stir to completely wet the PTFE powder, then add 100g of phenyltrimethoxysilane to stir evenly, then add 0.01g of concentrated sulfuric acid as catalyst to mix. Evenly, 10 g of water was finally added, and the reaction temperature was controlled to not exceed 45 ° C for 4 hours.

The mixture was heated to boiling to remove moisture, and then filtered with a 100 mesh filter cloth to obtain a wet powder. After drying the wet powder at 300 ° C for 4 hours, a dry powder (weight: 1053 g) was obtained. The dry powder was classified by gas jet pulverization to obtain a composite fine powder of polytetrafluoroethylene and polyoxymethane having an average particle diameter (D50) of 10 μm.

Example 2

Add 1000g of PTFE powder (CGM 031C) to the reaction vessel, add appropriate amount of methanol, stir to completely wet the PTFE powder, then add 120g of 3-(methacryloxy)propyltrimethoxydecane and mix well. Add 1 g of hydrochloric acid as a catalyst to mix well, and finally add 20 g of water to control the reaction temperature to not exceed 45 ° C for 6 hours.

The mixture was heated to boiling to remove moisture, and then filtered with a 100 mesh filter cloth to obtain a wet powder. After drying the wet powder at 200 ° C for 4 hours, a dry powder (weighing 1064 g) was obtained. The dry powder was classified by gas jet pulverization to obtain a composite fine powder of polytetrafluoroethylene and polyoxymethane having an average particle diameter (D50) of 6.0 μm.

Example 3

Add 1000g of PTFE powder (CGM 16 (F)) to the reaction vessel, add appropriate amount of methanol, stir to completely wet the PTFE powder, and then add 200g of 3-(2,3-epoxypropoxy)propyltrimethyl The oxoxane was stirred evenly, and then 0.1 g of hydrochloric acid was added as a catalyst mixture. Evenly, 40 g of water was finally added, and the reaction temperature was controlled to not exceed 45 ° C for 16 hours.

The mixture was heated to boiling to remove moisture, and then filtered with a 100 mesh filter cloth to obtain a wet powder. After drying the wet powder at 200 ° C for 2 hours, a dry powder (weighing 1098 g) was obtained. The dry powder was classified by gas jet pulverization to obtain a composite fine powder of polytetrafluoroethylene and polyoxymethane having an average particle diameter (D50) of 4.0 μm.

Example 4

Add 1000g of PTFE powder (CGM 031B) to the reaction vessel, add appropriate amount of isopropanol, stir to completely wet the PTFE powder, then add 160g of ethyl orthosilicate and 240g of cerium oxide sol and mix well, then add 1.2 The concentrated sulfuric acid of g is uniformly mixed as a catalyst, and finally 20 g of water is added to control the reaction temperature to not exceed 45 ° C for 12 hours.

The mixture was heated to boiling to remove water, and then filtered through a 100-mesh filter cloth to obtain a wet powder. After drying the wet powder at 300 ° C for 4 hours, a dry powder (weight: 1110 g) was obtained. The dry powder was classified by gas jet pulverization to obtain a composite fine powder of polytetrafluoroethylene and polyoxyalkylene having an average particle diameter (D50) of 2.0 μm.

Example 5

100 g of polyphenylene ether (SA-9000), 100 g of toluene, 20 g of triallyl isocyanurate (TAIC), 20 g of the composite fine powder of PTFE and polyoxyalkylene prepared in Example 1, 30 g of resistance A fuel, 1 g of 3-(methacryloxy)propyltrimethoxydecane coupling agent, 40 g of cerium oxide, 0.01 g of an initiator, and 0.2 g of a surfactant were uniformly mixed.

Example 6

100 g of polyphenylene ether (SA-9000), 100 g of toluene, 30 g of TAIC, 20 g of the composite fine powder of PTFE and polyoxyalkylene prepared in Example 2, 30 g of flame retardant, and 1 g of 3-(methacrylic acid) The oxime) propyltrimethoxydecane coupling agent, 40 g of cerium oxide, 0.03 g of the initiator, and 0.2 g of the surfactant were uniformly mixed.

Example 7

100 g of polyphenylene ether (SA-9000), 100 g of toluene, 25 g of TAIC, 5 g of the composite fine powder of PTFE and polyoxyalkylene prepared in Example 3, 30 g of flame retardant, and 1 g of 3-(methacrylic acid) The oxime) propyltrimethoxydecane coupling agent, 40 g of cerium oxide, 0.02 g of the initiator, and 0.05 g of the surfactant were uniformly mixed.

Example 8

100 g of polyphenylene ether (SA-9000), 100 g of toluene, 25 g of TAIC, 30 g of the composite fine powder of PTFE and polyoxyalkylene prepared in Example 4, 30 g of flame retardant, and 1 g of 3-(methacrylic acid) The oxime) propyltrimethoxydecane coupling agent, 40 g of cerium oxide, 0.02 g of the initiator, and 3 g of the surfactant were uniformly mixed.

Example 9

100 g of polyphenylene ether, 120 g of toluene, 30 g of TAIC, 4 g of polybutadiene, 8 g of SBS, 8 g of short-chain polymethylstyrene, 30 g of PTFE prepared in Example 1 and A composite micropowder of polyoxyalkylene, 30 g of a flame retardant, 0.01 g of an initiator, and 0.3 g of a surfactant are uniformly mixed.

Example 10

100 g of polyphenylene ether, 120 g of toluene, 20 g of TAIC, 6 g of polybutadiene, 12 g of SBS, 12 g of short-chain polymethylstyrene, 30 g of the composite of PTFE prepared in Example 2 and polyoxyalkylene Micronized powder, 30 g of flame retardant, 0.03 g of initiator, and 1.5 g of surfactant were uniformly mixed.

Comparative example 1

100g of polyphenylene ether (SA-9000), 100g of toluene, 25g of TAIC, 30g of flame retardant, 1g of 3-(methacryloxy)propyltrimethoxydecane coupling agent, 40g of dioxide矽, mix well with 0.02g of initiator.

Comparative example 2

100g polyphenylene ether (SA-9000), 100g toluene, 25g TAIC, 30g PTFE powder (CGM 031B), 30g flame retardant, 1g 3-(methacryloxy)propyltrimethoxy A decane coupling agent, 40 g of cerium oxide, 0.02 g of an initiator, and 0.3 g of a surfactant were uniformly mixed.

Comparative example 3

100 g of polyphenylene ether, 120 g of toluene, 20 g of TAIC, 4 g of polybutadiene, 8 g of SBS, 8 g of short-chain polymethylstyrene, 30 g of flame retardant, 1 g of 3-(methacryl oxime) The oxy)propyltrimethoxydecane coupling agent was uniformly mixed with 0.01 g of the initiator.

Comparative example 4

100 g of polyphenylene ether, 120 g of toluene, 20 g of TAIC, 4 g of polybutadiene, 8 g of SBS, 8 g of short-chain polymethylstyrene, 30 g of PTFE powder (CGM 031B), 30 g of flame retardant, 0.01 g of the initiator was uniformly mixed with 1.5 g of the surfactant.

Example 11

203 g of diphenylmethane diisocyanate (MDI) and 149.8 g of trimellitic anhydride (TMA) were added to 390 g of N-methylpyrrolidone (NMP), reacted at 120 ° C for 3 hours, and then 1.52 g of TMA was added to continue the reaction for 1 hour. A polyamidoximine was prepared, and 260 g of NMP was added to adjust the solid content to 35%.

100 g of bismaleimide was added to 200 g of the above polyamidamine solution (solid content 35%), and reacted at 120 ° C for 2 hours to form a PAI-BMI resin solution, followed by 40 g of dimethyl group. Acetamide (DMAC) regulates the solids to 50%.

Example 12

200 g of the PAI-BMI resin solution prepared in Example 11 (solid content: 50%) was taken, and 20 g of the composite fine powder of PTFE and polyoxymethane prepared in Example 1 was added, and 2 g of the surfactant was uniformly mixed.

Example 13

203 g of MDI and 149.8 g of TMA were added to 390 g of NMP, and reacted at 120 ° C for 3 hours, and then 1.52 g of TMA was further added to continue the reaction for 1 hour to obtain polyamidoximine, and then 260 g of NMP was added to adjust the solid. The content is up to 35%.

50 g of bismaleimide was added to 200 g of the above polyamidamine solution (solid content: 35%), and reacted at 120 ° C for 2 hours to form a PAI-BMI resin solution.

Example 14

208 g of the PAI-BMI resin solution of Example 13 was taken, and 30 g of the composite fine powder of PTFE and polyoxydecane prepared in Example 4 was added, and 3 g of the surfactant was uniformly mixed.

Comparative Example 5

200 g of the PAI-BMI resin solution of Example 11 was taken, 20 g of PTFE powder (CGM 031B) was added, and 2 g of the surfactant was uniformly mixed.

Comparative Example 6

200 g of the PAI-BMI resin solution of the above Example 11 was taken.

Prepreg and copper foil substrate manufacturing method

The resin compositions in Tables 2 and 3 were mixed with other ingredients and filtered through a sieve (100 to 200 mesh) to form a prepreg in a glue form. Next, the glass fiber cloth was impregnated into the prepreg by an impregnation machine (impregnation specification: 2116), and the glue content was controlled at 50 ± 2%. Next, the impregnated glass fiber cloth was baked at 170 ° C for 2-3 min to prepare a prepreg. After stacking six of the above prepregs, the dielectric constant and dielectric loss were measured as shown in Tables 4 and 5. Next, copper foil was placed on both sides of the prepreg stack, and then press-bonded (pressing temperature: 210 ° C, press time: 150 minutes, press pressure: 200 psi) to prepare a copper foil substrate.

It can be seen from Tables 4 and 5 that the composite fine powder of PTFE and polyoxyalkylene disclosed in the present invention has a high molecular weight characteristic of PTFE, but the composite fine powder obtained by pulverizing the surface due to the treatment of the surface by polyoxyalkylene. , can be easily and uniformly dispersed in a polyphenylene ether resin (or a copolymer of polyamidoximine and bismaleimide), and The dielectric constant (Dk) and dielectric loss (Df) of the polyphenylene ether resin (or a copolymer of polyamidoximine and bismaleimide) can be lowered. Generally, the high molecular weight PTFE powder is not easily dispersed in the polyphenylene ether resin (or the copolymer of polyamidoximine and bismaleimide). During the dispersion process, the PTFE powder is easily agglomerated and unevenly dispersed. The appearance of the prepreg is poor, uneven and granular PTFE.

The measurement methods in Tables 4 and 5 are as follows: The glass transition temperature (Tg) test method uses the US Electronic Circuit Forming Standard (IPC standard), IPC-TM-650-2.4.25 (DSC method).

Peel strength (PS) test: The peel strength of the metal cap layer was tested using the "Electric Stress After" experimental conditions in the US Electronic Circuit Forming Standard (IPC standard) and IPC-TM-650-2.4.8.

Immersion tin heat resistance test: A copper foil substrate of 50 × 50 mm was used, immersed in solder at 288 ° C, and the time for stratification foaming of the sample was recorded.

Moisture and heat resistance (PCT) test: Using a pressure cooker cooking experiment (PCT), the plate was continuously cooked for 120 minutes at 121 ° C in a pressure cooker (0.105 MPa), and then immersed in a solder at 288 ° C to record the time of stratification and foaming of the sample.

Dielectric constant and dielectric loss test method: The size of the test sample (length × width × thickness) is 70mm × 3.5mm × 0.75mm, using the Japanese AET instrument, measuring the dielectric constant and low dielectric loss of 2GHZ, used The method is in accordance with the Resonant Cavity method of JIS-Compliant C 2565.

The disclosure has been disclosed in the above several embodiments, but it is not intended to limit the disclosure, and any person skilled in the art can make any changes and refinements without departing from the spirit and scope of the disclosure. Therefore, the scope of protection of this disclosure is subject to the definition of the scope of the patent application.

Claims (9)

A precursor of a low dielectric constant material comprising: (a) a varnish composition; 5-30 parts by weight of (b) a composite fine powder of polytetrafluoroethylene and polyoxyalkylene; and 0.05 to 3 parts by weight of (c) a surfactant, wherein (a) the varnish composition comprises: (a1) 100 parts by weight of a polyphenylene ether resin, 20 to 30 parts by weight of triallyl isocyanurate, and 0.01 to 0.03 parts by weight of the initiator (a2) 100 parts by weight of a polyphenylene ether resin, 20 to 30 parts by weight of rubber, 20 to 30 parts by weight of triallyl isocyanurate, and 0.01 to 0.03 parts by weight of an initiator; or A3) 100 parts by weight of a copolymer of polyamidoximine and bismaleimide. The precursor of the low dielectric constant material according to claim 1, wherein the polyphenylene ether is a polyphenylene ether resin having a terminal group of methacrylofluorene, a polyphenylene ether resin of a terminal vinyl benzyl ether, Or a combination of the above. A precursor of a low dielectric constant material as described in claim 1, wherein the polyphenylene ether has a molecular weight of from 2,000 to 5,000. A precursor of a low dielectric constant material as described in claim 1, wherein (a3) polyamidoximine and bismaleimide, polyamidoximine and double malayan The weight ratio of amine is between 70:100 and 70:50. A precursor of a low dielectric constant material as described in claim 1, wherein the bismaleimide comprises 4,4'-bismaleimide diphenylmethane, bis(3-ethyl- 5-methyl-4-maleimidophenyl)methane, or a combination thereof. A precursor of a low dielectric constant material as described in claim 1, wherein the rubber comprises a polybutadiene, a styrene-butadiene-styrene block polymer (SBS), a short chain polymethyl group. Styrene, or a combination of the above. The precursor of the low dielectric constant material according to claim 1, wherein the weight ratio of the polytetrafluoroethylene to the polyoxyalkylene is between 95:5 and 90:10. A precursor of a low dielectric constant material as described in claim 1, wherein the polytetrafluoroethylene has a weight average molecular weight of between 2,000,000 and 5,000,000. The precursor of the low dielectric constant material according to claim 1, wherein the composite fine powder of polytetrafluoroethylene and polyoxyalkylene has an average particle diameter (D50) of between 2 μm and 10 μm.