TWI290945B - Application of electrical material in high frequency and manufacturing method of the same - Google Patents

Abstract

The present invention relates to an electrical material having a low dielectric constant and a low dielectric loss and comprising (a) phenylethylene maleic anhydride with the structure shown as the formula below: where m represents an integer of 1 to 6, and n represents an integer of 2 to 12; (b) benzoxazines with the structure shown as the formula, (c) epoxy resin; (d) flexibilizing agent; (e) catalyst; and (f) thinner.

Description

1290945 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to an electronic material, and more particularly, to a low dielectric constant and a low dielectric loss (Low Dissipation fact). 〇r) An electronic material of a characteristic that can be used to fabricate a copper foil substrate for use in high frequencies. [Prior Art] The copper foil substrate that the electronics industry has traditionally used is only regarded as the support plate for the mounting and circuit interconnection of electronic components. The requirement for the substrate (4) is

It is mainly based on the conductive Wei which does not affect the line. However, since the development of electronic products, the requirements for the material of the copper foil substrate are no longer only used as the support material, and the use of the circuit, and the secret traders also sell the requirements. Faster signal transmission time and clearer transmission signals. Due to the increasingly high density of line spacing and pitch, the requirements for the board are more stringent, to ensure that the board is operated under more severe high temperature, high humidity and high voltage environment, and there are still excellent (4) mechanical and upper However, there is an urgent need to develop a substrate material having a low dielectric constant and a low dielectric loss. Generally used in high-frequency copper-plated substrate materials, it is required to have low dielectric constant and age loss. In order to make the substrate material meet this standard, the copper box substrate material used for high frequency is formulated with epoxy resin. The first _, 5969771, 5141791, 526249, 5^5 = 5834565, and 6352782 are all in this way to achieve the low dielectric constant of 1 ^ 90945, but for low dielectric loss can not be far from the handle mm i ~

The main body is such that the substrate has both low dielectric constant and low dielectric loss, but the disadvantage is that the glass transition temperature Tg of the substrate is lower than that of the general FR_4 US plate and the price is the number of general FR-4 substrates. ten times. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide an electronic material having a low dielectric constant and a low dielectric loss characteristic, and a method of fabricating the same. The electronic material is a polymer material formulation, and the copper box 2 plate made of the electronic material has a female qualitative and expansion coefficient which is better than the general FR_4 copper foil substrate material, and can pass the UL-94V0 flame resistance test. In order to achieve the above object, the present invention provides an electronic material having low dielectric constant and low dielectric loss characteristics, the formulation of which comprises: (1) Stupid ethylene-maleic anhydride copolymer (Sty rene Maleic)

Copolymer), its structure is shown below:

Wherein m is an integer from 1 to 6, and 11 is an integer from 2 to 12, (7) oxo-nitrogen is Benz_zines, and its structure is as shown in the following figure: 11290945

N,

Rs

Among them, RAR3 is: methyl, phenyl, Epoxy group, Cyanate ester group, vinyl (vinyi gr0Up), maleimine (maleimide) Group), oxyalkenyl group, alkynyl group, Cycl〇allenyl group, bicycloalkenyl, styryl group, itaconate (itaconate group), benzocyclobutenyl gamma 112〇-1〇1)1^1^), aromatic propargyl ether (caffeine 111 (^〇1)-like initial pool, or aromatic acetylene (aromatic Acetylene), where R2 is:

(3) Epoxy Resin; (4) Enhanced Blade; (5) Catalyst; and (6) Diluent. The electronic material of the present invention contains the requirement of the number of hardening of the styrene-acrylic acid needle copolymer, and the requirement of low dielectric loss is achieved by oxo-nitrobenzene. The sub-material can be used as a printed circuit board, a 1C carrier board, or an electronic packaging material. In addition, the present invention provides a method for manufacturing an electronic material having a low dielectric constant and a low dielectric loss, comprising the following steps: (1) The epoxy resin is added to an eliminator; Γ290945 is used to force the styrene_Malay contact copolymer to recognize the agitator and/or add oxo-nitro-p- and cyclohexane; In the mixer, a charge is formed; () _- turn the machine to reduce the money of the lacquer varnish; clothing: Μ pure resin varnish is coated on the _ um material, the towel is the reinforcing material", Offset, glassy, or aramide fiber; and (6) a substrate formed by heat polymerization hardening. The above and other objects, features, aspects and advantages of the present invention will become apparent from [Embodiment] The present invention provides a low dielectric constant and a low dielectric loss characteristic of an electronic material by adding an appropriate weight of a hardened redox iron wire containing a styrene-maleic anhydride copolymer. The copper foil substrate made of electronic material can pass the 94V0 flame resistance test, and the dimensional stability and expansion coefficient of the copper foil substrate are better than the general FR_4 copper foil substrate material. The main components include: (1) epoxy resin (epoxyresin): a· using bromine-containing epoxy resin, the weight percentage of bromine is 15~5〇%, and the epoxy equivalent (Epoxy Equivalent Weight, EEW) is 250~1500 , the hydrolysis gas content is 500ppm or less; b· or using the phosphorus-containing epoxy resin, the phosphorus weight percentage is 2~1〇%, the epoxy equivalent is 250~2500, the hydrolysis chlorine content is 5〇〇ppm or less; /1290945 (2) Styrene-maleic anhydride copolymer, the structure of which is shown below

Wherein 'm is an integer from 1 to 6, and n is an integer from 2 to 12. (3) Oxygenated nitrobenzocyclohexane, the structure of which is shown in the following figure:

Rs and medium 'r^r3 are: mercapto, phenyl, epoxy, cyanate, ethenyl, maleic S& imine, oxohydrocarbyl, alkynyl, cyclopropadienyl a bicycloalkenyl group, a styryl group, an itaconate group, a benzocyclobutenyl group, an aromatic propargyl group, or an aromatic acetylene, wherein r2 is:

Ch3/C\ch3, cf3/C, cf3 human Η, or S; (4) Toughener, including: a epoxidized carboxyl terminated butyl-acrylonitrile (epoxy modified Carboxyl-Terminated Butadiene Acrylonitrile) Rubber): epoxy equivalent of 200~1000, hydrolyzed chlorine content of 500pprr or less, acrylonitrile (Acrylonitrile) weight percentage of 15~80%, /1290945 viscosity of 150,000~300000 cps, b·amine-terminated butadiene -Acrylonitrile rubber (Amine Terminated

Butadiene Acrylonitrile rubber): Amine Equivalent Weight (AEW) is 300~1500, acrylonitrile is 15~80% by weight, viscosity is 100000~500000 epS, c·Weiji-capped butyl-acrylonitrile Rubber: propylene guesses that the weight percentage is 15~80%, the viscosity is 150000~300,000 cps, d·high molecular weight epoxy resin: it is Bisphenol-A type Epoxy, or double hope !^ type epoxy resin (Bisphenol_FtypeEpoxy), or bisphenol M type epoxy resin (Bisphenol-M type Epoxy), its molecular weight is 1000~5〇〇〇〇; (5) Catalyst: the catalyst system used is three Amines, for example: 2-methylimidazole (2MI), 2-ethyl-4-methyl-imidazole; 2E4MI, 2-Phenyl-imidazole; 2PI), Benzyl dimethylamine (BDMA), etc.; and (6) Diluent · Acetone, methyl ethyl ketone (MEK), cyclohexanol, decyl isobutyl ketone (MIBK) ), propylene glycol oxime ether (PM), propylene glycol oxime ether acetate (PMA), or dimethyl decylamine (DMF)Forming the bromine-containing epoxy resin (when the exposed laminate is exposed to flame or high temperature, releasing bromide ions to slowly burn) to form a varnish, and after impregnating the woven glass cloth, forming a flame-retardant laminate, It has good solder heat resistance and anti-foaming property. The optimum weight percentage of bromine in the forming plate is 15~25%, so the weight percentage of bromine of the brominated epoxy resin used for 11 / 1290945 is 15~50wt%. The epoxy equivalent is 250 to 1500, and the amount used is 100 parts by weight. If the epoxy equivalent is 1500, the wetting state between the resin and the glass fiber bundle is & If the flow gel is too large, the hydrolysis gas content will be greater than 500 ppm, which will affect the progress of the hardening reaction. The phosphorus-containing epoxy resin (which is formed by exposing the laminate to flame or high temperature to form a flame-retardant layer to slowly burn) to form a varnish, and after impregnating the woven glass cloth, forming a flame-retardant laminate To make it have good solder heat resistance and anti-foaming property, the weight percentage of the best phosphorus in the forming plate is 2 to 6%, so the weight percentage of the selected epoxy resin containing the dish is 2 to 8%, epoxy The equivalent weight is 25 〇 15 15 〇〇, and the amount used is just parts by weight. If the epoxy equivalent is high, the wetting state between the resin and the glass fiber bundle will be deteriorated. If it is lower than the shift, the phenomenon that the knee is too large will occur. If the age of the towel is greater than 5G0Ppm, it will affect the progress of the hardening reaction. The styrene-maleic anhydride copolymer is a hardener and is used in a weight ratio of 20 to 70 (as opposed to the epoxy resin of the formulation). If the amount used is greater than 70%, the hardener is excessive, causing the unreacted hardener to absorb water, resulting in a f-constant and dielectric loss of the substrate. If the amount used is less than 20% by weight, the hardener is insufficient, resulting in too much unreacted epoxy resin, causing the adhesive to be too large and the unreacted epoxy resin to absorb water, so that the dielectric constant and dielectric loss of the substrate become high. The purpose of the use of the oxo-nitrobenzo benzocyclohexane is to reduce the electrical loss of the material, and the amount used is 5 to 5 parts by weight. If the amount used is too low, the dielectric material of the material is... and the effect of the taste of the electric charge, but if it exceeds 50 parts by weight, the formed plate will become 12 Ί290945

a. Epoxidized end-capped butadiene-acrylonitrile rubber: epoxy equivalent is 2〇0~1000, hydrolyzed chlorine content is less than 5〇〇ppm, and the weight percentage of propylene is 15~80%, b · Amine-terminated butadiene _ acrylonitrile rubber · ammonia equivalent is 300 ~ 1500, acrylonitrile weight percentage is 15 ~ 8 〇%, c · carboxyl terminated butadiene - acrylonitrile rubber: acrylonitrile weight The percentage is 15~80%, d. High molecular weight epoxy resin: it is a double-aged epoxy tree, or a double-type F-type epoxy resin, or a double-laid epoxy resin, and its molecular weight is 1000~ When the amount of epoxy resin used exceeds 1 part by weight, the wet state between the resin and the fiber-breaking bundle may be deteriorated, and the formed material (four) may be recorded, resulting in failure to carry more components. The catalyst is a tertiary amine, for example, Μ, 2E4MI, 2pj, BDMAf. The characteristic of the secondary amine is to lower the reaction temperature. If the tertiary amine is not used, the hardening reaction starts at about 170 〇C, but if When a tertiary amine is used, the hardening reaction occurs at about 12 (about TC, and the amount used is _~3 () by weight. If the amount used is too high, the reactivity is too fast, and the amount is too small. The effect of the thinner is that when it is impregnated onto the glass cloth, after being submerged at 6〇~i9〇c, * will be in the form of money, for example, acetone, nail (10), ring can be used. Hexanol, methyl isobutyl, propylene glycol methyl ether, propylene glycol 13 1290945 [Simple description of the diagram] No [Main component symbol description] None

17

Claims (1)

.1290945 X. Patent application scope: 1. An electronic material with low dielectric constant and low dielectric loss, the formulation of which includes: (a) - stupid ethylene _ maleic anhydride copolymer, the structure is as follows Nothing Wherein m is an integer from 1 to 6, and n is an integer from 2 to 12; (b) oxoazobenzocyclohexane having the structure shown in the following figure: <wherein, RAR3 is selected from the group consisting of methyl, phenyl, epoxy, nitroester, vinyl, maleimine, oxyalkenyl, alkyne, dioxin & dicycloalkenyl a group of styrene-based, itacona-based, stupid and ring-like, ^, steroidal propargyl ether, and aromatic acetylene, wherein r2 is selected from the group consisting of Η And in the group of S (c) a bad oxygen resin; Ί 290945 (d) - a toughening agent; (e) - a catalyst; and (f) a diluent. 2. The electronic material according to claim 1, wherein the epoxy resin has an epoxy equivalent of from 250 to 750 g/eq. The electronic material according to claim 1, wherein the bromine-containing epoxy resin has a weight percentage of bromine of 15 to 25%. 4. The electronic material according to claim 1, wherein the phosphorus-containing epoxy resin has a weight percentage of phosphorus of 2 to 10%. 5. The electronic material according to claim 1, wherein the epoxy resin has a hydrolyzed chlorine content of 500 ppm or less. 6. The electronic material of claim 1, wherein the catalyst is a tertiary amine. 7. The electronic material according to claim 1, wherein the catalyst Φ is 2-mercaptopurine. 8. The electronic material of claim 1, wherein the catalyst is 2-ethyl-4-mercaptoimidazole. 9. The electronic material of claim 1, wherein the catalyst is a 2-phenyl microphone bite. 10. The electronic material of claim 1, wherein the catalyst is benzoguanidine dimethylamine. 19 1229045 ιι. The electronic material of claim 5, wherein the 刃 刃 刃 包括 包括 包括 包括 包括 包括 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱 裱Nitrile rubber, monocarboxy-terminated butadiene-acrylonitrile rubber, and a high molecular weight epoxy resin. The electronic material according to claim 11, wherein the epoxidized carboxyl-terminated butadiene-acrylonitrile rubber has an epoxy equivalent of 200 to 1000' hydrolyzed chlorine content of 5 〇〇ppm or less. . The electronic material of claim n, wherein the weight percent of the acrylonitrile is 15 to 8 Å/〇. 14. The electronic material according to claim n, wherein the high molecular weight epoxy resin is selected from the group consisting of a surface type A epoxy resin, a double type epoxy resin, and a double antimony type epoxy resin. One of the groups has a molecular weight of 1000 to 50000. & - A method of manufacturing an electronic material having a low dielectric constant and a low dielectric loss, the manufacturing method comprising the steps of: (1) adding an epoxy resin to a stirrer; - adding the styrene-maleic anhydride copolymer to the donor, and then adding the oxoazobenzocyclohexane; (3) after uniformly mixing, adding a catalyst to the blending In the apparatus, forming a slurry; (4) using a diluent to adjust the slurry to an appropriate degree of dryness to obtain an epoxy resin varnish; (3) coating the epoxy resin varnish onto a reinforcing material; And (6) forming a substrate by heat polymerization hardening. The method for manufacturing an electronic lining according to claim 15 is characterized in that the material is a glass cloth, a glass fiber, or an aramide fiber. 17. The method of producing an electronic material according to claim 15, wherein the diluent is selected from the group consisting of acetone, methyl ethyl hydrazine, cyclohexanol, methyl isobutyl hydrazine, propylene glycol (tetra), propylene glycol, and A group of amines. 18. The method of producing an electronic material according to claim 15, wherein the step of covering the step (5) is a coating method. 19. The method of manufacturing an electronic material according to claim 15, wherein the method of the step (5) is an impregnation method. Eight