TWI424021B - Thermosetting resin composition and copper clad laminate - Google Patents

Description

Thermosetting resin composition and copper foil laminate

The present invention relates to a thermosetting resin composition, and more particularly to a thermosetting resin composition having a low dielectric constant and a low dissipation coefficient and used for making high-speed signal-transmitting copper foil laminates.

With the advancement of technology, people rely more and more on electronic products. The most representative electronic products such as personal computers, notebook computers, personal digital assistants (PDAs) and mobile phones are increasingly integrated. The function of the product is also within the product, and therefore, the circuit board of the electronic product begins to be highly integrated, multi-layered, and miniaturized.

With the development of integration and miniaturization, signals between circuits are transmitted at a very high speed, and thus the problem of signal delay and transmission loss becomes very serious and urgently needs to be solved. Since the degree of signal delay is proportional to the square root of the dielectric constant of the insulator on the board, and the transmission loss is proportional to the dielectric constant of the insulator and the dissipation factor. Therefore, it is our primary goal to prepare a circuit board made of a material having a low dielectric constant and a low dissipation coefficient.

In order to solve the above problem, Japanese Patent No. 2000-239496 discloses a method of mixing a cyanate resin with a dicyclopentadienyl epoxy resin having a low dielectric constant and a dissipation coefficient, thereby lowering the dielectric constant and dissipating. The method of the coefficient. However, this approach does not provide enough electrical characteristics to match the high speed transmission board.

A method for mixing a phenol-modified cyanate oligomer with a polyphenylene ether to reduce the dielectric constant and the dissipation coefficient is disclosed in U.S. Patent Nos. 6,162,876 and 6,245,841. However, the circuit board manufactured by this method is inferior in heat resistance after absorbing moisture.

In order to solve the problems of the above-mentioned various conventional techniques, the Republic of China Patent No. I297346 discloses a thermosetting resin mixed with a cyanate ester-based resin, a dicyclopentadienyl epoxy resin, a smoked vermiculite, and a thermoplastic resin. Composition, the composition of such a thermosetting resin has a low dielectric constant and a low dissipation coefficient. However, this manufacturing method must use a flame retardant containing a halogen (especially bromine; Bromine; Br) component, such as tetrabromocyclohexane, hexabromocyclononane, and 2,4,6-tris(tribromobenzene). Oxy)-1,3,5-triazabenzene, and these bromine-containing flame retardants are easily contaminated by the environment when the product is manufactured, used, or even recycled or discarded.

In view of the above, in the conventional technology for manufacturing a circuit board, if a sufficient halogen-containing flame retardant is not added to the thermosetting resin, the circuit board cannot meet the UL94-V0 safety regulation after the circuit board is fabricated using the thermosetting resin. Flame resistance test; conversely, once enough halogen-containing flame retardant is added, it will pollute the environment. Therefore, whether or not sufficient halogen-containing flame retardant is added, the problem of poor flame resistance and environmental pollution cannot be effectively solved at the same time.

As can be seen from the above description, in the conventional technique for fabricating a circuit board, it is impossible to simultaneously add sufficient halogen-containing flame retardant to the thermosetting resin. Effectively solve the problem of poor flame resistance and environmental pollution; therefore, the main object of the present invention is to provide a composition of a thermosetting resin having a low dielectric constant and a low dissipation coefficient, and is halogen-free and flame-retardant in the production process. The ability of the flame retardant to replace the halogen-containing flame retardant in the prior art, thereby solving the above two problems at the same time.

A thermosetting resin composition comprising dicyclopentadiene epoxy resin, benzoxazine, maleic imide, styrene/maleic anhydride copolymer, a filler, a flame retardant, and an imidazole accelerator. The thermosetting resin is composed of an excellent dielectric property having a low dielectric constant and a low dissipation coefficient, and can be used for a copper foil laminate for high-speed signal transmission.

In the preferred embodiment of the present invention, a phosphorus-containing hardening resin (Phosphorous Content Resin) is used as a halogen-free flame retardant flame retardant to replace the halogen-containing flame retardant in the prior art.

Further, a copper foil laminate of the present invention is used for high-speed signal transmission, and the copper foil laminate comprises the above-mentioned thermosetting resin.

In the technique of adding a halogen-containing flame retardant, since the present invention adds a sufficient halogen-free flame retardant to the thermosetting resin composition, a circuit board produced by using the thermosetting resin of the present invention can be used. It has sufficient flame resistance and thermal cracking temperature of up to 360 °C, which can be applied to the lead-free reflow process.

Compared to the conventional technique of adding sufficient halogen-containing flame retardant, The composition of the thermosetting resin of the invention does not contain a halogen element; therefore, the thermosetting resin produced by using the composition provided by the invention has the characteristics of low dielectric constant and low dissipation coefficient, and has an effective adhesive metal foil (such as Copper foil) is used to make copper foil laminates for high-speed transmission applications and can effectively overcome environmental pollution problems.

The specific embodiments of the present invention will be further described by the following examples and drawings.

The present invention relates to a composition of a thermosetting resin for a high-speed transmission circuit board, and more particularly to a composition of a thermosetting resin having a low dielectric constant and a low dissipation coefficient. The invention is illustrated by the following description of the preferred embodiments of the invention, and is not intended to limit the invention. The contents of this preferred embodiment are detailed below.

The composition of the thermosetting resin of the present invention comprises Dicyclopentadiene epoxy resin (DCPD epoxy resin), Benzoxazine (BZ), Bismaleimide (BMI), styrene. /Styrene-Maleic Anhydride Copolymer (SMA), Filler, flame retardant, and Imidazole catalyst.

In a preferred embodiment of the present invention, the composition of the thermosetting resin of the present invention comprises: (a) 100 parts by weight of a dicyclopentadiene epoxy resin; (b) 20 to 70 parts by weight of a benzoic acid Qin (c) 30 to 90 parts by weight of a maleimide; (d) 40 to 120 parts by weight of a styrene/maleic anhydride copolymer; (e) 40 to 160 parts by weight of a filler; 60 to 120 parts by weight of a flame retardant; and (g) 0.1 to 1.0 part by weight of an imidazole accelerator.

Wherein the softening point of the dicyclopentadiene epoxy resin in (a) is between 45 and 105 ° C, and the dicyclopentadiene epoxy resin in (a) is one or less The column chemical structure is represented by:

The weight average molecular weights (Mw) of the benzoxoxine in (b) is between 200 and 2000, and the benzoxazine in (b) is one of the following chemistry The structure is represented by:

Among them, R1 is a group consisting of an alkyl group having 1 to 15 carbon atoms, a ketone group, and C(CH ₃ ) ₂ . R2 and R3 are groups of alkyl groups having 1 to 20 carbon atoms, phenyl groups and cyclic phenyl groups.

The maleated imine melting point in (c) is between 60 and 180 ° C, and the maleimide in (c) is one represented by the following chemical structural formula:

Wherein R is a group of CH ₂ , C ₂ H ₅ , phenyl or maleimide.

In the styrene/maleic anhydride copolymer of (d), the chemical structure ratio of styrene to maleic anhydride is 1 to 6, and the styrene/maleic anhydride copolymer in (d) is A type represented by the following chemical structural formula, m and n are both positive integers:

Further, the filler in (e) may be a molten cerium oxide (Fused Silica), and the diameter of the molten cerium oxide is less than 40 μm. Alternatively, the filler may be a calcined kaolin (Dehydroxylated Kaolin) and the diameter of the kaolin is less than 40 μm. Further, the flame retardant in (f) is a phosphorus-containing hardening resin (Phosphorous=Content Resin), and the phosphorus content of the phosphorus-containing hardening resin is between 3% and 15% by weight, instead of A flame retardant containing a halogen (especially bromine) component is used in the art.

The invention also provides a thermosetting resin comprising the invention described above The composition, the copper foil laminate for high-speed signal transmission, is prepared by dissolving or dispersing the composition of the thermosetting resin in a solvent, and immersing the fiber cloth in the composition. The fiber cloth was then dried at a temperature of 110 to 195 ° C for a predetermined period of time to prepare a prepreg for a printed circuit board having a B stage. Then, the adhesive sheet is laminated on at least one layer, and then covered with a copper foil on the upper and lower sides of the bonded adhesive sheet, and heated and pressed by a vacuum press to prepare a copper foil laminate for high-speed signal transmission.

Among them, the fiber cloth can be a general woven or non-woven fabric. In addition, the fiber cloth may be made of inorganic fibers such as glass, alumina, asbestos, boron, yttrium aluminum glass, yttrium glass, tantalum carbide, and tantalum nitride, or aromatic polyamines, polyether ketones, poly An organic fiber such as an ether imine or a cellulose. Preferably, in the embodiment, the fiber cloth is a glass woven fiber.

The technical documents disclosed in the Republic of China Invention Patent No. I297346 (hereinafter referred to as "the '346 patent") are also fabricated into four circuit boards using four different thermosetting resins (ie, Comparative Examples 1 to 4 below). And detecting the glass transition temperature, the heat resistance after absorbing moisture, the dielectric constant, the dissipation coefficient, and the adhesion to the copper film, respectively, for the four circuit boards produced; therefore, in order to prove the use of the present invention The copper foil laminate made of the composition of the thermosetting resin can also exhibit the results comparable to the 346' patent in the above-mentioned test items without adding a halogen, and the following specifically provides four different material ratios. The examples of the produced copper foil laminates (i.e., the following Examples 1 to 4) were compared with the above-mentioned five test items by the 346' patent.

Please refer to Table 1 below. Table 1 is a thermosetting resin group material ratio table used in the four embodiments of the present invention. And, with the prior art, the Republic of China For comparison of comparative examples made of four different material ratios disclosed in Japanese Patent No. I297346, refer to the second drawing, which is a thermosetting resin group material used in four comparative examples of the prior art. Scale table.

Example 1

The composition of the thermosetting resin used in the present embodiment contains 100 parts by weight of a dicyclopentadiene epoxy resin, 100 parts by weight of a phosphorus-containing hardening resin as a flame retardant, and 65 parts by weight of a styrene/maleic anhydride copolymer, 40 parts by weight of benzoxazine, 50 parts by weight of maleimide, 0.12 parts by weight of an imidazole catalyst, and 90 parts by weight of molten cerium oxide as a filler.

The fiber cloth is immersed in a solution containing the composition of the thermosetting resin. Then, the fiber cloth was dried at a temperature of 110 to 195 ° C to prepare an adhesive sheet for a printed circuit board having a B state. Then, the adhesive sheet was covered with a copper foil having a thickness of 35 μm, and heated and pressed by a vacuum press to prepare a copper foil laminate for high-speed signal transmission of Example 1.

Example 2

In contrast to Example 1, the content of maleimide in the composition of the thermosetting resin was changed from 50 parts by weight to 35 parts by weight, and the filler was changed to 70 parts by weight of kaolin. The composition of the thermosetting resin and the copper foil laminate for high-speed signal transmission were prepared in the same manner as in Example 1.

Example 3

Different from Example 1, the content of the styrene/maleic anhydride copolymer in the composition of the thermosetting resin is changed from 65 parts by weight to 80 parts by weight, and the content of benzoxazine is changed from 40 parts by weight to 30 parts by weight, and melting. The content of cerium oxide was changed from 90 parts by weight to 70 parts by weight. The composition of the thermosetting resin and the copper foil laminate for high-speed signal transmission were prepared in the same manner as in Example 1.

Example 4

Different from Example 1, the content of benzoxazine in the composition of the thermosetting resin is changed from 40 parts by weight to 35 parts by weight, and the content of maleimide is changed from 50 parts by weight to 65 parts by weight, and the cerium oxide is melted. The content was changed from 90 parts by weight to 70 parts by weight. The composition of the thermosetting resin and the copper foil laminate for high-speed signal transmission were prepared in the same manner as in Example 1.

Comparative Example 1

The composition of the thermosetting resin used in Comparative Example 1 contained 40 parts by weight of polyphenylene ether (HPP820) as a thermoplastic resin, 7 parts by weight of smectite, and 60 parts by weight of 2,4,6-tris(tribromophenoxy). 1,3,5-triazabenzene as flame retardant, 20 parts by weight of a phenolic compound, 100 parts by weight of 2,2-bis(4-c-cyanylphenyl)propane prepolymer (BA230S) As a cyanate ester-based resin, 100 parts by weight of a dicyclopentadienyl epoxy resin, 0.01 part by weight of cobalt acetylacetonate as a cyanate-based resin curing accelerator, and 0.5 part by weight of an epoxy resin curing accelerator .

The fiber cloth is immersed in a solution containing the composition of the thermosetting resin. Connect The fiber cloth was dried at a temperature of 80 to 200 ° C to prepare an adhesive sheet for a printed circuit board having a B state. Then, the adhesive sheet was covered with a copper foil of 35 μm thick on the upper and lower sides, and then pressed by a vacuum press to prepare a copper foil laminate of Comparative Example 1.

Comparative Example 2

A thermosetting resin and a kind were prepared in the same manner as in Comparative Example 1, except that 100 parts by weight of tetra-o-methylbiphenyl F dicyanide prepolymer (ME240S) was used as the cyanate-based resin. Copper foil laminate.

Comparative Example 3

In addition to 80 parts by weight of 2,2-bis(4-cyanate) propane prepolymer as a cyanate-based resin, 120 parts by weight of dicyclopentadienyl epoxy resin, 10 parts by weight of smoked A thermosetting resin was prepared in the same manner as in Example 1 except that vermiculite, 0.008 parts by weight of a cyanate resin curing accelerator, 0.6 parts by weight of an epoxy resin curing accelerator, and 15 parts by weight of a first-grade phenolic compound. A copper foil laminate for high speed signal transmission.

Comparative Example 4

A thermosetting resin and a copper foil laminate for high-speed signal transmission were prepared in the same manner as in Example 1 except that 40 parts by weight of polystyrene (15 NFI) was used instead of polyphenylene ether and 10 parts by weight of smectite. .

For each of the copper foil laminates prepared in Example 1 to Example 4 and Comparative Example 1 to Comparative Example 4, the glass transition temperature and the adsorption were respectively measured. Heat resistance, dielectric constant, dissipation coefficient, and adhesion to copper foil after moisture is collected. Referring to Table 3, Table 3 is a test comparison table for Examples 1 to 4 and Comparative Examples 1 to 4.

It can be easily observed from the third figure that the composition of the thermosetting resin of the present invention can be exhibited regardless of the glass transition temperature, the heat resistance after moisture absorption, the dielectric constant, the dissipation coefficient, or the adhesion to the copper foil. 'No. patent phase As a result, however, further, the thermosetting resin composition of the present invention does not contain any halogen-containing flame retardant, but can reduce the degree of environmental pollution.

In summary, the thermosetting resin of the present invention has excellent dielectric properties with low dielectric constant and low dissipation coefficient, and at the same time maintains a good glass transition temperature, and can be used for preparing a copper foil layer for multilayer and high-speed signal transmission. Plywood, and the preparation process does not need to use bromine-containing flame retardant, it can reduce the degree of environmental pollution and improve the degree of environmental protection.

The features and spirit of the present invention will be more apparent from the detailed description of the preferred embodiments. On the contrary, the intention is to cover various modifications and equivalents within the scope of the invention as claimed.

Claims (12)

A thermosetting resin composition for producing a high-performance circuit board comprising: (a) 100 parts by weight of a dicyclopentadiene epoxy (DCPD epoxy); (b) 20 to 70 parts by weight of a Benzoxazine (BZ); (c) 30 to 90 parts by weight of a maleimine (BMI); (d) 40 to 120 parts by weight of a styrene / Styrene-Maleic Anhydride Copolymer (SMA); (e) 40 to 160 parts by weight of a filler (Filler); (f) 60 to 120 parts by weight of a flame retardant; And (g) 0.1 to 1.0 part by weight of an Imidazole catalyst. The composition of the thermosetting resin according to claim 1, wherein the dicyclopentadiene epoxy resin in the item (a) is one represented by the following chemical structural formula, and the softening point is 45 Between 105 ° C, The composition of the thermosetting resin according to claim 1, wherein the benzoxazinyl group in the item (b) is a weight average molecular weights (Mw) represented by the following chemical structural formula. ) is between 200 and 2000, R ₁ is a group of alkyl groups having 1 to 15 carbon atoms, a ketone group, and C(CH ₃ ) ₂ , and R ₂ and R 3 are alkyl groups having 1 to 20 carbon atoms, and benzene. Groups of groups and epoxy groups The composition of the thermosetting resin according to claim 1, wherein the maleimide in the item (c) is one represented by the following chemical structural formula, and the melting point is between 60 and 180 ° C. Between the R system is a group of CH ₂ , C ₂ H ₅ , phenylene and maleimine. The composition of the thermosetting resin according to claim 1, wherein the styrene/maleic anhydride copolymer of the item (d) is one represented by the following chemical structural formula, wherein the copolymer is m and n is a positive integer, the ratio of m / n is 1 ~ 6 The composition of the thermosetting resin according to claim 1, wherein the filler in the item (e) is a molten cerium oxide (Fused Silica). The composition of the thermosetting resin according to claim 6, wherein the molten cerium oxide has a diameter of less than 40 μm. The composition of the thermosetting resin according to claim 1, wherein the filler in the item (e) is a dehydroxylated kaolin. The composition of the thermosetting resin according to claim 8, wherein the diameter of the calcined kaolin is less than 40 μm. The thermosetting resin composition according to claim 1, wherein the flame retardant in the item (f) is a phosphorus-containing hardening resin (Phosphorous Content Resin). The composition of the thermosetting resin according to claim 10, wherein the phosphorus-containing hardening resin has a phosphorus content of 3% to 15% by weight. A copper foil laminate for use in high-speed signal transmission, the copper foil laminate comprising the thermosetting resin composition as described in claim 1.