TW201518403A - Low dielectric resin composition and prepreg, copper-clad laminate and circuit board using the same - Google Patents

Abstract

The present invention provides a low dielectric resin composition, comprising: (A) vinylbenzyl polyphenylene oxide resin and (B) dicyclopentadiene-vinylbenzyl polyphenylene oxide resin. This invention, through the inclusion of specific components, may attain circuit board properties such as high glass transition temperature, low dielectric property (Df < 0.006 at 10 GHz measurement frequency) and high thermal resistance. It can be made as prepregs or resin films and applicable to copper-clad laminates and printed circuit boards.

Description

Low dielectric resin composition, semi-cured film, copper foil substrate and circuit board using the same

The present invention relates to a low dielectric resin composition, and more particularly to a low dielectric resin composition for use in a printed circuit board.

In order to adapt to the world's environmental protection trends and green regulations, halogen-free is the current environmental trend of the global electronics industry. Countries around the world and related electronics manufacturers have successively developed mass production schedules for halogen-free electronic products for their electronic products. After the implementation of the European Restriction of Hazardous Substances (RoHS), substances including lead, cadmium, mercury, hexavalent chromium, polybrominated biphenyls and polybrominated diphenyl ethers have not been used to manufacture electronic products or Its zero components. Printed Circuit Board (PCB) is the basis of electronic motor products. Halogen-free is the first key control item for printed circuit boards. International organizations have strict requirements on the halogen content of printed circuit boards, including the International Electro-Electrical Committee ( IEC) 61249-2-21 requires bromine, chloride content of less than 900 ppm, and total halogen content must be less than 1500 ppm; Japan Electronic Circuit Industry Association (JPCA) specifies bromide and chloride content limits At 900 ppm; Greenpeace’s greening policy, which is currently being promoted, requires all manufacturers to completely eliminate PVC and bromine-based flame retardants in their electronic products to meet both lead-free and halogen-free green electronics. Therefore, the halogen-free material has become a key development project for the current industry.

In the new era, electronic products tend to be light and thin, and are suitable for high-frequency transmission. Therefore, the wiring of the circuit board is becoming higher density, and the material selection of the circuit board is more stringent. The high-frequency electronic components are bonded to the circuit board. In order to maintain the transmission rate and maintain the integrity of the transmission signal, the substrate material of the circuit board must have a lower dielectric constant (Dk) and a dielectric loss (also called a loss factor). Dissipation factor, Df). At the same time, in order to maintain the normal operation of electronic components in high temperature and high humidity environments, the circuit board must also have the characteristics of heat resistance, flame retardancy and low water absorption. Since epoxy resin is excellent in adhesiveness, heat resistance, and moldability, it is widely used for a copper foil substrate or a sealing material for an electronic component and a motor machine. In terms of safety against fire, the material is required to have flame retardancy. Generally, it is a flame retardant epoxy resin, and a flame retardant is added in combination with a flame retardant, for example, in an epoxy resin. The introduction of a halogen, especially bromine, imparts flame retardancy and improves the reactivity of the epoxy group. However, recent electronic products tend to be lightweight, miniaturized, and circuit miniaturized. Under such requirements, a relatively large halide is not preferable in terms of weight reduction. In addition, after a long period of use at a high temperature, the dissociation of the halide may occur, and there is a risk of corrosion of the fine wiring. In addition, the used electronic components after use will produce harmful compounds such as halides after combustion, and are not environmentally friendly.

CN 102134431 B (CN431 for short) discloses a thermosetting resin composition using a biscyclopentadiene phenol resin which can be used to produce a low dielectric constant resin varnish which can be applied to a printed circuit laminate, the resin composition comprising: (A a dicyclopentadiene-phenolic resin; (B) one or more dicyclopentadiene epoxy resins; or (C) a novel dicyclopentadiene-dihydrobenzo resin; or (B) and (C) a mixed resin; and (D) a flame retardant, a curing agent, a curing accelerator, and a solvent. The component (A), the component (B) and the component (C) in the resin composition both contain a saturated polycyclic dicyclopentadiene structure, which can reduce the dipole moment, dielectric constant and dielectric loss of the resin varnish. And a bromine- or phosphorus-based flame retardant added to impart a high thermal stability property to the composition. However, the dielectric loss factor of the substrate fabricated by CN431 cannot reach the dielectric measured at 10 GHz with a Df of less than 0.009 (typically a material with a Df of 0.009 at 1 GHz, and a Df measured at 10 GHz is approximately equal to 0.012). Loss characteristics requirements.

Copper foil substrates and printed circuit boards, in terms of electrical properties, mainly include dielectric constants and dielectric losses of materials. In general, since the signal transmission speed of the substrate is inversely proportional to the square root of the dielectric constant of the substrate material, the dielectric constant of the substrate material is generally as small as possible; on the other hand, the smaller the dielectric loss represents the loss of signal transmission. The less the material, the lower the dielectric loss, the better the transmission quality.

Therefore, how to develop materials with low dielectric constant and low dielectric loss under 10 GHz measurement and apply them to the manufacture of high-frequency printed circuit boards is the current solution for printed circuit board materials. problem.

In view of the above-mentioned shortcomings of the prior art, the inventors felt that they have not perfected their efforts, exhausted their mental and careful research and overcoming, and developed a low dielectric resin composition based on their years of accumulated experience in the industry.

SUMMARY OF THE INVENTION A primary object of the present invention is to provide a low dielectric resin composition which can be applied to a circuit substrate by using a specific component to achieve a high glass transition temperature and low dielectric properties (Df < Good characteristics such as 0.006 at 10 GHz measurement frequency), high heat resistance, etc. The low dielectric resin composition disclosed in the present invention can be applied to a copper foil substrate and a printed circuit board by forming a semi-cured film or a resin film. the goal of.

To achieve the above object, the present invention provides a low dielectric resin composition comprising: (A) a vinyl benzyl poly-phenyl ether resin; and (B) dicyclopentadiene-ethylene Dicyclopentadiene-vinyl benzyl phenyl ether resin.

The above composition, wherein the (A) vinylbenzyl polyphenylene ether resin comprises a structure represented by the following formula (1):

Wherein R ₁ and R ₂ are each a hydrogen atom, and R ₃ , R ₄ , R ₅ , R ₆ and R _{7 are the} same or different and represent a hydrogen atom, a halogen atom, an alkyl group or a halogen-substituted alkyl group;

-(OXO)- represents one of the formula (2) or the formula (3);

Wherein R ₈ , R ₉ , R ₁₄ and R _{15 are the} same or different and represent a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group; and R ₁₀ , R ₁₁ , R ₁₂ and R _{13 are the} same Or different, representing a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group;

Wherein R ₁₆ , R ₁₇ , R ₂₂ and R _{23 are the} same or different and represent a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group; and R ₁₈ , R ₁₉ , R ₂₀ and R _{21 are the} same Or different, representing a halogen atom, an alkyl group having 6 or fewer carbon atoms or a phenyl group, and A is a linear, branched or cyclic hydrocarbon having 20 or fewer carbon atoms;

-(YO)- represents the general formula (4);

Wherein R ₂₄ and R _{25 are the} same or different and represent a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group; R ₂₆ and R _{27 are the} same or different and represent a hydrogen atom, a halogen atom, and have 6 An alkyl group of one or less carbon atoms or a phenyl group;

Z represents an organic group having 1 carbon atom, and the group may contain an oxygen atom, a nitrogen atom, a sulfur atom and/or a halogen atom, for example, Z may be a methylene group (−CH ₂ −);

a and b are integers from 1 to 30, respectively, and c and d are both 1.

According to an embodiment of the present invention, the (A) vinylbenzyl polyphenylene ether resin is preferably selected from one or a combination of the structures represented by the following formulas (5), (6) and (7). (5) (6) (7) wherein R ₈ , R ₉ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₂₂ and R _{23 are the} same or different and represent a halogen atom, an alkyl group having 6 or less carbon atoms or Phenyl; R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₈ , R ₁₉ , R ₂₀ and R _{21 are the} same or different and represent a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group; Wherein R ₂₄ and R _{25 are the} same or different and represent a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group; and R ₂₆ and R _{27 are the} same or different and each represents a hydrogen atom, a halogen atom, or An alkyl group of 6 or less carbon atoms or a phenyl group; a and b are each independently an integer of from 1 to 30.

Among them, the above vinylbenzyl polyphenylene ether resin is commercially available as a terminal vinylbenzyl biphenyl polyphenylene ether resin produced by Mitsubishi Gas Chemical Co., Ltd. under the trade name of OPE-2st.

The vinylbenzyl polyphenylene ether resin of the present invention has lower dielectric properties, i.e., lower dielectric constant and dielectric loss than the polyfunctional ether resin having a bifunctional terminal hydroxyl group.

The above composition, wherein the (B) dicyclopentadiene-vinylbenzyl phenyl ether resin comprises a structure represented by the following formula (8): (8)

Wherein T is hydrogen, a linear alkyl group of 1 to 20 carbons, a cycloalkyl group or an aryl group; n is an integer of 1-10; and T is preferably hydrogen or a methyl group.

The dicyclopentadiene-vinylbenzyl phenyl ether resin of the present invention can be obtained by reacting a compound having the structure of the following formula (9) with a styrene compound to obtain a dicyclopentadiene. - ethylene benzyl phenyl ether resin. (9)

Wherein T is hydrogen, a linear alkyl group of 1 to 20 carbons, a cycloalkyl group or an aryl group; n is an integer of 1-10; and T is preferably hydrogen or a methyl group.

The above reaction method can be carried out by converting different reactants into a plurality of types of products, for example, the styrene compound can be selected from 4-chlro-methyl styrene, 3 One of or any combination of 3-chlro-methyl styrene and 2-chlro-methyl styrene.

The above reaction method preferably carries out the reaction under the following two kinds of compounds, for example, in the presence of sodium hydroxide and tetrabutylammonium iodide, but is not limited to these two compounds.

The method for synthesizing the dicyclopentadiene-ethylenebenzyl phenyl ether resin according to the present invention is preferably a reaction of a dicyclopentadiene-phenol resin having a hydroxyl group and 4-chloro-methylstyrene in a toluene solvent. It is formed into a dicyclopentadiene-vinylbenzyl phenyl ether resin, and is preferably reacted in the presence of two compounds of sodium hydroxide and tetrabutylammonium iodide. In addition, the method for producing a dicyclopentadiene-vinylbenzyl phenyl ether resin according to the present invention is preferably subjected to methanol cleaning after the reaction to remove impurities such as a halogen-containing substance in the reactant, which may be produced after the reaction. The sodium halide (e.g., sodium chloride) can be removed by washing with methanol to make the dicyclopentadiene-vinylbenzyl phenyl ether resin product a dark brown viscous liquid resin.

The dicyclopentadiene-vinylbenzyl phenyl ether resin of the present invention has the advantage of having a vinyl functional group compared to a general phenolic resin and reacting with other compounds having a styryl functional group. Further, the dicyclopentadiene-vinylbenzyl phenyl ether resin has better properties as compared with a conventional phenol resin, a phenol resin having a hydroxyl group or a dicyclopentadiene-phenol resin when added to a resin composition of a substrate. Dielectric properties.

The low dielectric resin composition of the present invention, wherein the (B) dicyclopentadiene-vinylbenzyl phenyl ether resin is 10 to 500 based on 100 parts by weight of the (A) ethylene benzyl polyphenylene ether resin. The parts by weight are preferably 25 to 400 parts by weight, more preferably 25 to 50 parts by weight.

The low dielectric resin composition of the present invention is crosslinked by a dicyclopentadiene-vinylbenzyl phenyl ether resin and an ethylene benzyl polyphenylene ether resin, since no hydroxyl functional group is generated during the reaction. The substrate produced by the resin composition of the present invention has a better (lower) dielectric constant and dielectric loss, and can provide a substrate having better dielectric properties to the circuit board industry.

The low dielectric resin composition of the present invention further comprises: (C) a diene polymer in which a ratio of 5 to 100 is added based on 100 parts by weight of the (A) ethylene benzyl polyphenylene ether resin. It is preferably 10 to 50 parts by weight. The diene-based polymer can further reduce the dielectric properties of the substrate, and is not particularly limited. Among them, diene polymers such as styrene-butadiene copolymer, polybutadiene homopolymer, hydrogenated diene-butadiene-styrene copolymer (such as H-1052, sold by Asahi Kasei), horse Anhydride-diene-butadiene-styrene copolymer, styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-butadiene-divinyl A benzene copolymer (such as Ricon® 257, sold from Sartomer) or a maleated styrene-butadiene copolymer.

The low dielectric resin composition of the present invention further comprises: (D) a petroleum resin (Hydrocarbon resin) in which the ratio is from 1 to 100 based on 100 parts by weight of the (A) ethylene benzyl polyphenylene ether resin. The parts by weight are preferably 5 to 20 parts by weight.

The petroleum resin according to the present invention is, for example, a methylstyrene copolymer having a structure represented by the following formula (10) or (11): (10) (11)

The petroleum resin such as C5 Aliphatic Resins from EASTMAN, Hydrogenated C5 Aliphatic Resins, C9 Aromatic Resins, Pure Monomer C9 Aromatic Resin (Pure Monomer C9) Aromatic Resins), Hydrogenated C9 Aromatic Resins and C5/C9 Aliphatic/Aromatic Resins. It has been found in the experiment that the addition of the petroleum resin improves (improves) the fluidity of the resin composition, so that the semi-cured film containing the resin composition increases the fluidity of the resin during the process of producing the multilayer circuit board, which facilitates the hole filling process.

The low dielectric resin composition of the present invention further comprises: (E) a cyclic olefin copolymer in which a ratio is added based on 100 parts by weight of the (A) ethylene benzyl polyphenylene ether resin. It is 1 to 100 parts by weight, preferably 5 to 20 parts by weight, which can further lower the dielectric properties (Dk and Df) of the substrate.

The cyclic olefin copolymer of the present invention has a structure represented by the following formula (12): (12)

The cyclic olefin copolymers are, for example, Topas 5013, Topas 6013, Topas 6017 and Topas 6015 available from Polyplastic.

In the low dielectric resin composition of the present invention, in order to improve the substrate characteristics, at least one selected from the group consisting of a cyanate resin, a maleic imide resin, an isocyanate resin, and a benzene may be further added. Vinyl resin, polybutadiene resin, polyamide resin, polyimide resin, polyester resin and triallyl isocyanurate (TAIC) and triallyl cyanurate (TAC).

The low dielectric resin composition of the present invention preferably comprises a cyanate resin and a maleic imide resin, in addition to improving crosslinkability, and further increasing the glass transition temperature, heat resistance and adhesion to the copper foil. force.

The cyanate resin is not particularly limited, and any of the cyanate resins known to be used may be, for example, a compound having an (Ar−O−C≡N) structure in which Ar may be substituted or unsubstituted benzene, Biphenyl, naphthalene, phenol novolac, bisphenol A, bisphenol A novolac, bisphenol F, bisphenol F novolac or phenolphthalein ). Further, the above Ar may be further bonded to a substituted or unsubstituted dicyclopentadienyl (DCPD).

According to an embodiment of the invention, the cyanate resin is preferably selected from the group consisting of:

Wherein X ₁ and X ₂ are each independently at least one of R, Ar', SO ₂ or O; R is selected from the group consisting of −C(CH ₃ ) ₂ −, −CH(CH ₃ )−, −CH ₂ − and contains dicyclopentan a dienyl group; Ar' is selected from the group consisting of benzene, biphenyl, naphthalene, phenolic aldehyde, bisphenol A, cyclic hydrazine, hydrogenated bisphenol A, bisphenol A phenolic, bisphenol F, and bisphenol F phenolic functional group; An integer greater than or equal to 1; and Y is an aliphatic functional group or an aromatic functional group.

The aforementioned "aliphatic functional group" means a C1-C30 alkane, an alkene, an alkyne, a cycloalkane, a cycloalkene, and a derivative thereof. The aforementioned "aromatic functional group" means a compound having a benzene ring of C1-C14, such as benzene, naphthalene, anthracene, and derivatives thereof.

Examples of the cyanate resin are, for example but not limited to, the trade names Primaset PT-15, PT-30S, PT-60S, CT-90, BADCY, BA-100-10T, BA-200, BA-230S, BA. -3000S, BTP-2500, BTP-6020S, DT-4000, DT-7000, Methylcy, ME-240S, etc. Cyanate resin produced by Lonza.

The maleic imine resin is not particularly limited, and any of the maleimide resins known to be used may be used. The maleimide resin is preferably selected from at least one of the group consisting of 4, 4'- Diphenylmethane of phenylmethane Bismaleimide), bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenyl Methyl bismaleimide (3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide), 4-methyl-1,3-phenylene bismaleimide ( 4-methyl-1,3-phenylene bismaleimide) and 1,6-bismaleimide-(2,2,4-trimethyl)hexane (1,6-bismaleimide-(2,2,4- Trimethyl) hexane).

The resin composition of the present invention may further optionally comprise a flame retardant inorganic filler, a curing accelerator, a surfactant, a silane coupling agent. Additives such as toughening agents or solvents.

The low dielectric resin composition of the present invention may further comprise a flame retardant such that the substrate reaches a UL94 V-0 flame retardant rating. The flame retardant is not particularly limited, and any flame retardant known to those skilled in the art can be used. Halogen-free flame retardants, bromine-containing flame retardants, nitrogen-containing flame retardants or phosphorus-containing flame retardants are commonly used.

Examples of such flame retardants are, for example but not limited to, bisphenol diphenyl phosphate, ammonium polyphosphate, hydroquinone bis -(diphenyl phosphate), bisphenol A bis-(diphenylphosphate), tri(2-carboxyethyl)phosphine, TCEP , tris (isopropyl chloride) phosphate, trimethyl phosphate (TMP), dimethyl methyl phosphonate (DMMP), resorcinol dixylenyl phosphate (resorcinol dixylenylphosphate) , RDXP, such as PX-200), phosphorus-nitrogen compound (phosphazene), such as SPB-100, SPH-100, SPE-100, or FP-110, purchased from Otsuka Pharmaceutical, FP-110, FP -300), m-phenylene methylphosphonate (PMP), melamine polyphosphate (such as Melapur 200 from BASF), melamine cyanurate, Aluminum diethylphosphinate (OP-935, sold from Clariant) and tris-hydroxy Tri-hydroxy ethyl isocyanurate or the like. In addition, the halogen-free flame retardant may also be 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, DOPO), DOPO-containing phenol resin (such as DOPO-HQ, DOPO-PN, DOPO-BPN), DOPO-containing epoxy resin, DOPO-HQ-containing epoxy resin, etc., DOPO-BPN can be DOPO-BPAN, DOPO-BPFN , bisphenol phenolic compounds such as DOPO-BPSN.

According to an embodiment of the present invention, the flame retardant which is suitable for use in the resin composition of the present invention is preferably selected from at least one of the following flame retardants: ethyl-bis(tetrabromophenenyldimethylimine) ( Such as SAYTEX BT-93 from Albemarle and ethane-1,2 bis(pentabromobenzene) (such as SAYTEX 8010 from Albemarle), resorcinol dixylenylphosphate (RDXP) PX-200), a phosphorus-nitrogen compound (phosphazene, such as SPB-100, SPH-100, SPE-100 or FP-110, FP-300 from Fushimi) M-phenylene methylphosphonate (PMP), melamine polyphosphate (such as Melapur 200 from BASF).

The low dielectric resin composition of the present invention may further contain an inorganic filler, the main function of which is to increase the thermal conductivity of the resin composition, to improve characteristics such as thermal expansion and mechanical strength, and the inorganic filler is preferably uniformly distributed. In the resin composition.

The inorganic filler may comprise cerium oxide (molten state, non-molten state, porous or hollow type), aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, Aluminum tantalum carbide, tantalum carbide, sodium carbonate, titanium dioxide, zinc oxide, zirconium oxide, quartz, diamond powder, diamond powder, graphite, magnesium carbonate, potassium titanate, ceramic fiber, mica, boehmite, AlOOH, Zinc molybdate, ammonium molybdate, zinc borate, calcium phosphate, strontium talc, talc, tantalum nitride, mullite, calcined kaolin, clay, basic magnesium sulfate whisker, mullite whisker, barium sulfate, Magnesium hydroxide whiskers, magnesium oxide whiskers, calcium oxide whiskers, carbon nanotubes, nano-sized cerium oxide and related inorganic powders, or powder particles modified with an organic core outer shell as an insulator. The inorganic filler may be in the form of spheres, fibers, plates, granules, flakes or whiskers, and may be optionally pretreated via a decane coupling agent.

Further, the resin composition of the present invention may optionally further contain an additive such as a hardening accelerator, a surfactant, a decane coupling agent, a toughening agent or a solvent. The main function of adding a hardening accelerator is to increase the reaction rate of the resin composition. The main purpose of adding the surfactant is to improve the uniform dispersibility of the inorganic filler in the resin composition and to avoid aggregation of the inorganic filler. The main purpose of adding a toughening agent is to improve the toughness of the resin composition. The main purpose of adding a solvent is to change the solid content of the resin composition and adjust the viscosity of the resin composition.

The hardening accelerator may include a catalyst such as Lewis base or Lewis acid. Among them, the Lewis base may comprise imidazole, boron trifluoride amine complex, ethyltriphenyl phosphonium chloride, 2-methylimidazole (2MI), 2-benzene. 2-phenyl-1H-imidazole (2PZ), 2-ethyl-4-methylimidazole (2E4MZ), triphenylphosphine (TPP) and 4-dimethyl One or more of 4-dimethylaminopyridine (DMAP). The Lewis acid may include a metal salt compound such as a metal salt compound such as manganese, iron, cobalt, nickel, copper or zinc, such as a metal catalyst such as zinc octoate or cobalt octoate.

The hardening accelerator preferably comprises a peroxide hardening accelerator capable of generating a radical, such as but not limited to: dicumyl peroxide, tert-butyl peroxybenzoate (tert-butyl) Peroxybenzoate) and di(tert-butylperoxyisopropyl)benzene (BIPB). According to an embodiment of the present invention, the hardening accelerator suitable for use in the resin composition of the present invention is preferably 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne. (2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, purchased from Japanese fats and oils).

The decane coupling agent may include a silane compound and a siloxane compound, and may be further classified into an amino silane, an amino siloxane, and a ring depending on the functional group. An epoxy silane and an epoxy siloxane.

The toughening agent is selected from the group consisting of rubber resin, carboxyl-terminated butadiene acrylonitrile rubber (CTBN), and core-shell rubber.

The solvent may comprise methanol, ethanol, ethylene glycol monomethyl ether, acetone, methyl ethyl ketone (methyl ethyl ketone), methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxy ethyl A solvent such as an acid ester, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide or propylene glycol methyl ether or a mixed solvent thereof.

It is still another object of the present invention to provide a prepreg having characteristics such as high glass transition temperature, low dielectric properties, and high heat resistance. Accordingly, the prepreg film disclosed in the present invention may comprise a reinforcing material and the foregoing resin composition, wherein the resin composition is attached to the reinforcing material by impregnation or the like, and is heated to a semi-cured state by high temperature. Among them, the reinforcing material may be a fiber material, a woven fabric and a non-woven fabric, such as a glass fiber cloth, etc., which can increase the mechanical strength of the prepreg film. In addition, the reinforcing material can be selectively pretreated via a decane coupling agent.

The prepreg film can be cured by high temperature heating or heating under high temperature and high pressure to form a cured film or a solid insulating layer. If the resin composition contains a solvent, the solvent is volatilized and removed during high temperature heating.

Another object of the present invention is to provide a resin film having characteristics such as high glass transition temperature, low dielectric properties, and high heat resistance. This resin film contains the above resin composition. The resin film can be applied on a PET film, a polyimide film, or a resin coated copper (RCC) and then baked and heated.

It is still another object of the present invention to provide a laminate, such as a copper clad laminate, which has high glass transition temperature, low dielectric properties, and high heat resistance, and is particularly suitable for high speed and high speed. Frequency signal transmission board. Accordingly, the present invention provides a laminate comprising two or more metal foils and at least one insulating layer. The metal foil is, for example, a copper foil, and may further comprise at least one metal alloy such as aluminum, nickel, platinum, silver, gold, etc.; the insulating layer is formed by curing the above-mentioned semi-cured film or resin film under high temperature and high pressure, such as the aforementioned half The cured film is laminated between two metal foils and laminated under high temperature and high pressure.

The laminated board of the present invention is further processed by a process such as a circuit to form a circuit board, and the circuit board is engaged with the electronic component and operated under a severe environment such as high temperature and high humidity without affecting the quality thereof.

Accordingly, it is still another object of the present invention to provide a printed circuit board having high glass transition temperature, low dielectric properties, and high heat resistance, and is suitable for high speed and high frequency signal transmission. Wherein, the circuit board comprises at least one of the aforementioned laminated boards, and the circuit board can be fabricated by a known process.

The invention will be further described in the following examples in order to explain the invention. However, it should be noted that the following examples are only intended to illustrate the invention and are not intended to limit the scope of the invention, and any one of ordinary skill in the art to which the invention pertains can be practiced without departing from the spirit of the invention. Modifications and variations are within the scope of the invention.

In order to fully understand the objects, features and effects of the present invention, the present invention will be described in detail by the following specific embodiments.

Manufacturing example 1

80 g (0.1 mole) of PD-9110 (number average molecular weight Mn = 800 g / mol, such as the structural formula 13, n = 10 ~ positive integer) and 64 grams (0.42 mole) of 4-chloro-methylbenzene Ethylene (CMS-P) and 100 g of toluene were placed in a reaction tank apparatus, the temperature was set at 50-80 ° C and stirring reaction was started for 6 hours, and 16.8 g (0.42 mol) of sodium hydroxide and 11 g (0.03 mol) were added. The tetrabutyl iodide amine was continuously mixed for 4 hours, and then washed with methanol and distilled water to obtain a dicyclopentadiene-ethylenebenzyl phenyl ether resin, and the product was a dark brown viscous liquid. (13) Equation (13), where n = 1 to 10 are positive integers.

The method for detecting the above-mentioned synthesized dicyclopentadiene-vinylbenzyl phenyl ether resin can be detected by FTIR as shown in Fig. 1, Fig. 2, and Fig. 3. Fig. 1 shows an FTIR spectrum of a biscyclopentadiene phenol resin (Compound A) having a hydroxyl group, and a peak representing a hydroxyl group (OH functional group) appears at 3300 to 3400 cm ^-1 . Figure 2 shows the FTIR spectrum of the dicyclopentadiene-vinylbenzyl phenyl ether resin (Compound B). It is obvious that the peak of the hydroxyl group (OH functional group) at 3300~3400 cm ^-1 in Figure 2 is significantly reduced to Only a trace amount was left, and a peak representing an ethylene functional group (carbon-carbon double bond) appeared at 1600 to 1700 cm ^-1 , and it was confirmed that the present invention has synthesized a dicyclopentadiene-vinylbenzyl phenyl ether resin.

Thereafter, the dicyclopentadiene-vinylbenzyl phenyl ether resin synthesized in Production Example 1 was used in the examples and compared with a comparative example using a biscyclopentadiene phenol resin having a hydroxyl group.

Example 1 to 11 (E1-E11)

Each of the resin compositions was uniformly mixed according to the respective components and ratios shown in Table 1.

Comparative example 1 to 6 (C1-C6)

Each of the resin compositions was uniformly mixed according to the respective components and ratios shown in Table 3.

The names of the chemicals used in the above production examples, examples and comparative examples are as follows. PD-9110: a dicyclopentadiene phenolic resin having a hydroxyl group, available from Changchun resin. SA-90: Bisphenol A polyphenylene ether resin having a difunctional terminal hydroxyl group available from Sabic Corporation. SA-9000: Bisphenol A polyphenylene ether resin with terminal methyl polyacrylate available from Sabic. OPE-2st: a biphenyl polyphenylene ether resin having a terminal vinyl group, purchased from Mitsubishi Gas Chemical. Ricon 257: a styrene-butadiene-divinylbenzene copolymer available from Cray Valley. H-1052: hydrogenated diene-butadiene-styrene copolymer available from Asahi Kasei. BA-230S: bisphenol A cyanate resin available from Lonza Corporation. BTP-6020S: Cyanate resin, available from Lonza Corporation. C5, C9: petroleum resin, purchased from EASTMAN. BMI-2300: Benzene methane quinone imine, purchased from Daiwa Chemical. BMI-1700: 4,4'-diphenylmethane bismaleimide, purchased from Daiwa Chemical. 25B: 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne (2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne) , purchased from Japanese fats. SPB-100: phosphazene compound, purchased from Otsuka Chemical. Saytex 8010: Ethane-1,2 bis(pentabromobenzene) available from Albemarle. PX-202: resorcinol bis-xylyl phosphate, purchased from Japan Daiba Chemical Co., Ltd. TAIC: triallyl isocyanurate available from Evonik Industries. Molten cerium oxide: Fused silica, purchased from the genus.

The resin compositions of the above Examples 1 to 11 and Comparative Examples 1 to 6 were uniformly mixed in a stirred tank, placed in a dipping tank, and the glass fiber cloth was passed through the above-mentioned impregnation tank to adhere the resin composition to the resin composition. The glass fiber cloth is heated and baked into a semi-cured state to obtain a semi-cured film.

The semi-cured film prepared in batches above is taken from the same batch of semi-cured film four sheets and two 18 μm copper foils, laminated in the order of copper foil, four-ply semi-cured film and copper foil, and then vacuumed. A copper foil substrate was formed by pressing at 210 ° C for 2 hours, in which four sheets of semi-cured film were cured to form an insulating layer between the two copper foils.

The copper-containing substrate after etching the copper-containing foil substrate and the copper foil was separately measured for physical properties, and the physical property measurement items included: glass transition temperature (Tg, DMA instrument (dynamic thermomechanical analysis instrument) measurement), heat resistance (T288, TMA) Thermomechanical analysis instrument measurement, measuring the temperature of the non-explosive plate at 288 °C with a copper-containing substrate), copper-plated substrate immersion tin test (solder dip, S/D, 288 ° C, 10 seconds, measured heat-resistance count), excluding Copper substrate PCT (pressure cooker cooking test) moisture immersion tin test (pressure cooking at 121 ° C (at 121 ° C high pressure cooking), after 3 hours, measured solder dip 288 ° C (at 288 ° C immersion tin test), 20 seconds to see if there is Explosion), tensile strength between copper foil and substrate (peeling strength, measured by universal tension machine), P/S, half ounce copper foil (half ounce copper foil), the higher the tensile force between copper foil and substrate, the better) Dielectric constant (Dk, the lower the Dk value, the better, the Ak microwave inductive analyzer measures the Dk value of the copper-free substrate), the dielectric loss (dissipation factor, Df, the lower the Df value, the better, to AET Microwave induction analyzer measures Df value without copper substrate), flame resistance (flaming test Burning test), UL94, wherein a ranking V-0 V-1 better than V-2).

The physical property measurement results of the substrates prepared in the resin compositions of Examples 1 to 11 are shown in Table 2, and the physical property measurement results of the substrates prepared in the resin compositions of Comparative Examples 1 to 6 are shown in Table 4. From Tables 2 and 4, comparing Comparative Examples 1 to 11 and Comparative Examples 1 to 6, it can be found that the low dielectric resin composition of the present invention can achieve a high glass transition temperature and low by including a specific composition component. Circuit board characteristics such as dielectric characteristics (Df < 0.006 at 10 GHz measurement frequency), high heat resistance, and good flame retardancy. The results of Comparative Examples 1 to 6 show that the substrate produced has a significantly lower glass transition temperature and is inferior in dielectric properties and heat resistance.

From Examples 1 to 3, it was found that the content of the dicyclopentadiene-vinylbenzyl phenyl ether resin was increased relative to the ethylene benzyl polyphenylene ether resin, and the glass transition temperature of the substrate and the pulling force against the copper foil were improved.

It can be found from Examples 4 and 5 that the addition of the styrene-butadiene copolymer can further reduce the dielectric loss of the substrate and obtain better dielectric properties, and further addition of the maleic imine resin can further improve the heat resistance of the substrate. Sex (T288).

It can be found from Examples 6 and 7 that the addition of the petroleum resin C5 or C9 does not affect the substrate characteristics, but the resin filling hole fluidity can be effectively improved when the multilayer board of the printed circuit board is produced.

It can be found from Examples 8 and 9 that the addition of the cyanate resin further enhances the copper foil pulling force and the substrate heat resistance (T288) of the substrate.

It can be found from Example 10 that the addition of an appropriate amount of the phosphorus-based flame retardant can improve the flame resistance of the substrate and achieve the flame resistance of UL94 V-0. It can be found from Example 11 that the addition of an appropriate amount of the bromine-based flame retardant can improve the flame resistance of the substrate. It can also achieve the flame resistance rating of UL94 V-0.

Comparing Examples 1 to 3 and Comparative Examples 1 to 3, it was found that a substrate prepared by combining a dicyclopentadiene-vinylbenzyl phenyl ether resin and an ethylene benzyl polyphenylene ether resin is compared with a dicyclopentadiene having a hydroxyl group. A substrate produced by combining a phenol resin and a polyphenylene ether resin, the former having good heat resistance, dielectric properties, and copper foil tensile force. Because the biscyclopentadiene-vinylbenzyl phenyl ether resin has an ethylenic reaction functional group, it can react with the same ethylene or styrene resin (such as OPE-2st); while the hydroxy dicyclopentadiene-phenol resin is difficult to react with ethylene. Or the styrene resin reacts, resulting in poor substrate properties.

Further comparing Example 1 with Comparative Example 1, it was confirmed that the above-mentioned inference that the dicyclopentadiene-phenol resin having a hydroxyl group could not react with the ethylene benzyl polyphenylene ether resin, resulting in heat resistance (T288 and S/D) of the substrate and The dielectric properties are not good. In addition, the test results of Comparative Example 3 have poor Dk and Df values because the use of a dicyclopentadiene-phenol resin having a hydroxyl group and a polyphenylene ether resin having a terminal hydroxyl group results in an increase in the content of the hydroxyl group-containing substrate of the substrate. The substrate has poor Tg, dielectric properties, and moisture absorption heat resistance.

Therefore, from the test results of the above examples and comparative examples, it can be found that the low dielectric resin composition of the present invention can achieve high glass transition temperature, low dielectric properties, high heat resistance, etc. by including a specific composition component. Circuit board characteristics.

As described above, the present invention fully complies with the three elements of the patent: novelty, advancement, and industrial applicability. In terms of novelty and advancement, the low dielectric resin composition of the present invention can achieve circuit board characteristics such as high glass transition temperature, low dielectric property, and high heat resistance by including a specific composition component; Sexually, the products derived from the present invention can fully satisfy the needs of the current market.

The invention has been described above in terms of the preferred embodiments, and it is understood by those skilled in the art that the present invention is not intended to limit the scope of the invention. It should be noted that all variations and permutations equivalent to the embodiments are intended to be within the scope of the invention. Therefore, the scope of protection of the present invention should be determined by the scope defined by the scope of the patent application.

Table 3

no

Fig. 1 shows an FTIR spectrum of a dicyclopentadiene phenol resin (Compound A) having a hydroxyl group. Fig. 2 shows an FTIR spectrum of a dicyclopentadiene-vinylbenzyl phenyl ether resin (Compound B). Fig. 3 is a FTIR spectrum comparison chart of a biscyclopentadiene phenol resin (compound A) having a hydroxyl group and a dicyclopentadiene-vinylbenzyl phenyl ether resin (compound B).

Claims (12)

A resin composition comprising: (A) an ethylene benzyl polyphenylene ether resin; and, (B) a dicyclopentadiene-vinylbenzyl phenyl ether resin. The composition according to claim 1, wherein the (A) vinylbenzyl polyphenylene ether resin comprises a structure represented by the following formula (1): Wherein R ₁ and R ₂ are each a hydrogen atom, and R ₃ , R ₄ , R ₅ , R ₆ and R _{7 are the} same or different and represent a hydrogen atom, a halogen atom, an alkyl group or a halogen-substituted alkyl group; (OXO)- represents a formula (2) or a formula (3); Wherein R ₈ , R ₉ , R ₁₄ and R _{15 are the} same or different and represent a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group; and R ₁₀ , R ₁₁ , R ₁₂ and R _{13 are the} same Or different, representing a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group; Wherein R ₁₆ , R ₁₇ , R ₂₂ and R _{23 are the} same or different and represent a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group; and R ₁₈ , R ₁₉ , R ₂₀ and R _{21 are the} same Or different, representing a halogen atom, an alkyl group having 6 or fewer carbon atoms or a phenyl group, A being a linear, branched or cyclic hydrocarbon having 20 or fewer carbon atoms; -(YO)- represents General formula (4); Wherein R ₂₄ and R _{25 are the} same or different and represent a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group; R ₂₆ and R _{27 are the} same or different and represent a hydrogen atom, a halogen atom, and have 6 An alkyl group of one or less carbon atoms or a phenyl group; Z represents an organic group having one carbon atom, and the group may contain an oxygen atom, a nitrogen atom, a sulfur atom and/or a halogen atom; a and b respectively Independently any integer from 1 to 30, both c and d are 1. The composition according to claim 2, wherein the (A) vinylbenzyl polyphenylene ether resin is one selected from the group consisting of the following formula (5), formula (6) and formula (7) or combination: (5) (6) (7) wherein R ₈ , R ₉ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₂₂ and R _{23 are the} same or different and represent a halogen atom, an alkyl group having 6 or less carbon atoms or Phenyl; R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₈ , R ₁₉ , R ₂₀ and R _{21 are the} same or different and represent a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group; Wherein R ₂₄ and R _{25 are the} same or different and represent a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group; and R ₂₆ and R _{27 are the} same or different and each represents a hydrogen atom, a halogen atom, or An alkyl group of 6 or less carbon atoms or a phenyl group; a and b are each independently an integer of from 1 to 30. The composition according to claim 1, wherein the (B) biscyclopentadiene-vinylbenzyl phenyl ether resin comprises a structure represented by the following formula (8): (8) wherein, T is hydrogen, a linear alkyl group of 1 to 20 carbons, a cycloalkyl group or an aromatic group; and n is an integer of 1-10. The composition of claim 1, wherein the (B) dicyclopentadiene-vinylbenzyl phenyl ether resin is 10 to 500 based on 100 parts by weight of the (A) ethylene benzyl polyphenylene ether resin. Parts by weight. The composition of claim 5, further comprising (C) a diene-based polymer, (D) a petroleum resin or (E) a cyclic olefin copolymer, wherein 100 parts by weight of (A) ethylene benzyl chloride Based on the polyphenylene ether resin, the (C) diene polymer is 5 to 100 parts by weight, the (D) petroleum resin is 1 to 100 parts by weight, and the (E) cyclic olefin copolymer is 1 to 100. Parts by weight. The composition of claim 5, wherein the (C) diene polymer is selected from one or a combination of the following: styrene-butadiene copolymer, polybutadiene homopolymer , hydrogenated diene-butadiene-styrene copolymer, maleic anhydride diene-butadiene-styrene copolymer, styrene-butadiene-styrene copolymer, styrene-isoprene Styrene copolymer, styrene-butadiene-divinylbenzene copolymer or maleic anhydride styrene-butadiene copolymer. The composition of claim 1, which further comprises at least one of the following group of substances or a modified substance thereof: cyanate resin, maleimide resin, isocyanate resin, styrene resin, polybutadiene Resin, polyamide resin, polyimide resin, polyester resin and triallyl isocyanurate and triallyl cyanurate. The composition of claim 1, further comprising at least one of the following additives: a flame retardant, an inorganic filler, a hardening accelerator, a surfactant, a decane coupling agent, a toughening agent, and a solvent. A semi-cured film comprising the resin composition according to any one of claims 1 to 9. A copper foil substrate comprising the prepreg as described in claim 10. A printed circuit board comprising the copper foil substrate of claim 11.