TWI405787B - Thermosetting resin composition - Google Patents

Abstract

A thermosetting resin composition and a prepreg or laminate using the same are provided. The thermosetting resin composition includes an epoxy resin and curing agent, in which the curing agent is a dual-curing agent system formed with a multi-functional aromatic polyester curing agent in combination with a phenolphthalein benzoxazine phenol aldehyde or a poly(styrene-co-maleic anhydride). An organic or inorganic fiber reinforced material is impregnated with the thermosetting resin composition to form a prepreg, and the prepreg is bonded to a substrate with a metal foil disposed thereon, to form a laminate.

Description

Thermosetting resin composition

The present invention relates to a thermosetting epoxy resin composition capable of producing a low dielectric constant and a low dissipation coefficient (or dielectric tangent, dielectric loss) and which is flame retardant, and the invention can be widely applied to prepreg Film composition, printed circuit laminates, build-up bonding adhesives, adhesives, encapsulants and FRP articles are particularly useful in the manufacture of printed circuit laminates and build-up bonding adhesives.

Epoxy resin is widely used in Varnish for Copper Clad Laminate, Epoxy Encapsulant for Semiconductor, and high-density build-up due to its excellent electrical insulation properties, mechanical properties and adhesion properties. In the field of electrical and electronic components such as Resin Coated Thin Core for HDI Application and Solder Mask. A curing agent generally used in combination with an epoxy resin is an amine curing agent such as dicyandiamide, a phenol phenolic curing agent, and an acid anhydride curing agent.

Due to the increase in signal transmission and low signal transmission, the application of electrical or electronic components has the demands of Cloudy computing and Green material. Therefore, material development requires characteristics such as low dielectric constant and low dissipation factor and no added halogen flame retardant. At present, the hardener produced by the epoxy resin used in combination with the epoxy resin has a high polarity of hydroxyl groups, so it is difficult to reduce the dissipation factor (dielectric tangent or dielectric loss), and the composition needs to add bromide (for example, Tetra-Bromine). -Bis-phenol A; TBBPA) or brominated epoxy resin to achieve flame retardant properties (94-V0), so it is impossible to achieve halogen-free and flame-retardant properties. Therefore, how to develop an environmentally friendly halogen-free material with a low dielectric constant and a low dissipation factor has become a very important issue.

In the case of a hardening agent which does not generate a hydroxyl group when the epoxy resin is hardened, Japanese Patent Laid-Open No. Hei 5-51517, the Japanese Patent No. Hei 5-51517, discloses that the use of an aromatic polyfunctional polyester as a curing agent can produce a high crosslinking density (Tg = 210~290°C by DMA), it can meet the heat resistance of electronic parts or electrical insulation materials. However, the above cured products have unreacted hydroxyl or carboxyl groups, so the hardener dissipation coefficient instead Will rise, and the hardened material does not have flame retardant properties (cannot reach the UL 94-V0 rating). Japanese Patent Laid-Open 2002-12650 of Dainippon Ink Co., Ltd. uses an aromatic polyester hardener obtained by reacting naphthalene dicarboxylic acid with α-naphthol to impart a low dissipation coefficient to the cured epoxy resin, and the same hardening The material does not have a flame retardant property, and the end does not participate in cross-linking based on the hardening reaction, resulting in poor heat resistance. On the other hand, U.S. Patent No. 5,945,222, the disclosure of which is incorporated herein by reference to U.S. Patent No. 5,945,222, the disclosure of which is incorporated herein by reference. It can quickly harden and obtain a hardened material (94-V0) with good mechanical properties and flame retardancy. However, the hardened material still produces more hydroxyl groups due to the matching of the novolac, and the dielectric constant and the dissipation coefficient cannot be effectively reduced. Further, U.S. Patent No. 6,534,181 discloses that a reaction of a styrene maleic anhydride copolymer with a multifunctional amine cross-linking agent with an epoxy resin can be applied to high speed and low loss circuit board applications. It is not disclosed whether the use of a phosphorus-based epoxy resin can achieve a flame retardant rating (94-V0) and whether it changes the low dielectric constant and low dissipation factor of the original design.

SUMMARY OF THE INVENTION A primary object of the present invention is to provide a thermosetting epoxy resin composition having a low dielectric constant (Low Dielectric Constant) and a low dissipation factor (Low Dissipation Factor) and containing no halogen.

To achieve the above object, the present invention provides a thermosetting resin composition comprising an epoxy resin and a hardener, wherein the hardener is a polyfunctional aromatic polyester hardener formulated with a phenolphthalein An oxo-nitrobenzocyclohexane phenol or a styrene maleic anhydride copolymer to form a double hardener system for impregnating an organic or inorganic woven or non-woven fibrous reinforcing material with the thermosetting resin The composition is formed into a dip film composition, and after being bonded to a substrate provided with a metal foil, a laminate can be formed.

When implemented, the polyfunctional aromatic polyester hardener is formed by reacting an aromatic polyvalent carboxylic acid residue having an aryloxycarbonyl group at a molecular chain terminal with an aromatic polyvalent hydroxy compound, and the ester equivalent thereof is Ester Equivalent. 180~500. The phenolphthalein oxycarbazobenzocyclohexane phenolic has an -OH value of 200 to 700, wherein the nitrogen content is 4 to 20% by weight. The styrene maleic anhydride copolymer has an acid value of 100 to 600.

When implemented, the epoxy resin is one of a phosphorus-containing epoxy resin, a nitrogen-containing epoxy resin, a bisphenol F epoxy resin, or a combination thereof. Wherein, the phosphorus-containing epoxy resin is a modified epoxy resin of DOPO-PNE, DOPO-CNE or DOPO-HQ, and the phosphorus content thereof 2~10wt%, the epoxy equivalent is 250~800; the nitrogen-containing epoxy resin is N, N-Diglycidyl epoxy resin, epoxy resin with Oxazolidone ring, polyamidoguanidine One of polyamine-imide-epoxy (PAI-epoxy) having a nitrogen content of 5 to 20% by weight and an epoxy equivalent of 100 to 1000; the bisphenol F epoxy resin having an epoxy equivalent It is 150~1000.

When implemented, the thermosetting resin composition is added with a hardening catalyst, and the thermosetting resin composition comprises 10 to 90% by weight of epoxy resin, 90 to 10% by weight of a double hardener system, and 0.01 to 5% by weight. Hardening catalyst. Wherein the double hardener system comprises 20 to 95% by weight of a polyfunctional aromatic polyester hardener and 5 to 80% by weight of a phenolphthalein oxy azabenzocyclohexane phenol aldehyde, or the double hardener system comprises 20 to 95% by weight of a polyfunctional aromatic polyester hardener and 5 to 80% by weight of a styrene maleic anhydride copolymer. The hardening catalyst is one of an imidazole compound, an organic phosphorus compound, an organic phosphate compound, a phosphate, a trialkylamine, a 4-(dimethylamino)pyridine, a quaternary ammonium salt, or a urea compound.

In practice, the thermosetting resin composition further uses a solvent to dissolve the thermosetting resin composition to form a varnish-like composition. The solvent may be a guanamine solvent (N-methylpyrrolidone, N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide), a ketone One of a solvent (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), an ether solvent, an aromatic hydrocarbon solvent, and a monoether glycol solvent.

When implemented, the thermosetting resin composition is further provided with an inorganic filler, which is 1 to 30% by weight of the composition, and the inorganic filler is aluminum hydroxide, aluminum hydroxide, magnesium hydroxide, and cerium oxide. One of a spherical type and a crushed type alumina, and the inorganic filler has an average particle diameter of from 0.01 μm to 20 μm.

In practice, the thermosetting resin composition is further provided with a high thermal conductive inorganic filler, the inorganic high thermal conductive filler occupies 10 to 80% by weight of the composition, and the high thermal conductive inorganic filler may be hexagonal and spherical aluminum nitride, One of hexagonal crystal system and spherical boron nitride, spherical type, crushed aluminum oxide, tantalum carbide, and graphite, and the tantalum carbide includes hexagonal crystal α-carbonized germanium and cubic crystal β-carbonized germanium. Further, the highly thermally conductive inorganic filler has an average particle diameter of from 0.01 μm to 20 μm.

When implemented, the substrate of the laminate is composed of an organic or inorganic fiber reinforcing material, and the thermosetting resin composition is impregnated thereon.

In order to facilitate a more in-depth understanding of the present invention, an embodiment is described in detail below:

The thermosetting epoxy resin composition of the present invention is mainly composed of an epoxy resin and a hardener.

The epoxy resin is one of a phosphorus-containing epoxy resin, a nitrogen-containing epoxy resin, and a bisphenol F epoxy resin, or a combination thereof. The phosphorus-containing epoxy resin is a modified epoxy resin of DOPO-PNE, DOPO-CNE or DOPO-HQ, and has a phosphorus content of 2 to 10% by weight and an epoxy equivalent of 250 to 800. The specific structure thereof is as follows, wherein n=0.5~10, The preferred phosphorus content is 3 to 7 wt% and the epoxy equivalent (EEW) is 300 to 500.

The nitrogen-containing epoxy resin is N, N-Diglycidyl epoxy resin, epoxy resin with Oxazolidone ring, polyamide-imide-epoxy resin (PAI- Epoxy), such as a nitrogen content of 5 to 20% by weight, an epoxy equivalent of 100 to 1000, preferably a nitrogen content of 6 to 10% by weight and an epoxy equivalent (EEW) of 110 to 700.

The bisphenol F epoxy resin has an epoxy equivalent of 150 to 1000, and preferably has an epoxy equivalent (EEW) of 160 to 300.

The hardener is subjected to a ring-opening crosslinking reaction with an epoxy group by (1) a polyfunctional aromatic polyester hardener and a phenol oxynitride benzocyclohexane phenol phenolic hardener, or 2) The polyfunctional aromatic polyester hardener and the styrene maleic anhydride hardener simultaneously undergo ring-opening crosslinking reaction with the epoxy group to form a double hardener system, forming unreacted hydroxyl or carboxyl groups in the hardened product. Very low, cross-linking with phosphorus and nitrogen-containing bis (or poly) functional epoxy resins to produce a flame retardant ring Oxygen cured product. Wherein the hardener of (1) comprises 20 to 95% by weight of a polyfunctional aromatic polyester hardener which is an aromatic polyvalent carboxylic acid residue having an aryloxycarbonyl group at the end of the molecular chain and an aromatic polyvalent The hydroxy compound is formed and contains 5 to 80% by weight of a phenolphthalein oxodibenzobenzocyclo phenol phenolic hardener; (2) the hardener comprises 20 to 95% by weight of a polyfunctional aromatic polyester hardener and comprises 5~ 80wt% styrene maleic anhydride hardener.

a: a polyfunctional aromatic polyester hardener having an Ester Equivalent of 180 to 500 and having the following structure: Wherein Q is an atom of the formula: X: -CH ₂ , -C(CH ₃ ) ₂ , -SO ₂ , and n = 1 to 10.

b: phenol oxy-oxo-nitrobenzocyclohexane phenolic, the hardener has an -OH value of 200 to 700, wherein the nitrogen content is 4 to 20% by weight, preferably the nitrogen content is 5 to 10% by weight and the hydroxyl equivalent (-OH The value) is 200~400. The structure of phenolphthalein oxynitride benzocyclohexane phenolic is as follows:

Wherein R is allyl, unsubstituted or substituted phenyl, unsubstituted or substituted C ₁ -C ₈ -alkyl or unsubstituted or substituted C ₃ -C ₈ -cycloalkyl. R ₁ and R ₂ are hydrogen, aromatic compound or aliphatic compound

c: Styrene-co-Maleic Anhydride (SMA), the acid value of the hardener is 100-600, and the preferred acid value is 300-500. The structure is as follows:

Wherein m=2~12, n=1~8, an integer of m and n, preferably m/n=3~5.

In addition, the thermosetting resin composition of the present invention further comprises a curing catalyst, wherein the thermosetting resin composition comprises 10 to 90% by weight of epoxy resin, 90 to 10 A wt% double hardener system and 0.01 to 5% by weight of a hardening catalyst. Wherein the double hardener system comprises 20 to 95% by weight of a polyfunctional aromatic polyester hardener and 5 to 80% by weight of a phenolphthalein oxy azabenzocyclohexane phenol aldehyde, or the double hardener system comprises 20 to 95% by weight of a polyfunctional aromatic polyester hardener and 5 to 80% by weight of a styrene maleic anhydride copolymer. The hardening catalyst is one of an imidazole compound, an organic phosphorus compound, an organic phosphate compound, a phosphate, a trialkylamine, a 4-(dimethylamino)pyridine, a quaternary ammonium salt, a urea compound, and the like. When the compounding amount of the hardening catalyst is less than 0.01% by weight, the curing reaction rate becomes slow. If it is more than 5% by weight, the epoxy resin is autopolymerized (homogeneous), thereby hindering the hardening of the polyfunctional aromatic polyester. Hardening reaction of sclerosing agent and phenolphthalein oxynitride benzocyclohexane phenolic curing agent with epoxy resin.

Further, in order to prepare a printed circuit board, a build-up bonding adhesive, and an epoxy resin composition for CFRP (carbon fiber reinforced plastic), a solvent may be used to dissolve the epoxy resin composition to form a varnish-like composition (Varnish). It is prepared to be 10 to 70% by weight, preferably 15 to 65% by weight, and the solvent may be a guanamine solvent (N-methylpyrrolidone, N-methylformamide, N,N-dimethylmethyl) Indoleamine, N,N-dimethylacetamide, ketone solvent (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ether solvent, aromatic hydrocarbon solvent, single One of an ether glycol solvent and the like.

Further, the inorganic filler is added by the composition of the thermosetting epoxy resin composition of the present invention and the hardening catalyst and the solvent, and the inorganic filler accounts for 1 to 30% by weight of the composition, and the inorganic filler of the present invention includes aluminum hydroxide [ Al(OH) ₃ ], aluminum hydroxide [AlOOH], magnesium hydroxide [Mg(OH) ₂ ], cerium oxide [SiO ₂ ], spherical type and crushed alumina [Al ₂ O ₃ ] It has an average particle diameter of from 0.01 micrometers to 20 micrometers.

In addition, the thermosetting epoxy resin composition of the present invention and the composition of the curing catalyst and the solvent may also be added with a highly thermally conductive inorganic filler to form a heat-dissipating insulating adhesive layer or substrate having a high thermal conductivity and a low dissipation coefficient, and the inorganic filler accounts for the composition. 10 to 80% by weight, preferably 40 to 65% by weight, the inorganic filler of the present invention may be hexagonal and spherical aluminum nitride [AlN], hexagonal and spherical boron nitride [BN], spherical And one of crushed alumina [Al ₂ O ₃ ], lanthanum carbide [SiC], and graphite [Graphite] having an average particle diameter of from 0.01 μm to 20 μm.

Please refer to Table 1 below. Table 1 is the preparation process of the epoxy resin varnish (Varnish) in the first embodiment, the solid polyfunctional aromatic polyester hardener, phenolphthalein oxynitride benzocyclohexane phenolic or The styrene maleic anhydride copolymer is added to a mixed solvent of methyl ethyl ketone (MEK), cyclohexanone and glycol-methoxy ether acetate (PMA), stirred and slowly warmed to 70 ° C until The double hardener mixture is in a clear and clear state, and then the mixture is cooled to 25~30 ° C, and then the hardening catalyst, the phosphorus-containing nitrogen-containing epoxy resin is added and stirred to become an epoxy resin varnish, and the viscosity of the formed varnish is formed. About 15±5 seconds (@ 25°Cby Cup#3) and its gel time is about 250±20 seconds (@170°C by hot platen)

Example 2: Fiberglass Reinforced Prepreg, through the method of Table 1 above, the epoxy resin varnish prepared in the first embodiment is used to prepare a prepreg film, and a woven glass fiber reinforcing material (7628) E-glass; 210 g/m ² ) impregnated varnish, and excess resin was removed by a two-roller gap (Gap), with a typical gap distance of about 0.015", and passed through a 170 °C channel oven, prepreg Stay in the continuous oven for about 5~6 minutes. After cooling, test the resin content. The resin content can be adjusted by adjusting the gap of the roller. Organic or inorganic woven or non-woven fiber reinforcement The degree of curing of the dip film is measured by a static viscosity (Melt viscosity; CAP2000@145 ° C) or a gelation time (Gel time @ 171 ° C), and the viscosity is about 200 to 400 cp and the gelation time is about 100 to 140 seconds.

Embodiment 3: Laminated board (in this embodiment, taking a copper foil substrate as an example), the prepreg film prepared in the second embodiment is used for preparing a copper foil substrate, and the 7628 prepreg film is cut into 18" x 24", and Stacking 8 sheets of prepreg in two loz copper foils, then placing the Cu-prepreg-Cu composition in two mirror stainless steel sheets, and finally feeding the stack into a vacuum press for further hardening reaction. The prepreg film needs at least 190 ° C / 90 minutes of heat to complete the curing reaction. In addition, at least 285-psi pressure (90 minutes) is required to enhance the bond between the prepreg and the prepreg and the copper foil, while the vacuum of the vacuum press needs to be maintained above 700 torr to avoid air ( Gas) is attached to the prepreg during the hardening process.

Table 2 below shows the electrical, mechanical and physical properties of the copper foil substrate produced in the first embodiment to the third embodiment.

As can be seen from the results listed in the above table, the thermosetting epoxy resin composition of the present invention has low dielectric constant and low dissipation coefficient (or low dielectric tangent) characteristics, and good thermal stability (T-288), and The hardened product has excellent flame retardancy (UL-94-V0), electrical and mechanical properties. Therefore, the thermosetting epoxy resin composition of the present invention can be used for a printed circuit laminate, a build-up bonding adhesive, an adhesive, and an encapsulating material.

The above is a specific embodiment of the present invention and the technical means employed, and many variations and modifications can be derived therefrom based on the disclosure or teachings herein. The function shall not be considered to be within the technical scope of the present invention, and it shall be considered in the technical scope of the present invention.

According to the above disclosure, the present invention can achieve the intended purpose of the invention, and provides a thermosetting resin composition, which has the value of industrial utilization and practicality, and proposes an invention patent according to law.

Claims (19)

A thermosetting resin composition comprising an epoxy resin and a hardener, wherein the hardener is a Phenolphthalein Benzoxazine Phenol by a polyfunctional aromatic polyester hardener Or a styrene-co-Maleic Anhydride (SMA) to form a double hardener system, wherein the phenolphthalein oxodiazobenzocyclohexane phenolic has an -OH value of 200~ 700, wherein the nitrogen content is 4 to 20% by weight. The thermosetting resin composition according to claim 1, wherein the polyfunctional aromatic polyester hardener is an aromatic polyvalent carboxylic acid residue having an aryloxycarbonyl group at a molecular chain terminal and an aromatic polyvalent. The hydroxy compound is formed by a reaction having an Ester Equivalent of 180 to 500. The thermosetting resin composition according to claim 1, wherein the styrene maleic anhydride copolymer has an acid value of 100 to 600. The thermosetting resin composition according to claim 1, wherein the epoxy resin is one of a phosphorus-containing epoxy resin, a nitrogen-containing epoxy resin, and a bisphenol F epoxy resin, or a combination thereof. The thermosetting resin composition according to claim 4, wherein the phosphorus-containing epoxy resin is a modified epoxy resin of DOPO-PNE, DOPO-CNE or DOPO-HQ, and the phosphorus content thereof is 2 to 10 wt%. Its epoxy equivalent (EEW) is 250~800. The thermosetting resin composition according to claim 4, wherein the nitrogen-containing epoxy resin is an N,N-Diglycidyl epoxy resin having an oxazolidine Oxazolidone ring epoxy resin, polyamide-imide-epoxy (PAI-epoxy) and the like, the nitrogen content of which is 5-20% by weight, and the epoxy equivalent thereof is 100~1000. The thermosetting resin composition according to claim 4, wherein the bisphenol F epoxy resin has an epoxy equivalent of from 150 to 1,000. The thermosetting resin composition according to claim 1, wherein a hardening catalyst is added. The thermosetting resin composition according to claim 8, wherein the epoxy resin composition comprises 10 to 90% by weight of an epoxy resin, 90 to 10% by weight of a double hardener system, and 0.01 to 5% by weight of a hardening catalyst. The thermosetting resin composition according to claim 9, wherein the double hardener system comprises 20 to 95% by weight of a polyfunctional aromatic polyester hardener and 5 to 80% by weight of phenolphthalein oxygen Benzene cyclohexane phenolic. The thermosetting resin composition according to claim 9, wherein the double hardener system comprises 20 to 95% by weight of a polyfunctional aromatic polyester hardener and 5 to 80% by weight of styrene Malay. Anhydride copolymer. The thermosetting resin composition according to claim 8, wherein the hardening catalyst is an imidazole compound, an organic phosphorus compound, an organic phosphate compound, a phosphate, a trialkylamine, or a 4-(II) One of methylamino)pyridine, quaternary ammonium salt, urea compound and the like. The thermosetting resin composition according to claim 8, which further comprises using a solvent to dissolve the thermosetting resin composition to form a varnish-like composition. The thermosetting resin composition according to claim 13, wherein the solvent may be a guanamine solvent (N-methylpyrrolidone, N-methylformamide, N,N-dimethyl Methionamine, N,N-dimethylacetamide, ketone solvent (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ether solvent, aromatic hydrocarbon solvent, One of monoether glycol solvents and the like. The thermosetting resin composition according to claim 13, wherein an inorganic filler is added, the inorganic filler is 1 to 30% by weight of the composition, and the inorganic filler is aluminum hydroxide or aluminum hydroxide. One of magnesium hydroxide, cerium oxide, spherical type and crushed alumina. The thermosetting resin composition according to claim 15, wherein the inorganic filler has an average particle diameter of from 0.01 μm to 20 μm. The thermosetting resin composition according to claim 13 , wherein a high thermal conductive inorganic filler is added, wherein the inorganic high thermal conductive filler accounts for 10 to 80% by weight of the composition, and the high thermal conductive inorganic filler can be hexagonal crystal. And one of spherical aluminum nitride, hexagonal and spherical boron nitride, spherical, crushed alumina, tantalum carbide and graphite. The thermosetting resin composition according to claim 17, wherein the niobium carbide includes a hexagonal crystal α-carbonized niobium and a cubic crystal β-carbonized niobium. The thermosetting resin composition according to claim 17, wherein the high thermal conductive inorganic filler has an average particle diameter of from 0.01 μm to 20 μm.