TW201817806A - Non-halogen resin composition - Google Patents

Abstract

The present invention provides anon-halogenresincomposition. Thenon-halogenresincomposition comprises: (A) 100 parts by weight of an epoxy resin; (B) 25-50 parts by weight of a maleic anhydride modified curing agent; (C) 20-60 parts by weight of a benzoxazine resin; (D) 20-65 parts by weight of a flame retardant; and (E) 0.5-20 parts by weight of a curing accelerator. Thenon-halogenresincompositioncomprises a specific composition and ratio to exhibit excellent properties of a circuit board such as high Tg, low dielectric properties, high thermal resistance, flame retardant property, and halogen free. The non-halogenresincomposition is suitable to form prepregs and a resin film that can be used in a metallic laminate and a printed circuit board.

Description

Halogen-free resin composition

The present invention relates to a halogen-free resin composition, and more particularly to a halogen-free resin composition having a low dielectric constant.

Due to the rise of global environmental awareness and the implementation of RoHS environmental protection regulations in the European Union, copper foil substrates have gradually replaced traditional FR-4 substrates with lead-free processes and halogen-free environmentally friendly substrates. In addition to Japanese manufacturers, Samsung Electronics, Apple, Dell, LG and other international companies have gradually introduced environmentally friendly substrates into mobile phones, consumer electronics and notebook computers, which will drive the penetration of environmentally friendly substrates in recent years.

Moreover, with the rapid development of wireless transmission products and the leap of high-frequency transmission technology, the materials of existing epoxy resin and phenolic resin systems have been unable to meet advanced applications, especially the demand for high-frequency printed circuit boards.

In the circuit board technology of a conventional copper foil substrate (or copper foil laminate), an epoxy resin and a hardener are used as a raw material of a thermosetting resin composition, and a reinforcing material (such as a glass fiber cloth) and the thermosetting resin are used. The composition is combined with heat to form a semipreg film, and the prepreg film is pressed together with the upper and lower copper foils under high temperature and high pressure. In the prior art, an epoxy resin and a phenol novolac resin hardener having a hydroxyl group (-OH) are generally used as a raw material of a thermosetting resin, and the combination of the phenol resin and the epoxy resin causes the epoxy group to form another hydroxyl group after ring opening. The hydroxyl group itself increases the dielectric constant and the dielectric loss value, and is easily combined with moisture to increase hygroscopicity.

There is a literature disclosed in which a cyanate resin, a dicyclopentadienyl epoxy resin, vermiculite, and a thermoplastic resin are used as a thermosetting resin composition having characteristics such as low dielectric constant and low dielectric loss. However, this manufacturing method must use a flame retardant containing a halogen (such as bromine) component, such as tetrabromocyclohexane, hexabromocyclodecane, and 2,4,6-tris(tribromophenoxy)-1. , 3,5-triazabenzene, and these bromine-containing flame retardants are easily polluted by the environment when the product is manufactured, used, or even recycled or discarded. In order to improve the heat and flame resistance of the copper foil substrate, low dielectric loss, low moisture absorption, high crosslink density, high glass transition temperature, high bondability, and appropriate thermal expansion, epoxy resin, hardener and reinforcing material Material selection has become a major factor.

Therefore, how to develop materials with excellent dielectric properties and other characteristics of printed circuit boards, such as high Tg, low coefficient of thermal expansion, and low water absorption, and applied to the manufacture of high frequency printed circuit boards is At this stage, the supplier of printed circuit board materials is eager to solve the problem.

It is an object of the present invention to provide a halogen-free resin composition which can achieve high glass transition temperature, low dielectric properties, high heat resistance, flame retardancy and halogen-free by containing specific component parts and ratios. Circuit board characteristics.

In order to achieve the above object, the present invention provides a halogen-free resin composition comprising: (A) 100 parts by weight of an epoxy resin; (B) 25-50 parts by weight of a maleic anhydride-modified hardener; (C) 20-60 parts by weight of a benzoxazine resin; (D) 20-65 parts by weight of a flame retardant; and (E) 0.5-20 parts by weight of a hardening accelerator.

In one aspect of the invention, the epoxy resin is selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac ring Oxygen resin, bisphenol A phenolic epoxy resin, bisphenol F phenolic epoxy resin, stilbene epoxy resin, epoxy resin containing triazine skeleton, epoxy resin containing ruthenium skeleton, trisphenol phenol methane Epoxy resin, biphenyl type epoxy resin, bismuth-based epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, alicyclic ring a polyglycidyl ether compound such as an oxygen resin, a polyfunctional phenol or a polycyclic aromatic compound such as hydrazine, a trifunctional or tetrafunctional epoxy resin having three or four epoxy groups in the molecule, and a phosphorus compound introduced therein One or more of the phosphorus-containing epoxy resins obtained in the like have a function of effectively increasing the glass transition temperature Tg (~175o).

The maleic anhydride-modified hardener is selected from one or more of the following materials, which has a function of effectively reducing the wear factor Df.

(1) Styrene-maleic anhydride copolymer Where m and n are the same or different positive integers;

(2) a modified maleic anhydride copolymer having the following formula 1 Where m and n are positive integers, which can be the same or different numbers, and R is: Wherein x, y and z are 0 or a positive integer, or a modified maleic anhydride copolymer having the following formula 2

Equation 2 Wherein X, Y and n are the same or different positive integers, and R is a cyclic olefin copolymer: or Wherein R ¹ , R ² , and R ³ are each a separate halogen atom, a carbon-containing alkyl group or an aromatic group, m and n are the same or different positive integers, or R is an acetic anhydride:

(3) Maleic anhydride modified polyimine resin having the following formula 3 Wherein X is a structure representing a carbon chain group having 10 or more carbon atoms, a benzene ring-containing group or a carbon chain having 10 or more carbon atoms and a benzene ring group, and m, n and l are integers and larger than Equal to 1.

The benzoxazine resin is selected from the group consisting of BPA type benzoxazine, BPF type benzoxazine, BPS type benzoxazine, DDM type benzoxazine, ODA type benzoxazine, and polyamidated benzene. One or more of polybenzoxazine with polyimide, which has an effective reduction in dielectric constant Dk (1-10 GHz, average about 4.1), loss factor Df (1-10 GHz, average about 0.008), and improvement Heat resistance function.

A flame retardant such as a non-dopo flame retardant, which is a compound containing phosphorus and/or a vinyl group, which has a flame retarding function as shown in the following structural formula;

Formula one Where R is selected from: One or more of the groups formed;

Formula 2 Where X is selected from: One or more of the group consisting of; Y is selected from: One or more of the group, n is an integer from 0 to 500;

Three Where X is selected from: One or more of the group consisting; A is selected from: One or more of the groups formed;

When n is 0, Y is:

When n is an integer from 1 to 500, Y is selected from: One or more of the group consisting of m≧0;

Z is selected from: One or more of the group consisting of m≧0.

The resin composition of the present invention does not use a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivative because of its disadvantage that the POC bond in the DOPO structure is easily hydrolyzed to P-OH will increase the dielectric constant and low dielectric loss of the material, so Non-dopo type flame retardant is used to avoid the Dk/Df of the material.

In addition to the non-dopo type flame retardant, the present invention may optionally further add at least one of the following specific flame retardant compounds. The flame retardant compound selected may be a phosphate compound or a nitrogen-containing phosphate compound, but is not limited thereto, for example: resorcinol dixylenyl phosphate (RDXP (such as PX-200) ), melamine polyphosphate, tri(2-carboxyethyl)phosphine (TCEP), trimethyl phosphate (TMP), tris(isopropyl chloride) Phosphate, dimethyl methyl phosphonate (DMMP), bisphenol diphenyl phosphate, ammonium polyphosphate, hydroquinone-bis-(biphenyl One or more of (hydroquinone bis-(diphenyl phosphate)), bisphenol A bis-(diphenylphosphate).

The hardening accelerator is selected from the group consisting of imidazole, boron trifluoride complex, 2-ethyl-4-methylimidazole (2E4MI), and 2-methylimidazole (2). -methylimidazole (2MI)), 2-phenyl-1H-imidazole (2PZ), ethyltriphenyl phosphonium chloride, triphenylphosphine (TPP) and One or more of 4-dimethylaminopyridine (DMAP) and a terminal bromine-based liquid butadiene rubber (BTPB).

The resin composition of one aspect of the present invention may further contain an inorganic filler to increase the thermal conductivity of the resin composition, to improve characteristics such as thermal expansion properties and mechanical strength. The inorganic filler is preferably uniformly distributed in the resin composition. The inorganic filler may be subjected to surface treatment in advance via a decane coupling agent. The inorganic filler may be in the form of a sphere, a sheet, a pellet, a column, a plate, a needle or an irregular shape. 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 carbide One or more of cerium, lanthanum carbide, titanium dioxide, zinc oxide, zirconium oxide, barium sulfate, magnesium carbonate, barium carbonate, mica, talc, and graphene.

In order to make those skilled in the art understand the technical content of the present invention and implement it, and according to the disclosure, the patent scope and the drawings, the related objects and advantages of the present invention can be easily understood by those skilled in the art. The detailed features and advantages of the present invention will be described in detail in the embodiments.

In order to make the above and other objects, features and advantages of the present invention more apparent, the embodiments of the present invention are described in detail as follows. The resin compositions of Examples 1 to 4 are listed in Table 1, Comparative Example 1 to The resin composition of 5 is listed in Table 3.

Example 1 (E1) A resin composition comprising the following components: (A) 40 parts by weight of dicyclopentadiene epoxy resin (HP-7200); (B) 60 parts by weight of biphenyl epoxy resin (NC) - 3000); (C) 25 parts by weight of styrene maleic anhydride (EF-60); (D) 50 parts by weight of benzoxazine resin (LZ 8280); (E) 35 parts by weight of a flame retardant (F) 1.5 parts by weight of the flame retardant compound (PX-200); (G) 35 parts by weight of molten cerium oxide; (H) 1 part by weight of a hardening accelerator (2E4MI); (I) 45 weight Methyl ethyl ketone solvent (MEK); (J) 20 parts by weight of propylene glycol methyl ether acetate solvent (PMA).

Example 2 (E2) A resin composition comprising the following components: (A) 40 parts by weight of dicyclopentadiene epoxy resin (HP-7200); (B) 60 parts by weight of biphenyl epoxy resin (NC) -3000); (C) 15 parts by weight of the modified maleic anhydride copolymer of the formula 1; (D) 15 parts by weight of the modified maleic anhydride copolymer of the formula 2; (E) 25 parts by weight of benzene And oxazin resin (LZ 8280); (F) 55 parts by weight of a three-type flame retardant; (G) 8 parts by weight of a flame retardant compound (TCEP); (H) 42 parts by weight of molten cerium oxide; I) 1 part by weight of a hardening accelerator (2E4MI); (J) 35 parts by weight of a methyl ethyl ketone solvent (MEK).

Example 3 (E3) A resin composition comprising the following components: (A) 40 parts by weight of dicyclopentadiene epoxy resin (HP-7200); (B) 60 parts by weight of biphenyl epoxy resin (NC) - 3000); (C) 35 parts by weight of a maleic anhydride-modified polyimine resin of the formula 3; (D) 37 parts by weight of a benzoxazine resin (LZ 8280); (E) 49 parts by weight 2 flame retardant; (F) 7 parts by weight of flame retardant compound (TMP); (G) 38 parts by weight of molten cerium oxide; (H) 1 part by weight of hardening accelerator (2E4MI); (I) 77 Parts by weight of methyl ethyl ketone solvent (MEK).

Embodiment 4 (E4) A resin composition comprising the following components: (A) 40 parts by weight of dicyclopentadiene epoxy resin (HP-7200); (B) 60 parts by weight of biphenyl epoxy resin (NC) - 3000); (C) 10 parts by weight of styrene maleic anhydride (EF-60); (D) 10 parts by weight of the modified maleic anhydride copolymer of the formula 1; (E) 10 parts by weight of the formula 2 a modified maleic anhydride copolymer; (F) 20 parts by weight of a maleic anhydride modified polyimine resin of the formula 3; (G) 20 parts by weight of a benzoxazine resin (LZ 8280); (H) 22 parts by weight of a flame retardant of formula 2; (I) 30 parts by weight of a flame retardant of formula 3; (J) 1 part by weight of a flame retardant compound (PX-200); (K) 3.5 parts by weight of flame retardant Compound (TCEP); (L) 1 part by weight of flame retardant compound (TMP); (M) 30 parts by weight of molten cerium oxide; (N) 10 parts by weight of spherical cerium oxide; (O)1 Parts by weight of a hardening accelerator (2E4MI); (P) 58 parts by weight of methyl ethyl ketone solvent (MEK); (Q) 20 parts by weight of propylene glycol methyl ether acetate solvent (PMA).

Comparative Example 1 (C1) A resin composition comprising the following components: (A) 40 parts by weight of dicyclopentadiene epoxy resin (HP-7200); (B) 60 parts by weight of biphenyl epoxy resin (NC) - 3000); (C) 30 parts by weight of styrene maleic anhydride (EF-60); (D) 36 parts by weight of a flame retardant; (E) 28 parts by weight of molten cerium oxide; (F) 1 part by weight of a hardening accelerator (2E4MI); (G) 42 parts by weight of methyl ethyl ketone solvent (MEK); (H) 20 parts by weight of propylene glycol methyl ether acetate solvent (PMA).

Comparative Example 2 (C2) A resin composition comprising the following components: (A) 40 parts by weight of dicyclopentadiene epoxy resin (HP-7200); (B) 60 parts by weight of biphenyl epoxy resin (NC) (C) 60 parts by weight of benzoxazine resin (LZ 8280); (D) 62 parts by weight of a three-type flame retardant; (E) 57 parts by weight of molten cerium oxide; (F) 1 Parts by weight of hardening accelerator (2E4MI); (G) 80 parts by weight of methyl ethyl ketone solvent (MEK).

Comparative Example 3 (C3) A resin composition comprising the following components: (A) 40 parts by weight of dicyclopentadiene epoxy resin (HP-7200); (B) 60 parts by weight of biphenyl epoxy resin (NC) (C) 20 parts by weight of the modified maleic anhydride copolymer of the formula 1; (D) 20 parts by weight of the modified maleic anhydride copolymer of the formula 2; (E) 60 parts by weight Two flame retardants; (F) 47 parts by weight of molten cerium oxide; (G) 1 part by weight of a hardening accelerator (2E4MI); (H) 114 parts by weight of a methyl ethyl ketone solvent (MEK).

Comparative Example 4 (C4) A resin composition comprising the following components: (A) 40 parts by weight of dicyclopentadiene epoxy resin (HP-7200); (B) 60 parts by weight of biphenyl epoxy resin (NC) - 3000); (C) 40 parts by weight of a maleic anhydride modified polyimine resin of the formula 3; (D) 50 parts by weight of a benzoxazine resin (LZ 8280); (E) 30 parts by weight Brominated flame retardant (SAYTEX 8010 (10Br)); (F) 41 parts by weight of molten cerium oxide; (G) 1 part by weight of hardening accelerator (2E4MI); (H) 97 parts by weight of methyl ethyl ketone Solvent (MEK).

Comparative Example 5 (C5) A resin composition comprising the following components: (A) 40 parts by weight of dicyclopentadiene epoxy resin (HP-7200); (B) 60 parts by weight of biphenyl epoxy resin (NC) - 3000); (C) 35 parts by weight of a maleic anhydride-modified polyimine resin of the formula 3; (D) 20 parts by weight of a benzoxazine resin (LZ 8280); (E) 30 parts by weight of the melt Cerium oxide; (F) 1 part by weight of a hardening accelerator (2E4MI); (G) 56 parts by weight of a methyl ethyl ketone solvent (MEK).

The resin compositions of the above Examples 1 to 4 and Comparative Examples 1 to 5 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, which are 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 220 ° 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 and the copper foil-etched copper-free substrate were respectively measured for physical properties, and the physical property measurement items included glass transition temperature (Tg), copper-containing substrate heat resistance (T288), and copper-containing substrate immersion tin test ( Solder dip 288 ° C, 10 seconds, measured heat resistance, S / D), copper-free substrate PCT moisture immersion tin test (pressure cooking at 121 ° C, after 1 hour, measured solder dip 288 ° C, 20 seconds to see if there is Explosive plate, PCT), copper foil and substrate lining copper foil (P/S), dielectric constant (the lower the Dk is better), dielectric loss (the lower the Df, the better), flame resistance (flaming test, UL94, where the ranks are ranked as V-0>V-1>V-2).

The substrate physical property measurement results of the resin compositions of Examples 1 to 4 are listed in Table 2, and the substrate physical property measurement results of the resin compositions of Comparative Examples 1 to 5 are listed in Table 4. From Tables 2 and 4, comparing Comparative Examples 1 to 4 and Comparative Examples 1 to 5, it can be found that, according to the content ratio of each component of the resin composition disclosed in the present invention, a substrate having better physical properties can be obtained, and a comparative example can be obtained. The substrate properties of 1 to 5 are poor. Among them, Examples 1 to 3 use different maleic anhydride modified hardeners, respectively, and the results show that the modified maleic anhydride copolymer of Formula 1 and Formula 2 is combined with the benzoxazine resin to obtain a better substrate heat resistance. Properties (Tg, T288, S/D) and copper foil tension (P/S), using a maleic anhydride modified polyimine resin of formula 3 with a benzoxazine resin, a better dielectric constant (Dk) And dielectric loss (Df).

As a result of Comparative Example 1, it was revealed that the substrate to which styrene maleic anhydride (EF60) was added but contained no benzoxazine resin was inferior in heat resistance (Tg, T288, S/D, PCT). The results of Comparative Example 2 show that the substrate to which the benzoxazine resin is added but does not contain the maleic anhydride-modified hardener has poor heat resistance (T288, S/D), poor copper foil pull (P/S), and dielectric properties. The constant (Dk) value is also poor. The results of Comparative Example 3 show that the substrate to which the modified maleic anhydride copolymer of Formula 1 and Formula 2 is added but does not contain the benzoxazine resin is inferior in heat resistance (Tg, T288, S/D, PCT), Copper foil pull (P/S) is poor, dielectric constant (Dk) and dielectric loss (Df) values are poor. As a result of Comparative Example 4, it was revealed that the substrate of the maleic anhydride-modified polyimine resin and the benzoxazine resin of the formula 3 was added to have poor electrical properties, and Comparative Example 4 used a bromine-containing compound as a flame retardant component. Although the UL94 V-0 flame resistance rating can be achieved, the halogen-free resin composition disclosed in the present invention does not use a halogen-containing (bromine) compound and is environmentally friendly. The result of the comparative example 5 shows that the resin composition disclosed in the present invention uses the maleic anhydride modified polyimine resin of the formula 3 in combination with the substrate of the benzoxazine resin, but does not add any flame retardant, and is resistant to flame. The rating is only a poor UL94 V-2 rating and does not reach the better V-0 rating.

Table I

Table II

Table 3

Table 4

The halogen-free resin composition of the present invention can be made into a semi-cured film or resin by including a specific composition and ratio so as to achieve low dielectric constant, low dielectric loss, high heat resistance and high flame resistance; The film can be applied to a copper foil substrate and a printed circuit board; in terms of industrial availability, the products derived from the present invention can fully satisfy the needs of the current market.

The above is only the preferred embodiment of the present invention, and is not intended to limit the scope of the invention, and other equivalent variations of the patent spirit of the present invention are all within the scope of the invention.

no

no

Claims (8)

A halogen-free resin composition comprising: (A) 100 parts by weight of an epoxy resin; (B) 25-50 parts by weight of a maleic anhydride modified hardener; (C) 20-60 parts by weight of a benzoxazine Resin; (D) 20-65 parts by weight of a flame retardant; and (E) 0.5-20 parts by weight of a hardening accelerator. The halogen-free resin composition of claim 1, wherein the epoxy resin is selected from at least one of the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin. , phenol novolak type epoxy resin, cresol novolac type epoxy resin, bisphenol A phenolic epoxy resin, bisphenol F phenolic epoxy resin, stilbene type epoxy resin, epoxy resin containing triazine skeleton Epoxy resin containing ruthenium skeleton, trisphenol phenol methane type epoxy resin, biphenyl type epoxy resin, exfoliating type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, two a cyclopentadiene type epoxy resin, an alicyclic epoxy resin, a polyfunctional phenol, a polyglycidyl ether compound such as fluorene, or a trifunctional group having three or four epoxy groups in the molecule; A tetrafunctional epoxy resin and a phosphorus-containing epoxy resin obtained by introducing a phosphorus compound thereto. The halogen-free resin composition of claim 1, wherein the maleic anhydride-modified hardener is at least one selected from the group consisting of: (1) a styrene-maleic anhydride copolymer. Wherein m and n are the same or different positive integers, (2) a modified maleic anhydride copolymer having the following formula 1: Where m, n are positive integers, which can be the same or different numbers, and R is: Wherein x, y, z are 0 or a positive integer, or a modified maleic anhydride copolymer having the following formula 2: Wherein X, Y and n are the same or different positive integers, and R is a cyclic olefin copolymer: or Wherein R ¹ , R ² and R ³ are each a separate halogen atom, a carbon-containing alkyl group or an aromatic group, m and n are the same or different positive integers, or R is acetic anhydride: (3) Maleic anhydride modified polyimine resin having the following formula 3 Wherein X is a structure representing a carbon chain group having 10 or more carbon atoms, a benzene ring-containing group or a carbon chain having 10 or more carbon atoms and a benzene ring group, and m, n and l are integers and Greater than or equal to 1. The halogen-free resin composition of claim 1, wherein the benzoxazine resin is selected from at least one of the group consisting of BPA type benzoxazine, BPF type benzoxazine, BPS type benzoxazine, DDM type benzoxazine, ODA type benzoxazine and polyamidated benzoxazine. The halogen-free resin composition of claim 1, wherein the flame retardant is selected from at least one of the group consisting of flame retardants having the following structural formula: Where R is selected from: One or more of the grouped groups; Where X is selected from: One or more of the group consisting of; Y is selected from: One or more of the group, n is an integer from 0 to 500; Where X is selected from: One or more of the group consisting; A is selected from: One or more of the groupings; when n is 0, Y is: When n is an integer from 1 to 500, Y is selected from: One or more of the group consisting of m≧0; Z is selected from: One or more of the group consisting of m≧0. The halogen-free resin composition of claim 1, further comprising a flame retardant compound selected from at least one of the group consisting of resorcinol bis-xylyl phosphate, melamine polyphosphate, and tri-2-carboxyethyl group. Phosphine, trimethyl phosphate, tri-isopropyl chloride-phosphate, dimethyl-methyl phosphate, bisphenol biphenyl phosphate, ammonium polyphosphate, hydroquinone-bis-biphenyl phosphate And bisphenol A-bis-biphenyl phosphate. The halogen-free resin composition of claim 1, wherein the hardening accelerator is selected from at least one of the group consisting of imidazole, boron trifluoride complex, 2-ethyl-4-methylimidazole, 2- Methylimidazole, 2-phenylimidazole, ethyltriphenylphosphonium chloride, triphenylphosphine and 4-dimethylaminopyridine. The halogen-free resin composition of claim 1, further comprising molten cerium oxide or spherical cerium oxide.