CN111205595A - Halogen-free low dielectric composition, laminate and printed wiring board - Google Patents

Halogen-free low dielectric composition, laminate and printed wiring board Download PDF

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Publication number
CN111205595A
CN111205595A CN202010098572.3A CN202010098572A CN111205595A CN 111205595 A CN111205595 A CN 111205595A CN 202010098572 A CN202010098572 A CN 202010098572A CN 111205595 A CN111205595 A CN 111205595A
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epoxy resin
halogen
low dielectric
resin
dielectric composition
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于达元
陈凯杨
林鸿名
苑绍杰
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ITEQ Corp
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ITEQ Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/02—Coating on the layer surface on fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The invention discloses a halogen-free low dielectric composition, a laminated board and a printed circuit board, wherein the halogen-free low dielectric composition (a) comprises 100 parts by weight of epoxy resin; (b)10 to 25 parts by weight of a DOPO-modified hardener; (c)10 to 20 parts by weight of a benzoxazine resin; (d)100 to 120 parts by weight of an active ester compound; (e)10 to 20 parts by weight of a maleic anhydride-modified hardener; and (f)20 to 45 parts by weight of a non-DOPO flame retardant. The halogen-free low dielectric composition can provide a halogen-free epoxy resin composition with specific components and proportions, and has the characteristics of high glass transition temperature, low dielectric constant, low dielectric loss, high heat resistance and high storage modulus.

Description

Halogen-free low dielectric composition, laminate and printed wiring board
Technical Field
The present invention relates to a low dielectric composition, a laminate and a printed circuit board, and more particularly to a halogen-free low dielectric composition, a laminate and a printed circuit board.
Background
In the printed circuit board technology, a thermosetting resin composition mainly comprising epoxy resin and a hardening agent is heated and combined with a reinforcing material to form a semi-cured film (prepreg), and then the semi-cured film is laminated with an upper copper foil and a lower copper foil at high temperature and high pressure to form a copper foil laminated board (or called a copper foil substrate). In general, a phenol formaldehyde (phenolic) resin hardener having hydroxyl group (-OH) is used in the thermosetting resin composition, which is combined with an epoxy resin to open the epoxy group to form hydroxyl group, and the hydroxyl group increases the dielectric constant and dielectric loss value, and is easily combined with H2O bonds, resulting in increased hygroscopicity.
The prior art epoxy resin composition uses flame retardants containing halogen components (especially bromine-based flame retardants), such as tetrabromocyclohexane, hexabromocyclodecane, and 2,4, 6-tris (tribromophenoxy) -1,3, 5-triazabenzene, etc., which have the advantages of good flame retardancy and less addition, however, under the new global environmental awareness, together with the RoHS environmental regulations implemented by the european union, lead-free processed copper foil substrates and halogen-free environment-friendly substrates gradually replace the conventional FR-4 substrates.
Therefore, how to develop a material with excellent dielectric properties and meeting the requirements of other characteristics of printed circuit boards, such as high glass transition temperature (Tg), low thermal expansion coefficient and low water absorption, and apply it to the manufacture of high frequency printed circuit boards is a problem that printed circuit board material suppliers are in urgent need of solution at present.
Disclosure of Invention
The present invention provides a halogen-free low dielectric constant composition, a laminate and a printed circuit board, which are directed to overcome the disadvantages of the prior art.
In order to solve the above technical problems, one of the technical solutions adopted by the present invention is to provide a halogen-free low dielectric composition, which comprises:
(a)100 parts by weight of an epoxy resin;
(b)10 to 25 parts by weight of a DOPO-modified hardener;
(c)10 to 20 parts by weight of a benzoxazine resin;
(d)100 to 120 parts by weight of an active ester compound;
(e)10 to 20 parts by weight of a maleic anhydride-modified hardener; and
(f)20 to 45 parts by weight of a non-DOPO flame retardant.
Preferably, the epoxy resin is at least one selected from the group consisting of a bisphenol a-type epoxy resin, a bisphenol F-type epoxy resin, a bisphenol S-type epoxy resin, a phenol novolac-type epoxy resin, a cresol novolac-type epoxy resin, a bisphenol a novolac-type epoxy resin, a bisphenol F novolac-type epoxy resin, a stilbene-type epoxy resin, a triazine skeleton-containing epoxy resin, a fluorene skeleton-containing epoxy resin, a triphenol methane-type epoxy resin, a biphenyl-type epoxy resin, a xylylene-type epoxy resin, a biphenyl aralkyl-type epoxy resin, a naphthalene-type epoxy resin, a dicyclopentadiene-type epoxy resin, an alicyclic epoxy resin, a diglycidyl ether compound of a polyfunctional phenol and a condensed ring aromatic group, a trifunctional and tetrafunctional epoxy resin having 3 or 4 epoxy groups in a molecule, and a phosphorus-containing epoxy resin.
Preferably, the DOPO-modified hardener is selected from the group consisting of DOPO-hydroquinone resin, DOPO-naphthalene diol resin, DOPO-novolac resin and DOPO-bisphenol novolac resin.
Preferably, the benzoxazine resin is at least one selected from the group consisting of: BPA-type benzoxazines, BPF-type benzoxazines, BPS-type benzoxazines, DDM-type benzoxazines, ODA-type benzoxazines and polyimidized benzoxazines.
Preferably, the active ester compound has the following structure:
Figure BDA0002386105930000021
wherein X is a benzene ring or a naphthalene ring, R1Is CH2Or
Figure BDA0002386105930000022
R2Is selected from the group consisting of naphthol, phenol, biphenol, bisphenol A, bisphenol F, bisphenol S and dicyclopentadiene (DCPD), l, m, k are 0 or 1, n is between 0.25 and 2.
Preferably, wherein the maleic anhydride modified hardener is at least one selected from the group consisting of:
(1) a styrene-maleic anhydride copolymer having the following structure;
Figure BDA0002386105930000031
wherein m and n are the same or different positive integers;
(2) a modified maleic anhydride copolymer having the structure:
Figure BDA0002386105930000032
wherein X, Y and n are the same or different positive integers, R is acetic anhydride; or
(3) A maleic anhydride-modified polyimide resin having the following structure:
Figure BDA0002386105930000033
wherein X represents a carbon chain group containing more than 10 carbon atoms, a benzene ring group or a structure of a carbon chain containing more than 10 carbon atoms and a benzene ring group, and m, n and l are integers and are more than or equal to 1.
Preferably, the halogen-free low dielectric composition further comprises: a hardening accelerator selected from the group consisting of boron trifluoride amine complex, 2-ethyl-4-methylimidazole, 2-phenylimidazole, ethyltriphenylphosphonium chloride, triphenylphosphine, cobalt (II) acetylacetonate, 4-dimethylaminopyridine, bromine-terminated liquid butadiene rubber, cobalt (II) bisacetylacetonate, cobalt (III) trisacetylacetonate, triethylamine, tributylamine, diazabicyclo [2,2,2] octane.
Preferably, the halogen-free low dielectric composition further comprises: an inorganic filler selected from the group consisting of silica, alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, barium sulfate, magnesium carbonate, barium carbonate, mica, talc, and graphene.
Preferably, the halogen-free low dielectric composition further comprises: a solvent selected from the group consisting of acetone, butanone, propylene glycol methyl ether acetate, dimethylacetamide, and cyclohexanone.
Preferably, the halogen-free low dielectric composition further comprises: a toughening agent, said toughening agent being a core shell polymer having a volume average particle size of from 0.01 to 1 μm.
Preferably, the core-shell polymer further comprises a core portion and a core shell, and the glass transition temperature of the core portion is less than 0 ℃ and the glass transition temperature of the core shell is less than 20 ℃.
Preferably, the core-shell polymer further comprises an intermediate layer, and the intermediate layer comprises 30 to 100 wt% of polyfunctional monomer and 0 to 70 wt% of vinyl monomer; wherein the shell portion of the core-shell polymer comprises an epoxy-based monomer.
In order to solve the above technical problem, another technical solution adopted by the present invention is to provide a laminate, including: a resin substrate comprising a plurality of semi-cured films, wherein each semi-cured film is prepared by coating a glass fiber cloth with the halogen-free low dielectric composition; and a metal foil layer disposed on at least one surface of the resin substrate.
In order to solve the above technical problem, another technical solution adopted by the present invention is to provide a printed circuit board, which includes the laminate according to the present invention.
One of the advantages of the present invention is that the halogen-free low dielectric composition can provide a halogen-free epoxy resin composition with specific components and ratios, and has the characteristics of high glass transition temperature, low dielectric constant, low dielectric loss, high heat resistance and high storage modulus. The semi-cured film or the resin film can be manufactured, and the purpose of being applied to a copper foil substrate and a printed circuit board is achieved; in terms of industrial applicability, the products derived from the invention can fully meet the current market demands.
For a better understanding of the features and technical aspects of the present invention, reference should be made to the following detailed description of the present invention, which is provided for purposes of illustration and description only and is not intended to be limiting.
Detailed Description
The following embodiments of the halogen-free low dielectric composition, laminate and printed circuit board disclosed in the present invention are illustrated by specific examples, and those skilled in the art can understand the advantages and effects of the present invention from the disclosure in the present specification. The invention is capable of other and different embodiments and its several details are capable of modification and various other changes, which can be made in various details within the specification and without departing from the spirit and scope of the invention. The following embodiments will further explain the related art of the present invention in detail, but the disclosure is not intended to limit the scope of the present invention.
It will be understood that, although the terms "first," "second," "third," etc. may be used herein to describe various components or signals, these components or signals should not be limited by these terms. These terms are used primarily to distinguish one element from another element or from one signal to another signal. In addition, the term "or" as used herein should be taken to include any one or combination of more of the associated listed items as the case may be.
A first embodiment of the present invention provides a halogen-free low dielectric composition comprising:
(a)100 parts by weight of an epoxy resin;
(b)10 to 25 parts by weight of a DOPO-modified hardener;
(c)10 to 20 parts by weight of a benzoxazine resin;
(d)100 to 120 parts by weight of an active ester compound;
(e)10 to 20 parts by weight of a maleic anhydride-modified hardener; and
(f)20 to 45 parts by weight of a non-DOPO flame retardant.
In one embodiment of the present invention, the epoxy resin of the present invention is selected from the group consisting of bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol a novolac type epoxy resin, bisphenol F novolac type epoxy resin, stilbene type epoxy resin, triazine skeleton-containing epoxy resin, fluorene skeleton-containing epoxy resin, at least one member selected from the group consisting of triphenol methane type epoxy resins, biphenyl type epoxy resins, xylylene type epoxy resins, biphenyl aralkyl type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, alicyclic epoxy resins, diglycidyl ether compounds of polyfunctional phenols and condensed ring aromatics, trifunctional and tetrafunctional epoxy resins having 3 or 4 epoxy groups in the molecule, and phosphorus-containing epoxy resins.
More specifically, the phosphorus-containing epoxy resin is a phosphorus-containing epoxy resin obtained by introducing a phosphorus compound into the epoxy resin; and the diglycidyl ether compounds of polyfunctional phenols and condensed ring aromatics may further include: glycidyl amine type epoxy resin (hydantoin epoxy resin) containing hydantoin rings (five-membered diazacyclo) in the molecular structure, which has the following formula:
Figure BDA0002386105930000061
wherein R is1And R2Is methyl or ethyl, n is a positive integer between 0 and 10;
Figure BDA0002386105930000062
wherein R is a benzene ring or a naphthalene ring.
Figure BDA0002386105930000063
In detail, the hydantoin Epoxy Resin (Hydantion) is a glycidyl amine type Epoxy Resin containing a hydantoin ring (five-membered diazacycle) in a molecular structure, and the most common is dimethyl hydantoin Epoxy Resin. Specifically, the hydantoin rings are effective in increasing toughness, rigidity, water solubility, and increasing the glass transition temperature Tg (to about 175 ℃). In addition, the low molecular weight dimethyl hydantoin epoxy resin can be further modified with an active toughening agent to improve the toughness of the epoxy resin (shown as a formula II); or reacting with acrylic acid to open the ring of the glycidyl group and introduce double bonds, and modifying the epoxy resin into water-soluble light-cured resin (shown as a formula III).
Preferably, the epoxy resin may be composed of the aforementioned types of resins in various proportions, for example, the epoxy resin of the present invention may be composed of 20 to 40 parts by weight of a dicyclopentadiene type epoxy resin, 10 to 20 parts by weight of a diglycidyl ether compound of polyfunctional phenols and condensed ring aromatics, and 40 to 60 parts by weight of a cresol novolac type epoxy resin. In more detail, the dicyclopentadiene type (DCPD) epoxy resin is effective in reducing the dielectric constant (Dk) value to 4.0. The diglycidyl ether compounds of the multifunctional phenols and the condensed ring aromatics can improve the glass transition temperature (Tg) and further improve the structural toughness of the product. Cresol novolac type epoxy resins can increase the glass transition temperature (Tg) and lower the electrical properties.
The modified 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, DOPO) hardener is mainly used as a hardener combined with epoxy resin, the modified hardener can provide good thermal stability and low dielectric property and can also improve the flame retardant effect, and the DOPO modified hardener in the halogen-free low dielectric composition is selected from a group consisting of DOPO-hydroquinone resin, DOPO-naphthalene diol resin, DOPO-novolac resin and DOPO-bisphenol phenol resin. Further, the DOPO-bisphenol A novolac resin is selected from the group consisting of DOPO-bisphenol A novolac resin (DOPO-BPAN), DOPO-bisphenol F novolac resin (DOPO-BPSN), and DOPO-bisphenol S novolac resin (DOPO-BPSN).
In one embodiment of the present invention, the benzoxazine resin is at least one selected from the following group: BPA-type benzoxazines, BPF-type benzoxazines, BPS-type benzoxazines, DDM-type benzoxazines, ODA-type benzoxazines, and polyimidized benzoxazines (polybenzoxazines with polyimines). The benzoxazine resin can reduce the dielectric constant Dk (1-10GHz, about 4.1 on average), dielectric loss factor Df (1-10GHz, about 0.008 on average) and improve the heat resistance.
In one embodiment of the present invention, the active ester compound has the following structure:
Figure BDA0002386105930000071
wherein X is a benzene ring or a naphthalene ring, R1Is CH2Or
Figure BDA0002386105930000072
R2Is selected from the group consisting of naphthol, phenol, biphenol, bisphenol A, bisphenol F, bisphenol S and dicyclopentadiene (DCPD), l, m, k are 0 or 1, n is between 0.25 and 2. Specifically, the active ester compound can effectively reduce the dielectric constant Dk and the loss factor Df and improve the flame retardant effect.
In one embodiment of the present invention, the maleic anhydride modified hardener is selected from at least one of the following groups:
(1) a styrene-maleic anhydride copolymer having the structure:
Figure BDA0002386105930000081
wherein m and n are the same or different positive integers;
(2) a modified maleic anhydride copolymer having the structure:
Figure BDA0002386105930000082
wherein X, Y and n are the same or different positive integers, and R is acetic anhydride; or
(3) A maleic anhydride-modified polyimide resin having the following structure:
Figure BDA0002386105930000083
wherein X represents a carbon chain group containing more than 10 carbon atoms, a benzene ring group or a structure of a carbon chain containing more than 10 carbon atoms and a benzene ring group, and m, n and l are integers and are more than or equal to 1.
Specifically, the maleic anhydride modified hardener can reduce the dielectric loss factor Df (1-10GHz, about 0.008 on average) and improve the heat resistance.
In one embodiment of the invention, the flame retardant of the invention uses a non-DOPO flame retardant, i.e. does not contain a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivative. In detail, the P-O-C bond in the DOPO structure is easily hydrolyzed into P-OH, which increases the dielectric constant and dielectric loss of the material, so the non-DOPO flame retardant can avoid increasing the dielectric constant Dk and dielectric loss Df of the material.
In more detail, the non-DOPO flame retardant may be selected from the group consisting of compounds of structural formula (I), structural formula (II), and structural formula (III):
Figure BDA0002386105930000091
Figure BDA0002386105930000092
and
Figure BDA0002386105930000093
wherein R is1Is that
Figure BDA0002386105930000094
Figure BDA0002386105930000101
Wherein R is2Is that
Figure BDA0002386105930000102
Wherein R is3Is that
Figure BDA0002386105930000103
Or CH2CH2OCH＝CH2；
Wherein n is an integer of 0 to 500;
wherein R is4Is that
Figure BDA0002386105930000111
Wherein m is ≧ 1;
wherein R is5Is that
Figure BDA0002386105930000112
Wherein R is6Is that
Figure BDA0002386105930000113
Figure BDA0002386105930000114
In particular, the non-DOPO flame retardant may be selected from phosphate compounds or nitrogen-containing phosphate compounds, for example, may be selected from the group consisting of resorcinol dixylylphosphates (RDXP (e.g., PX-200)), melamine polyphosphates (melamine polyphosphate), tris (2-carboxyethyl) phosphine (tri (2-carboxyethyl) phosphine, TCEP), Trimethylphosphates (TMP), tris (isopropylchloride) phosphate, dimethyl-methyl phosphate (DMMP), bisphenol diphenyl phosphate (biphenol diphosphate), ammonium polyphosphate (ammoniumphosphate), hydroquinone-bis- (biphenylphosphate), bisphenol a-bis- (biphenylphosphate), and Phosphazene compounds (Phosphazene, e.g., SPB-100).
Preferably, the hardening accelerator of the present invention may be at least one selected from the group consisting of imidazole, metal salt, tertiary amine or piperidine compounds or a mixture thereof, and further may be selected from boron trifluoride amine complex, 2-ethyl-4-methylimidazole (2-ethyl-4-methylimidazole, 2E4MI), 2-methylimidazole (2-methylimidazole, 2MI), 2-phenylimidazole (2-phenylimidazole-1H-imidazolidone, 2PZ), ethyltriphenylphosphonium chloride (ethyltriphenylphosphonium chloride), Triphenylphosphine (TPP), cobalt (ii) acetylacetonate (cobalt (ii) acetate), and 4-dimethylaminopyridine (4-dimethylammonium pyrrolidone, DMAP), low molecular weight terminal brominated liquid butadiene rubber (pb), such as acetylacetone (btii) sulfate, and a mixture thereof, Cobalt (III) triacetylacetonate, tertiary amines such as triethylamine, tributylamine, etc., diazabicyclo [2,2,2] octane, etc. More preferably, the hardening accelerator is 4-dimethylaminopyridine (4-dimethylamino-pyridine). Specifically, the imidazole compound has particularly good compatibility with the resin component, whereby a cured product having high uniformity can be obtained. Preferably, the amount of the hardening accelerator may be 1% based on 100 parts by weight of the epoxy resin.
On the other hand, the inorganic filler can increase the thermal conductivity of the halogen-free low dielectric composition, improve the thermal expansion and mechanical strength thereof, and is preferably uniformly distributed in the halogen-free low dielectric composition. Preferably, the inorganic filler may be previously surface-treated with a silane coupling agent. Preferably, the inorganic filler may be spherical, flaky, granular, columnar, plate-like, needle-like or irregular. Preferably, the inorganic filler is selected from the group consisting of silica (e.g., fused, non-fused, porous or hollow silica), alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, barium sulfate, magnesium carbonate, barium carbonate, mica, talc, and graphene. Preferably, the inorganic filler may be added in an amount of 100 to 120 parts by weight based on 100 parts by weight of the epoxy resin.
In addition, the halogen-free low dielectric constant composition of the present invention further comprises a suitable amount of solvent, such as ketones, esters, ethers, alcohols, etc., and more specifically, the solvent of the present invention is selected from the group consisting of acetone, methyl ethyl ketone, propylene glycol methyl ether acetate, dimethylacetamide, and cyclohexanone. For example, the solvent may be selected from a combination of 25 to 35 parts by weight of Methyl Ethyl Ketone (MEK) and 20 to 30 parts by weight of propylene glycol methyl ether acetate (PMA), or other solvents, and the like.
Furthermore, the halogen-free low dielectric composition of the present invention optionally further comprises a toughening agent, such as a core-shell polymer, for improving the toughness of the board and improving the heat resistance. Preferably, the toughening agent may be selected from epoxy type toughening agents such as MX series products of KANEKA and W series products of Metablen, and may be added in an amount of 2 parts by weight based on 100 parts by weight of the epoxy resin. Specifically, the volume average particle diameter of the core-shell polymer is 0.01 to 1 μm, preferably 0.1 to 0.5 μm, and the glass transition temperature (Tg) of the core portion of the core-shell polymer is less than 0 ℃, and the glass transition temperature (Tg) of the shell portion of the core-shell polymer is less than 20 ℃, more specifically, the core-shell polymer includes an intermediate layer between the core portion and the shell portion, the intermediate layer includes 30 to 100 wt% of a polyfunctional monomer and 0 to 70 wt% of a vinyl monomer, and the shell portion of the core-shell polymer includes an epoxy group-containing monomer, and the heat resistance of the composition of the present invention can be further improved by combining the epoxy group monomer of the core-shell polymer with an epoxy group of an epoxy resin.
The present invention also provides another technical solution, which is a laminate, comprising: (a) a resin substrate including a plurality of semi-cured films, each of the semi-cured films being made of a glass cloth coated with the halogen-free low dielectric composition according to the present invention; and (b) a metal foil layer disposed on at least one surface of the resin substrate, or the metal foil layer may be disposed on the resin substrate up and down as required.
In addition, another technical solution of the present invention is a printed circuit board including the laminate of the present invention.
Examples
The following examples E1-E5 illustrate the use of the halogen-free low dielectric composition of the present invention to make prepreg in a continuous process. Usually, a glass fiber cloth is used as a substrate. The rolled glass fiber cloth continuously passes through a series of rollers and enters a sizing groove, and the groove is filled with the halogen-free low dielectric composition. Fully soaking glass fiber cloth in resin in a glue feeding groove, scraping redundant resin through a metering roller, baking the glass fiber cloth in a glue feeding furnace for a certain time to evaporate a solvent and solidify the resin to a certain degree, cooling and rolling the glass fiber cloth to form a semi-solidified film, taking four semi-solidified films and two 18 mu m copper foils of the same batch of semi-solidified films, superposing the semi-solidified films and the copper foils in sequence, and pressing the semi-solidified films at 220 ℃ for 2 hours under a vacuum condition to form a copper foil substrate, wherein the four semi-solidified films are solidified to form an insulating layer between the two copper foils.
TABLE 1
Figure BDA0002386105930000131
Figure BDA0002386105930000141
Comparative example
Prepreg was manufactured in a continuous process according to the components and proportions of comparative examples C1 to C5 of table 2 below. Usually, a glass fiber cloth is used as a substrate. The rolled glass fiber cloth continuously passes through a series of rollers and enters a sizing groove, and the groove is filled with the halogen-free low dielectric composition. Fully soaking glass fiber cloth in resin in a glue feeding groove, scraping redundant resin through a metering roller, baking the glass fiber cloth in a glue feeding furnace for a certain time to evaporate a solvent and solidify the resin to a certain degree, cooling and rolling the glass fiber cloth to form a semi-solidified film, taking four semi-solidified films and two 18 mu m copper foils of the same batch of semi-solidified films, superposing the semi-solidified films and the copper foils in sequence, and pressing the semi-solidified films at 220 ℃ for 2 hours under a vacuum condition to form a copper foil substrate, wherein the four semi-solidified films are solidified to form an insulating layer between the two copper foils.
TABLE 2
Figure BDA0002386105930000151
Figure BDA0002386105930000161
HP-7200: DCPD (dicyclopentadiene type) epoxy resin
NC-3000: biphenyl epoxy resin of Japan chemical Co
Physical Property test
Physical properties of the copper clad laminates of examples E1 to E5 and comparative examples C1 to C5 were measured, and the test results were recorded in table 3:
(1) glass transition temperature (Tg): according to Differential Scanning Calorimetry (DSC), the measurement was carried out according to the DSC method specified by IPC-TM-6502.4.25.
(2) Heat resistance of copper foil laminate (T288): also known as the "tin floating result", the heat resistance test was conducted by immersing the copper clad laminate in a tin furnace at 288 ℃ for the time required for board explosion according to the industry standard IPC-TM-6502.4.24.1.
(3) And (3) carrying out wicking test on the copper foil-containing laminated plate after moisture absorption: the prepreg containing copper foil layer was used for heat resistance (T288) test and the copper clad laminate was immersed in a tin furnace at 288 ℃ for the time required for board burst according to industry standard IPC-TM-6502.4.24.1.
(4) Heat resistance (S/D) test of copper foil laminate: copper-containing substrates were tested for wicking (solder dip 288 ℃,10 seconds, heat cycle resistance).
(5) Heat resistance (PCT) test of copper foil laminate: no copper substrate PCT immersion tin test after moisture absorption (pressing at 121 deg.C, 1 hour later, the solder dip 288 deg.C, 20 seconds to see if there is a plate explosion).
(6) Tension (P/S) between copper foil and substrate: the determination was made according to the IPC-TM-6502.4.1 test specification.
(7) Dielectric constant (Dk): the dielectric constant represents the electrical insulation property of the film produced, and lower values represent better electrical insulation properties, as determined by IPC-TM-6502.5.5 test specifications.
(8) Dielectric loss (Df): dielectric loss, measured according to IPC-TM-6502.5.5 test specifications, indicates the ability of a substance to absorb microwaves of a certain frequency at a certain temperature, and generally, in the specifications of communication products, the lower the dielectric loss value, the better.
Flame resistance (flaming test, UL 94): the flame resistance rating of the plastic material is determined according to the UL94 vertical combustion method by the spontaneous combustion time, spontaneous combustion speed and falling particle state of the standard test piece of the plastic material after flame combustion. And HB, V-2, V-1 and V-0 are sequentially arranged according to the grade of flame resistance, and the highest grade is 5V. Whereas the UL94 test method refers to the burning of plastic material in a vertical manner on a flame. Every ten seconds is taken as a test period, and the steps are as follows: the method comprises the following steps: placing the test piece in the flame for ten seconds and removing the test piece, and measuring the burning time of the test piece after the removal (T1); step two: when the flame of the test piece is extinguished, putting the test piece into the flame for ten seconds, removing the test piece, and measuring the continuous burning time of the test piece after the removal (T2); step three: repeating the experiment for a plurality of times and taking the average value; step four: the total of T1+ T2 was calculated. The UL 94V-0 rating is required to satisfy the UL 94V-0 requirement that neither the average of T1 nor the average of T2 should exceed 10 seconds, and the sum of T1 and T2 should not exceed 50 seconds.
Figure BDA0002386105930000181
Advantageous effects of the embodiments
One of the advantages of the present invention is that the halogen-free low dielectric composition can provide a halogen-free epoxy resin composition with specific components and ratios, and has the characteristics of high glass transition temperature, low dielectric constant, low dielectric loss, high heat resistance and high storage modulus. The semi-cured film or the resin film can be manufactured, and the purpose of being applied to a copper foil substrate and a printed circuit board is achieved; in terms of industrial applicability, the products derived from the invention can fully meet the current market demands.
The disclosure is only a preferred embodiment of the invention and should not be taken as limiting the scope of the invention, which is defined by the appended claims.

Claims (14)

1. A halogen-free low dielectric composition, comprising:
(a)100 parts by weight of an epoxy resin;
(b)10 to 25 parts by weight of a DOPO-modified hardener;
(c)10 to 20 parts by weight of a benzoxazine resin;
(d)100 to 120 parts by weight of an active ester compound;
(e)10 to 20 parts by weight of a maleic anhydride-modified hardener; and
(f)20 to 45 parts by weight of a non-DOPO flame retardant.
2. Halogen free low dielectric composition according to claim 1, the epoxy resin is at least one selected from the group consisting of bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol a novolac type epoxy resin, bisphenol F novolac type epoxy resin, stilbene type epoxy resin, triazine skeleton-containing epoxy resin, fluorene skeleton-containing epoxy resin, triphenol methane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, alicyclic epoxy resin, diglycidyl ether compounds of polyfunctional phenols and condensed ring aromatics, trifunctional and tetrafunctional epoxy resins having 3 or 4 epoxy groups in a molecule, and phosphorus-containing epoxy resins.
3. The halogen-free low dielectric composition of claim 1 wherein the DOPO modified hardener is selected from the group consisting of DOPO-hydroquinone resin, DOPO-naphthalene diol resin, DOPO-novolac resin, and DOPO-bisphenol phenol resin.
4. The halogen-free low dielectric composition of claim 1 wherein the benzoxazine resin is at least one selected from the group consisting of: BPA-type benzoxazines, BPF-type benzoxazines, BPS-type benzoxazines, DDM-type benzoxazines, ODA-type benzoxazines and polyimidized benzoxazines.
5. The halogen-free low dielectric composition of claim 1 wherein the active ester compound has the structure:
Figure FDA0002386105920000011
wherein X is a benzene ring or a naphthalene ring, R1Is CH2Or
Figure FDA0002386105920000024
R2Is selected from the group consisting of naphthol, phenol, biphenol, bisphenol A, bisphenol F, bisphenol S and dicyclopentadiene (DCPD), l, m, k are 0 or 1, n is between 0.25 and 2.
6. The halogen-free low dielectric 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 having the following structure;
Figure FDA0002386105920000021
wherein m and n are the same or different positive integers;
(2) a modified maleic anhydride copolymer having the structure:
Figure FDA0002386105920000022
wherein X, Y and n are the same or different positive integers, R is acetic anhydride; or
(3) A maleic anhydride-modified polyimide resin having the following structure:
Figure FDA0002386105920000023
wherein X represents a carbon chain group containing more than 10 carbon atoms, a benzene ring group or a structure of a carbon chain containing more than 10 carbon atoms and a benzene ring group, and m, n and l are integers and are more than or equal to 1.
7. The halogen-free low dielectric composition of claim 1 further comprising: a hardening accelerator selected from the group consisting of boron trifluoride amine complex, 2-ethyl-4-methylimidazole, 2-phenylimidazole, ethyltriphenylphosphonium chloride, triphenylphosphine, cobalt (II) acetylacetonate, 4-dimethylaminopyridine, bromine-terminated liquid butadiene rubber, cobalt (II) bisacetylacetonate, cobalt (III) trisacetylacetonate, triethylamine, tributylamine, diazabicyclo [2,2,2] octane.
8. The halogen-free low dielectric composition of claim 1 further comprising: an inorganic filler selected from the group consisting of silica, alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, barium sulfate, magnesium carbonate, barium carbonate, mica, talc, and graphene.
9. The halogen-free low dielectric composition of claim 1 further comprising: a solvent selected from the group consisting of acetone, butanone, propylene glycol methyl ether acetate, dimethylacetamide, and cyclohexanone.
10. The halogen-free low dielectric composition of claim 1 further comprising: a toughening agent, said toughening agent being a core shell polymer having a volume average particle size of from 0.01 to 1 μm.
11. The halogen-free low dielectric composition of claim 10 wherein the core-shell polymer further comprises a core portion and a core-shell, and wherein the glass transition temperature of the core portion is less than 0 ℃ and the glass transition temperature of the core-shell is less than 20 ℃.
12. The halogen-free low dielectric composition of claim 11 wherein the core-shell polymer further comprises an intermediate layer, and the intermediate layer comprises 30 to 100 wt% of a multifunctional monomer and 0 to 70 wt% of a vinyl monomer; wherein the shell portion of the core-shell polymer comprises an epoxy-based monomer.
13. A laminate panel, comprising:
a resin substrate comprising a plurality of prepreg sheets, each of the prepreg sheets being made of a glass cloth coated with the halogen-free low dielectric composition according to claim 1; and
and the metal foil layer is arranged on at least one surface of the resin substrate.
14. A printed circuit board comprising the laminate of claim 13.
CN202010098572.3A 2020-02-18 2020-02-18 Halogen-free low dielectric composition, laminate and printed wiring board Pending CN111205595A (en)

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CN116970260A (en) * 2023-09-22 2023-10-31 深圳先进电子材料国际创新研究院 Epoxy plastic package material and preparation method and application thereof
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