CN114806078B - Low expansion coefficient halogen-free resin composition, laminated board and printed circuit board - Google Patents

Low expansion coefficient halogen-free resin composition, laminated board and printed circuit board Download PDF

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CN114806078B
CN114806078B CN202110060714.1A CN202110060714A CN114806078B CN 114806078 B CN114806078 B CN 114806078B CN 202110060714 A CN202110060714 A CN 202110060714A CN 114806078 B CN114806078 B CN 114806078B
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weight
halogen
resin composition
expansion coefficient
parts
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CN114806078A (en
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于达元
陈凯杨
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ITEQ Corp
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ITEQ Corp
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with 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
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/036—Multilayers with layers of different types
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2307/30—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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
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Abstract

The application discloses a halogen-free resin composition with low expansion coefficient, a laminated board and a printed circuit board. The halogen-free resin composition of the present application comprises: (a) 30 to 40 parts by weight of an o-cresol formaldehyde epoxy resin, (b) 50 to 70 parts by weight of a bismaleimide resin, (c) 75 to 105 parts by weight of a cyanate ester hardener, (d) 30 to 45 parts by weight of a bisphenol a type DOPO hardener, (e) 10 to 20 parts by weight of a non-DOPO phosphorus-containing flame retardant, and (f) 2 to 12 parts by weight of a DOPO flame retardant. The halogen-free resin composition of the application can provide the epoxy resin composition with low expansion coefficient, low dielectric loss and high rigidity, and provides better material toughness and heat resistance through specific components and proportions.

Description

Low expansion coefficient halogen-free resin composition, laminated board and printed circuit board
Technical Field
The present application relates to a resin composition, a laminate and a printed circuit board using the same, and more particularly, to a halogen-free resin composition, a laminate and a printed circuit board having a low expansion coefficient, a low dielectric loss and a high rigidity.
Background
Under the continuous fever of the communication electronic market, high-frequency high-speed transmission has become a necessary option, and a circuit board playing a role in bearing components, power supply and signal transmission is a key in the development of the field, but the prior art of printed circuit boards made of epoxy resin and phenolic resin materials cannot meet the advanced application of high frequency.
In the printed circuit board technology, mainly comprises a thermosetting resin composition of epoxy resin and a hardener, and is combined with a reinforcing material (such as glass fiber cloth) by heating to form a prepreg, and then is pressed 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). A typical thermosetting resin composition uses a phenolic (phenolic) resin hardener having hydroxyl groups (-OH) which, when combined with an epoxy resin, open the epoxy groups to form hydroxyl groups which, in turn, increase the dielectric constant and dielectric loss value and are liable to react with H 2 O bonds, resulting in increased hygroscopicity.
The epoxy resin composition of the prior art uses a flame retardant (particularly, a brominated flame retardant) containing a halogen component, such as tetrabromocyclohexane, hexabromocyclodecane, 2,4, 6-tris (tribromophenoxy) -1,3, 5-triazabenzene, etc., which has advantages of good flame retardance and less addition, however, halogen products are liable to cause environmental pollution even when being recycled or discarded, in addition to which corrosive, toxic gas and smoke are generated when the halogen-containing electronic device waste is burned, and the carcinogenic substances such as dioxin, dibenzofuran, etc. are detected after the combustion. Therefore, halogen-free flame retardant printed circuit boards have become an important development point in the art.
In addition to the development of halogen-free flame retardant printed circuit boards, the characteristics of heat resistance, flame retardancy, low dielectric loss, low hygroscopicity, high crosslinking density, high glass transition temperature, high bondability, proper thermal expansion and the like of copper foil substrates are important subjects for the development and manufacture of printed circuit boards, and therefore, the selection of materials of epoxy resin, hardener and reinforcing material is a main influencing factor.
Disclosure of Invention
The application aims to solve the technical problem of providing a halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity, a laminated board and a printed circuit board aiming at the defects of the prior art.
In order to solve the above-mentioned problems, one of the technical solutions adopted in the present application is to provide a halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity, which comprises:
(a) 30 to 40 parts by weight of an o-cresol formaldehyde epoxy resin;
(b) 50 to 70 parts by weight of a bismaleimide resin;
(c) 75 to 105 parts by weight of a cyanate ester hardener;
(d) 30 to 45 parts by weight of a bisphenol a type DOPO hardener;
(e) 10 to 20 parts by weight of a non-DOPO phosphorus containing flame retardant; and
(f) 2 to 12 parts by weight of a DOPO flame retardant;
wherein the DOPO flame retardant is selected from the group consisting of the following chemical formulas (I) and (II):
wherein R is 1 Is C (R) 4 ) 2 ；R 2 R is R 3 Each independently is hydrogen, C1-C15 alkyl, C6-C12 aryl, C7-C15 aralkyl, or C7-C15 alkaryl; or R is 2 And R is R 3 A saturated or unsaturated cyclic ring substituted or unsubstituted with a C1-C6 alkyl group; each R is 4 Independently hydrogen, C1-C6 alkyl, C6-C12 aryl or C3-C12 cycloalkyl; and each m is independently selected from a positive integer of 1 to 4;
wherein A is a direct bond, C6-C12 aryl, C3-C12 cycloalkyl or C3-C12 cycloalkenyl, and cycloalkyl or cycloalkenyl may be optionally substituted with C1-C6 alkyl;
wherein R is 1 、R 2 、R 3 R is R 4 Independently hydrogen, C1-C15 alkyl, C6-C12 aryl, C7-C15 aralkyl or C7-C15 alkaryl; or R is 1 And R is R 2 Or R is 3 And R is R 4 Can form a warpA C1-C6 alkyl substituted or unsubstituted saturated or unsaturated cyclic ring; each m is independently selected from a positive integer of 1 to 4, each R 5 And R is 6 Independently hydrogen or C1-C6 alkyl; each n is independently selected from positive integers from 0 to 5.
Still further, the bismaleimide is selected from the group consisting of bis (4-maleimidophenyl) methane, 2-bis (4- (4-maleimidophenoxy) -phenyl) propane, bis (3, 5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, and bis (3, 5-diethyl-4-maleimidophenyl) methane.
Still further, the cyanate ester hardener includes 45 to 55 parts by weight of a phenolic cyanate ester hardener and 30 to 50 parts by weight of a bisphenol a type cyanate ester hardener.
Still further, the bisphenol a type DOPO hardener has the following structure:
still further, the non-DOPO flame retardant is selected from the group consisting of resorcinol bisxylyl phosphate, melamine polyphosphate, tris (2-carboxyethyl) phosphine, trimethyl phosphate, tris (isopropyl chloride) phosphate, dimethyl methylphosphonate, bisphenol diphenyl phosphate, ammonium polyphosphate, hydroquinone bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), and phosphazene compound.
Still further, the low expansion coefficient halogen-free resin composition further comprises: a hardening accelerator selected from the group consisting of phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, guanidine-based hardening accelerators, metal-based hardening accelerators, and peroxide-based hardening accelerators.
Still further, the hardening accelerator includes: 1 part by weight of a metal-based hardening accelerator, 1 part by weight of 2-ethyl-4-methylimidazole, and 1 part by weight of a peroxide-based hardening accelerator.
Still further, the low expansion coefficient halogen-free resin 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.
In order to solve the above technical problems, another technical solution adopted by the present application is to provide a laminated board, which includes: a resin substrate comprising a plurality of semi-cured films, each of the semi-cured films being made of a glass fiber cloth by coating the halogen-free resin composition of the present application having low expansion coefficient, low dielectric loss and high rigidity; and a metal foil layer disposed on at least one surface of the resin substrate.
In order to solve the above-mentioned problems, another aspect of the present application is to provide a printed circuit board, which includes a laminate according to the present application.
The halogen-free resin composition with low expansion coefficient, the laminated board and the printed circuit board provided by the application have the beneficial effects that the halogen-free resin composition with low expansion coefficient, the laminated board and the printed circuit board can be provided through specific components and proportions, and meanwhile, the toughness and the heat resistance of the board are improved, and the cost is reduced. In addition, the composition can be made into semi-cured films or resin films, so that the purpose of being applied to copper foil substrates and printed circuit boards is achieved, and the product derived by the composition can fully meet the current market demands in terms of industrial availability.
For a further understanding of the nature and the technical aspects of the present application, reference should be made to the following detailed description of the application, which is to be taken in a limiting sense, however, the present application is defined by the accompanying drawings.
Detailed Description
The following is a description of embodiments of the present application disclosed herein with respect to a low expansion coefficient halogen-free resin composition, a laminate, and a printed circuit board, and those skilled in the art will appreciate the advantages and effects of the present application from the disclosure herein. The application is capable of other and different embodiments and its several details are capable of modification and variation in various respects, all from the point of view and application, all without departing from the spirit of the present application. The following embodiments will further illustrate the related art content of the present application in detail, but the disclosure is not intended to limit the scope of the present application. In addition, the term "or" as used herein shall include any one or combination of more of the associated listed items as the case may be.
The term "alkyl" as used herein includes saturated monovalent hydrocarbon radicals having straight or branched chain moieties. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, and hexyl.
The term "alkenyl" as used herein includes alkyl moieties having at least one carbon-carbon double bond, wherein alkyl is as defined above. Examples of alkenyl groups include, but are not limited to, ethenyl and propenyl.
The term "aryl" as used herein includes organic groups derived from aromatic hydrocarbons by removal of one hydrogen, such as phenyl, naphthyl, indenyl and fluorenyl. "aryl" encompasses fused ring groups in which at least one ring is an aromatic ring.
The term "aralkyl" as used herein is an "aryl-alkyl-" group. Non-limiting examples of aralkyl groups are benzyl (C6H 5CH 2-) and methylbenzyl (CH 3C6H4CH 2-).
The term "alkylaryl" as used herein is an "alkyl-aryl-" group. Non-limiting examples of alkylaryl groups are methylphenyl-, dimethylphenyl-, ethylphenyl-, propylphenyl-, isopropylphenyl-, butylphenyl-, isobutylphenyl-, and tert-butylphenyl-.
As used herein, the term "cycloalkyl" includes non-aromatic saturated cyclic alkyl moieties, wherein alkyl is as defined above. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.
Unless otherwise indicated, all of the above hydrocarbon-derived groups may have from about 1 to about 20 carbon atoms (e.g., C1-C20 alkyl, C6-C20 aryl, C7-C20 alkylaryl, C7-C20 aralkyl) or from 1 to about 12 carbon atoms (e.g., C1-C12 alkyl, C6-C12 aryl, C7-C12 alkylaryl, C7-C12 aralkyl), or from 1 to about 8 carbon atoms, or from 1 to about 6 carbon atoms.
The application aims to solve the technical problem of providing a halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity, a laminated board and a printed circuit board aiming at the defects of the prior art.
In order to solve the above-mentioned problems, one of the technical solutions adopted in the present application is to provide a halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity, which comprises:
(a) 30 to 40 parts by weight of an o-cresol formaldehyde epoxy resin;
(b) 50 to 70 parts by weight of a bismaleimide resin;
(c) 75 to 105 parts by weight of a cyanate ester hardener;
(d) 30 to 45 parts by weight of a bisphenol a type DOPO hardener;
(e) 10 to 20 parts by weight of a non-DOPO phosphorus containing flame retardant; and
(f) 2 to 12 parts by weight of a DOPO flame retardant.
The molecular structure of the o-cresol formaldehyde epoxy resin is that each benzene ring is connected with one epoxy group, compared with bisphenol A epoxy resin in the prior art, the epoxy value of the o-cresol formaldehyde epoxy resin is more than 0.5eq/100g, 2.5 times of crosslinking points can be provided when the resin is cured, a three-dimensional structure with high crosslinking density is extremely easy to form, the o-cresol formaldehyde epoxy resin has better thermal stability, mechanical strength, electrical insulation performance, water resistance, chemical resistance and higher glass transition temperature (Tg), and can still maintain good electrical insulation performance in a high-temperature and humid environment when the o-cresol formaldehyde epoxy resin is applied to electronic components. Preferably, the o-cresol formaldehyde epoxy resin may be NPCN-701, NPCN-702, NPCN-703, NPCN-704 (all trade names) manufactured by Nanya plastics industry Co., ltd; CNE202 manufactured by vinca resin works; n-665, N-670, N-673, N-680, N-690, N-695 manufactured by Dai Kagaku Kogyo Co., ltd; YDCN-701, YDCN-702, YDCN-703, YDCN-704, YDCN-701P, YDCN-702P, YDCN-703P, YDCN-704P, YDCN-701S, YDCN-702S, YDCN-703S manufactured by Tokyo Kabushiki Kaisha; SQCN700-1, SQCN700-2, SQCN700-3, SQCN700-4, SQCN700-4.5, SQCN702, SQCN703, SQCN700-1, SQCN704L, SQCN ML, SQCN707, SQCN704H manufactured by Shandong Shengquan chemical industry.
The bismaleimide resin of the present application is not particularly limited, and mainly a compound having two maleimide groups in the molecule, a prepolymer of a bismaleimide compound, or a prepolymer of a bismaleimide compound and an amine compound may be used. Preferably, the bismaleimide is selected from the group consisting of bis (4-maleimidophenyl) methane, 2-bis (4- (4-maleimidophenoxy) -phenyl) propane, bis (3, 5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, and bis (3, 5-diethyl-4-maleimidophenyl) methane.
The hardener of the application can increase the reactive functional groups in the resin structure and raise the glass transition temperature. 45 to 55 parts by weight of a phenolic cyanate ester hardener, 30 to 50 parts by weight of a bisphenol a cyanate ester hardener, and 30 to 45 parts by weight of a bisphenol a DOPO hardener. The phenolic cyanate hardener has the heat resistance and flame retardance of phenolic resin and the dielectric property of cyanate. Preferably, the phenolic cyanate ester hardener comprises a commercially available Yangzhou Tianqi model CE-05CS, the bisphenol A cyanate ester hardener comprises a commercially available Lonza model ULL-950S, and the bisphenol A DOPO hardener comprises a commercially available Olin model XQ-83006.
Bisphenol a type DOPO type hardener may, for example, have the following structure:
the non-DOPO phosphorus-containing flame retardant as defined herein means that it does not contain 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivatives. In detail, the P-O-C bond in the DOPO structure is easy to hydrolyze into P-OH, which can raise the dielectric constant and dielectric loss of the material, so that the non-DOPO flame retardant is selected to avoid raising Dk and DF of the material, wherein Dk is the dielectric constant (Dielectric Constant, εr), and DF is the dielectric loss.
In more detail, the non-DOPO flame retardant is selected from the group consisting of resorcinol bisxylyl phosphate (resorcinol dixylenylphosphate, RDXP (such as PX-200)), melamine polyphosphate (melamine polyphosphate), tris (2-carboxyethyl) phosphine (TCEP), trimethyl phosphate (trimethyl phosphate, TMP), tris (isopropyl chloride) phosphate, dimethyl methylphosphonate (dimethyl methyl phosphonate, DMMP), bisphenol diphenyl phosphate (bisphenol diphenyl phosphate), ammonium polyphosphate (ammonium polyphosphate), hydroquinone bis (diphenyl phosphate) (hydroquinone bis- (diphenyl phosphate)), bisphenol A bis (diphenyl phosphate), and Phosphazene compounds (commercial products such as SPB-100, SPH-100, SPV-100). Preferably, 20 to 30 parts by weight of resorcinol bisxylyl phosphate is blended with 5 to 15 parts by weight of a phosphazene compound (e.g., SPB-100). Preferably, the non-DOPO flame retardant of the present application is 10 to 20 parts by weight of resorcinol bisxylyl phosphate (e.g., PX-200), which can provide excellent halogen-free flame retardant effect.
In another aspect, the DOPO flame retardant of the present application is selected from the group consisting of the following formulas (I) and (II):
wherein R is 1 Is C (R) 4 ) 2 ；R 2 R is R 3 Each independently is hydrogen, C1-C15 alkyl, C6-C12 aryl, C7-C15 aralkyl, or C7-C15 alkaryl; or R is 2 And R is R 3 A saturated or unsaturated cyclic ring substituted or unsubstituted with a C1-C6 alkyl group; each R is 4 Independently hydrogen, C1-C6 alkyl, C6-C12 aryl or C3-C12 cycloalkyl; and each m is independently selected from a positive integer of 1 to 4;
wherein A is a direct bond, C6-C12 aryl, C3-C12 cycloalkyl or C3-C12 cycloalkenyl, and cycloalkyl or cycloalkenyl may be optionally substituted with C1-C6 alkyl;
wherein R is 1 、R 2 、R 3 R is R 4 Independently hydrogen, C1-C15 alkyl, C6-C12 aryl, C7-C15 aralkyl or C7-C15 alkaryl; or R is 1 And R is R 2 Or R is 3 And R is R 4 A saturated or unsaturated cyclic ring substituted or unsubstituted with a C1-C6 alkyl group; each m is independently selected from a positive integer of 1 to 4, each R 5 And R is 6 Independently hydrogen or C1-C6 alkyl; each n is independently selected from positive integers from 0 to 5.
In particular, the DOPO flame retardant may be a flame retardant selected from the group consisting of 6H-ibenz [ c, e ] [1,2] oxaphosphinobenzene, 6'- (1, 2-ethanediyl) bis-, 6' -dioxide, 6H-diphenyl [ c, e ] [1,2] oxaphosphinobenzene, 6,6'- (1, 4-butanediyl) bis-, 6' -dioxide, or 6H-diphenyl [ c, e ] [1,2] oxaphosphinobenzene, 6'- (p-xylyl) bis-, 6' -dioxide.
In addition, the resin composition of the present application further comprises: the curing accelerator, which can react with cyanate ring opening, is selected from phosphorus curing accelerators, amine curing accelerators, imidazole curing accelerators, guanidine curing accelerators, metal curing accelerators, and peroxide curing accelerators. Preferably, the metal-based hardening accelerator is mixed with the peroxide-based hardening accelerator.
More specifically, examples of the metal hardening accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include an organocobalt complex such as cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, an organocopper complex such as copper (II) acetylacetonate, an organozinc complex such as zinc (II) acetylacetonate, an organoiron complex such as iron (III) acetylacetonate, an organonickel complex such as nickel (II) acetylacetonate, and an organomanganese complex such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. Preferably, the metal hardening accelerator is cobalt (III) acetylacetonate (Co (acac) 3).
Examples of peroxide curing accelerators include cyclohexanone peroxide, t-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, t-butyl cumyl peroxide, di-t-butyl peroxide, dicumyl hydroperoxide, cumene hydroperoxide, and t-butyl hydroperoxide. Preferably, the peroxide-based hardening accelerator is dicumyl peroxide (DCP) commercially available from Arkema.
The imidazole-based hardening accelerator may be selected from the group consisting of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4, 5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole.
More preferably, the hardening accelerator of the present application may be 1 part by weight of a metal-based hardening accelerator, 1 part by weight of 2-ethyl-4-methylimidazole, and 1 part by weight of a peroxide-based hardening accelerator based on 100 parts by weight of epoxy resin.
In addition, the resin composition of the present application further comprises: an inorganic filler which can increase the thermal conductivity of the halogen-free low dielectric epoxy resin composition and improve the thermal expansion and mechanical strength thereof, preferably, the inorganic filler is uniformly distributed in the halogen-free low dielectric epoxy resin composition. Preferably, the inorganic filler may be subjected to surface treatment in advance via a silane coupling agent. Preferably, the inorganic filler may be a spherical, flaky, granular, columnar, plate-like, needle-like or irregular inorganic filler. Preferably, the inorganic filler is selected from the group consisting of silica (e.g., molten, non-molten, 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, graphene. Preferably, the inorganic filler may be added in an amount of 200 to 200 parts by weight based on 100 parts by weight of the epoxy resin. Preferably, NQ-1035I manufactured by Nomoray corporation is used, which is effective in improving thermal conductivity, mechanical strength and reducing thermal expansion.
In addition, the halogen-free low dielectric epoxy resin composition of the present application further comprises a proper amount of a solvent, for example, ketones, esters, ethers, alcohols, etc., more specifically, the solvent of the present application is selected from the group consisting of acetone, butanone, propylene glycol methyl ether acetate, dimethylacetamide and cyclohexanone. For example, the solvent may be selected from a combination of 60 to 70 parts by weight of Methyl Ethyl Ketone (MEK) and 70 to 80 parts by weight of Cyclohexanone (Cyclohexanone) or other solvents, etc.
In order to solve the above technical problems, another technical solution adopted by the present application is to provide a laminated board, which includes: a resin substrate comprising a plurality of semi-cured films, each of the semi-cured films being made of a glass fiber cloth by coating the halogen-free resin composition of the present application having low expansion coefficient, low dielectric loss and high rigidity; and a metal foil layer disposed on at least one surface of the resin substrate.
The present application also provides another technical solution, which is a laminate, comprising: (a) A resin substrate comprising a plurality of semi-cured films, each of the semi-cured films being made of a glass cloth by coating a halogen-free low dielectric epoxy resin composition according to the present application; and (b) a metal foil layer disposed on at least one surface of the resin substrate, or the resin substrate may be provided with metal foil layers up and down as desired.
In addition, another embodiment of the present application is a printed circuit board, which includes the laminate of the present application.
The following description will be made of the halogen-free epoxy resin composition of the present application and the examples and comparative examples, which are carried out in plural, to explain the best laminate properties achieved by the specific composition ratio formulation of the present application.
Examples
The following examples E1 to E4 are semi-cured films produced in a continuous process using the halogen-free low dielectric epoxy resin composition of the present application. Glass fiber cloth is typically used as a substrate. The coiled glass fiber cloth continuously passes through a series of rollers to enter a sizing groove, and the groove is filled with the halogen-free low-dielectric epoxy resin composition. And fully soaking glass fiber cloth in a sizing tank by resin, scraping excess resin by a metering roller, baking in a sizing furnace for a certain time, evaporating a solvent, solidifying the resin to a certain degree, cooling, rolling to form a semi-solidified film, taking four and two 18 mu m copper foils of the semi-solidified film prepared by the batch, stacking the copper foils, the four semi-solidified films and the copper foils in sequence, and pressing for 2 hours at 220 ℃ under vacuum 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
* Cresol novolac epoxy: CNE-202 cresol formaldehyde epoxy resin manufactured by vinca resin Co.
* Bismaleimides: KI-70 manufactured by KI Co.
* Cyanate ester (PN type): CE-05CS manufactured by Yangzhou Tianqi corporation.
* BPAN-DOPO: XQ-83006 manufactured by Olin Co.
* Cyanate ester (BPA type): ULL-9505 manufactured by Lonza corporation.
Comparative example
Semi-cured films were produced in a continuous process according to the compositions and proportions of comparative examples C1 to C7 of table 2 below. Glass fiber cloth is typically used as a substrate. The coiled glass fiber cloth continuously passes through a series of rollers to enter a sizing groove, and the groove is filled with the halogen-free low-dielectric epoxy resin composition. And fully soaking glass fiber cloth in a sizing tank by resin, scraping excess resin by a metering roller, baking in a sizing furnace for a certain time, evaporating a solvent, solidifying the resin to a certain degree, cooling, rolling to form a semi-solidified film, taking four and two 18 mu m copper foils of the semi-solidified film prepared by the batch, stacking the copper foils, the four semi-solidified films and the copper foils in sequence, and pressing for 2 hours at 220 ℃ under vacuum 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
* HP-7200: DCPD (dicyclopentadiene) type epoxy resins.
* NC-3000: biphenyl type epoxy resin of japan chemical company.
* Maleic anhydride-modified polyimide resins of formulas 1 to 3 and flame retardants of formulas I to III: reference is made to TWI632190 and TW 109106662.
Physical property test
The copper foil laminate of each of examples E1 to E4 and comparative examples C1 to C7 was subjected to physical properties test, and the test results were recorded in table 3:
glass transition temperature (Tg): the measurement was carried out according to Differential Scanning Calorimetry (DSC) according to the DSC method specified in IPC-TM-650.2.4.25.
Copper foil laminate heat resistance (T288): also called as a tin-float result, the heat-resistant experiment is to soak the copper foil laminated plate in a tin furnace at 288 ℃ for a period of time required for plate explosion according to the industrial standard IPC-TM-650.2.4.24.1.
Tin immersion test after moisture absorption of copper foil-containing laminated plate: the heat resistance (T288) test was performed using a prepreg containing a copper foil layer, and the copper foil laminate was immersed in a 288 ℃ tin oven for the time required to burst the board according to industry standard IPC-TM-650.4.24.1.
Copper foil laminate heat resistance (S/D) test: copper-containing substrates were tested for wicking (holder dip 288 ℃,10 seconds, heat resistance number).
Copper foil laminate heat resistance (PCT) test: copper free substrates were subjected to PCT wicking post dip test (pressure cooking at ℃,1 hour later, holder dip 288 ℃,20 seconds for viewing of the presence of the burst plate).
Tension between copper foil and substrate (P/S, half ounce copper foil): the determination was made according to the IPC-TM-650.2.4.1 detection Specification.
Dielectric constant (Dk): the dielectric constant represents the electronic insulation properties of the films produced, and the lower the value the better the electronic insulation properties, as determined according to the IPC-TM-650.2.5.5 detection specification.
Dielectric loss (Df): the dielectric loss is measured according to IPC-TM-650.5.5 detection specifications, which indicate 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 is, the better.
Flame resistance (UL 94): the flame resistance rating of the plastic material is determined by the flame ignition time, the self ignition speed and the falling particle state of the plastic material standard test piece after flame combustion according to the UL94 vertical burning method. And HB, V-2, V-1, V-0 and 5V grades at most are adopted according to the flame resistance grade. Whereas UL94 test method refers to plastic materials burning in a vertical manner on a flame. Taking every ten seconds as a test period, the steps are as follows: step one: placing the test piece in a flame for ten seconds and then removing the test piece, and measuring the continuous burning time (T1) of the test piece after the test piece is removed; step two: after the flame of the test piece is extinguished, putting the test piece into the flame for ten seconds and then removing the test piece, and measuring the continuous burning time (T2) of the test piece after the removal; step three: the experiment was repeated several times and the average value was taken; step four: the sum of T1+T2 is calculated. The requirement of UL 94V-0 is that the average of the single burning time T1 and the average of T2 of the test piece are not more than 10 seconds, and the sum of T1 and T2 is not more than 50 seconds, which meets the requirement of UL 94V-0.
Coefficient of Thermal Expansion (CTE) in the X/Y axis: the determination was performed according to the IPC-TM-650-2.4.24 detection Specification.
Z-axis Coefficient of Thermal Expansion (CTE) (50-260 ℃ C.). The determination was performed according to the IPC-TM-650-2.4.24.1 detection Specification.
Modulus (X/Y) was measured according to the "IPC-TM-650.2.4.24.4" test Specification.
TABLE 3 Table 3
Advantageous effects of the embodiments
The halogen-free resin composition with low expansion coefficient, the laminated board and the printed circuit board provided by the application have the beneficial effects that the halogen-free resin composition with low expansion coefficient, the laminated board and the printed circuit board can be provided through specific components and proportions, and meanwhile, the toughness and the heat resistance of the board are improved, and the cost is reduced. In addition, the composition can be made into semi-cured films or resin films, so that the purpose of being applied to copper foil substrates and printed circuit boards is achieved, and the product derived by the composition can fully meet the current market demands in terms of industrial availability.
Furthermore, the copper foil laminated board prepared from the halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity has lower expansion coefficient, compared with the copper foil laminated board prepared from the copper foil laminated board with low expansion coefficient, the copper foil laminated board has the advantages that compared with the copper foil laminated board with the X/Y axis CTE lower than 10ppm/°c, the copper foil laminated board with the Z axis CTE lower than 1 percent and the dielectric loss (Df) lower than 0.008 at 10GHz, the copper foil laminated board has better rigidity in toughness and obviously better heat-resistant effect compared with the prior art.
The above disclosure is only an alternative embodiment of the present application and is not intended to limit the scope of the claims of the present application, so that all equivalent technical changes made by applying the content of the present application are included in the scope of the claims of the present application.

Claims (10)

1. A low expansion coefficient halogen-free resin composition, characterized in that the low expansion coefficient halogen-free resin composition comprises:
(a) 30 to 40 parts by weight of an o-cresol formaldehyde epoxy resin;
(b) 50 to 70 parts by weight of a bismaleimide resin;
(c) 75 to 105 parts by weight of a cyanate ester hardener;
(d) 30 to 45 parts by weight of a bisphenol a type DOPO hardener;
(e) 10 to 20 parts by weight of a non-DOPO phosphorus containing flame retardant; and
(f) 2 to 12 parts by weight of a DOPO flame retardant;
wherein the DOPO flame retardant is selected from the group consisting of the following chemical formulas (I) and (II):
wherein R is 1 Is C (R) 4 ) 2 ；R 2 R is R 3 Each independently is hydrogen, C1-C15 alkyl, C6-C12 aryl, C7-C15 aralkyl, or C7-C15 alkaryl; or R is 2 And R is R 3 A saturated or unsaturated cyclic ring substituted or unsubstituted with a C1-C6 alkyl group; each R is 4 Independently hydrogen, C1-C6 alkyl, C6-C12 aryl or C3-C12 cycloalkyl; and each m is independently selected from a positive integer of 1 to 4;
wherein A is a direct bond, C6-C12 aryl, C3-C12 cycloalkyl or C3-C12 cycloalkenyl, and cycloalkyl or cycloalkenyl may be optionally substituted with C1-C6 alkyl;
wherein R is 1 、R 2 、R 3 R is R 4 Independently hydrogen, C1-C15 alkyl, C6-C12 aryl, C7-C15 aralkyl or C7-C15 alkaryl; or R is 1 And R is R 2 Or R is 3 And R is R 4 May form saturated or unsubstituted C1-C6 alkyl groupsAnd or an unsaturated cyclic ring; each m is independently selected from a positive integer of 1 to 4, each R 5 And R is 6 Independently hydrogen or C1-C6 alkyl; each n is independently selected from positive integers from 0 to 5.
2. The low expansion coefficient halogen-free resin composition of claim 1, wherein the bismaleimide is selected from the group consisting of bis (4-maleimidophenyl) methane, 2-bis (4- (4-maleimidophenoxy) -phenyl) propane, bis (3, 5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, and bis (3, 5-diethyl-4-maleimidophenyl) methane.
3. The low expansion coefficient halogen-free resin composition according to claim 1, wherein the cyanate ester hardener comprises 45 to 55 parts by weight of phenolic cyanate ester hardener and 30 to 50 parts by weight of bisphenol a type cyanate ester hardener.
4. The low expansion coefficient halogen-free resin composition according to claim 1, wherein the bisphenol a type DOPO hardener has the following structure:
5. the low expansion coefficient halogen-free resin composition of claim 1, wherein the non-DOPO flame retardant is selected from the group consisting of resorcinol bis-xylyl phosphate, melamine polyphosphate, tris (2-carboxyethyl) phosphine, trimethyl phosphate, tris (isopropyl chloride) phosphate, dimethyl methylphosphonate, bisphenol diphenyl phosphate, ammonium polyphosphate, hydroquinone bis (diphenyl phosphate), bisphenol a bis (diphenyl phosphate) and phosphazene compound.
6. The low expansion coefficient halogen-free resin composition of claim 1, further comprising: a hardening accelerator selected from the group consisting of phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, guanidine-based hardening accelerators, metal-based hardening accelerators, and peroxide-based hardening accelerators.
7. The low expansion coefficient halogen-free resin composition according to claim 6, wherein the hardening accelerator comprises: 1 part by weight of a metal-based hardening accelerator, 1 part by weight of 2-ethyl-4-methylimidazole, and 1 part by weight of a peroxide-based hardening accelerator.
8. The low expansion coefficient halogen-free resin 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. A laminate panel, the laminate panel comprising:
a resin substrate comprising a plurality of semi-cured films, each of the semi-cured films being made of a glass fiber cloth by coating the low expansion coefficient halogen-free resin composition according to claim 1; and
and a metal foil layer arranged on at least one surface of the resin substrate.
10. A printed circuit board comprising the laminate of claim 9.
CN202110060714.1A 2021-01-18 2021-01-18 Low expansion coefficient halogen-free resin composition, laminated board and printed circuit board Active CN114806078B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110028758A (en) * 2018-01-12 2019-07-19 联茂(无锡)电子科技有限公司 Halogen-free epoxy resin composition, laminated plates and printed circuit board
TW201930447A (en) * 2018-01-02 2019-08-01 聯茂電子股份有限公司 Halogen-free epoxy resin composition, laminated substrate and printed circuit board thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201930447A (en) * 2018-01-02 2019-08-01 聯茂電子股份有限公司 Halogen-free epoxy resin composition, laminated substrate and printed circuit board thereof
CN110028758A (en) * 2018-01-12 2019-07-19 联茂(无锡)电子科技有限公司 Halogen-free epoxy resin composition, laminated plates and printed circuit board

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