TWI765504B - LOW EXPANSION COEFFICIENT, LOW Df, HIGH RIGIDITY, HALOGEN-FREE RESIN COMPOSITION, LAMINATES AND PRINTED CIRCUIT BOARDS - Google Patents

Abstract

A low expansion coefficient, low Df, high rigidity, halogen-free resin composition, laminate and printed circuit board are provided. The composition includes (a) 30 to 40 parts by weight of cresol novolac epoxy resin, (b) 50 to 70 parts by weight of bismaleimide resin, (c) 75 to 105 parts by weight of cyanate ester hardener, (d) 30 to 45 parts by weight of BPA-DOPO hardener and (e) 10 to 20 parts by weight of non-DOPO phosphorus-containing flame retardant and (f) 2 to 12 parts by weight of DOPO flame retardant . By the halogen-free epoxy resin composition with a specific composition and ratio, the halogen-free epoxy resin composition has a low dielectric loss, also improves the toughness and heat resistance of the board.

Description

Low expansion coefficient, low dielectric loss, high rigidity, halogen-free resin composition, laminates, and printed circuit boards

The invention relates to a resin composition, a laminate and a printed circuit board using the epoxy resin composition, in particular to a halogen-free resin composition, laminate and printed circuit board with low expansion coefficient, low dielectric loss and high rigidity.

Under the continuous fever of the communication electronics market, high-frequency and high-speed transmission has become a necessary option, and the circuit board, which plays the role of carrying components, power supply and signal transmission, has become the key to the development of this field. The existing epoxy resin and phenolic resin The printed circuit board of the material can no longer meet the advanced application of high frequency.

In the printed circuit board technology, it is mainly a thermosetting resin composition including epoxy resin and hardener, which is heated and combined with a reinforcing material (such as glass fiber cloth) to form a prepreg, which is then combined with the upper, The next two pieces of copper foil are pressed together to form a copper foil laminate (or copper foil substrate). Generally, a phenol novolac resin hardener with hydroxyl group (-OH) is used in the thermosetting resin composition. After combining with the epoxy resin, the epoxy group will open the ring to form a hydroxyl group, and the hydroxyl group will increase the dielectric constant and dielectric Loss value, and easy to bond with H ₂ O, resulting in increased hygroscopicity.

The epoxy resin composition of the prior art uses halogen-containing flame retardants (especially brominated flame retardants), such as tetrabromocyclohexane, hexabromocyclodecane and 2,4,6-tris(tribromobenzene) oxy)-1,3,5-triazabenzene, etc., halogen-containing flame retardants have the advantages of good flame retardancy and less addition. However, halogen products are used in product manufacturing, use, and even recycling or discarding. In addition, the halogen-containing electronic equipment waste will produce corrosive, toxic gas and smoke when burned, and the products after burning will detect carcinogens such as dioxin and dibenzofuran. substance. Therefore, halogen-free flame retardant printed circuit boards have become the focus of development in this field.

In addition to the development of halogen-free flame retardant printed circuit boards, copper foil substrates have heat resistance, flame retardancy, low dielectric loss, low moisture absorption, high crosslink density, high glass transition temperature, high bonding, and appropriate thermal expansion. Properties such as properties are more important issues in the development and manufacture of printed circuit boards. Therefore, the material selection of epoxy resin, hardener and reinforcing material has become the main influencing factor.

The technical problem to be solved by the present invention is to provide a halogen-free resin composition, a laminate and a printed circuit board with low expansion coefficient, low dielectric loss and high rigidity in view of the deficiencies of the prior art.

(I)； 其中，R ₁為C(R ₄) ₂；R ₂及R ₃各自獨立地為氫、C1-C15烷基、C6-C12芳基、C7-C15芳烷基或C7-C15烷芳基；或 R ₂與R ₃可形成經C1-C6烷基取代或未經取代的飽和或不飽和環狀環；各R ₄獨立地為氫、C1-C6烷基、C6-C12芳基或C3-C12環烷基；且各m獨立地選自1至4的正整數；

(II)； 其中，A是直接鍵、C6-C12芳基、C3-C12環烷基或C3-C12環烯基，且環烷基或環烯基可任選地被C1-C6烷基取代； 其中，R ₁、R ₂、R ₃及R ₄獨立地為氫、C1-C15烷基、C6-C12芳基、C7-C15芳烷基或C7-C15烷芳基；或者R ₁與R ₂或R ₃與R ₄可形成經C1-C6烷基取代或未經取代的飽和或不飽和環狀環；各m獨立地選自1至4的正整數，各R ₅和R ₆獨立地為氫或C1-C6烷基；各n獨立地選自0至5的正整數。 In order to solve the above-mentioned technical problems, one of the technical solutions adopted in the present invention is to provide a halogen-free resin composition with low coefficient of expansion, low dielectric loss and high rigidity, which comprises: (a) 30 to 40 parts by weight of o-cresol Epoxy resin; (b) 50 to 70 parts by weight of bismaleimide resin; (c) 75 to 105 parts by weight of cyanate hardener; (d) 30 to 45 parts by weight of 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 following chemical formula (I ) and group (II):

(I); wherein, R ₁ is C(R ₄ ) ₂ ; R ₂ and R ₃ are each independently hydrogen, C1-C15 alkyl, C6-C12 aryl, C7-C15 aralkyl or C7-C15 alkane Aryl; or R ₂ and R ₃ can form a saturated or unsaturated cyclic ring substituted or unsubstituted by C1-C6 alkyl; each R ₄ is independently hydrogen, C1-C6 alkyl, C6-C12 aryl or C3-C12 cycloalkyl; and each m is independently selected from a positive integer from 1 to 4;

(II); wherein A is a direct bond, C6-C12 aryl, C3-C12 cycloalkyl or C3-C12 cycloalkenyl, and the cycloalkyl or cycloalkenyl may be optionally substituted by C1-C6 alkyl wherein, R ₁ , R ₂ , R ₃ and R ₄ are independently hydrogen, C1-C15 alkyl, C6-C12 aryl, C7-C15 aralkyl or C7-C15 alkaryl; or R ₁ and R ₂ or R ₃ and R ₄ can form a saturated or unsaturated cyclic ring substituted or unsubstituted by C1-C6 alkyl; each m is independently selected from a positive integer from 1 to 4, and each R ₅ and R ₆ are independently is hydrogen or C1-C6 alkyl; each n is independently selected from a positive integer from 0 to 5.

In order to solve the above-mentioned technical problem, another technical solution adopted by the present invention is to provide a laminated board, which includes: a resin substrate, which includes a plurality of prepreg films, and each of the prepreg films is made of a glass fiber cloth It is made by coating the halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity of the present invention; and a metal foil layer, which is arranged 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 of the present invention.

One of the beneficial effects of the present invention is that the halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity, laminated board and printed circuit board provided by the present invention can be provided by specific components and proportions, and at the same time Improve sheet toughness and heat resistance, and reduce costs. Furthermore, the composition can be made into a prepreg or resin film, which can then be applied to copper foil substrates and printed circuit boards. It can fully meet the needs of the current market.

For a further understanding of the features and technical content of the present invention, please refer to the following detailed descriptions and drawings of the present invention. However, the drawings provided are only for reference and description, and are not intended to limit the present invention.

The following are specific specific examples to illustrate the embodiments of the “low expansion coefficient, low dielectric loss, high rigidity halogen-free resin composition, laminate and printed circuit board” disclosed in the present invention. Those skilled in the art can learn from this specification. The disclosure provides an understanding of the advantages and effects of the present invention. The present invention can be implemented or applied through other different specific embodiments, and various details in this specification can also be modified and changed based on different viewpoints and applications without departing from the concept of the present invention. The following embodiments will further describe the related technical contents of the present invention in detail, but the disclosed contents are not intended to limit the protection scope of the present invention. In addition, the term "or", as used herein, should include any one or a combination of more of the associated listed items, as the case may be.

The term "alkyl" as used herein includes saturated monovalent hydrocarbon groups having straight or branched chain moieties. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, and hexyl.

The term "alkenyl" as used herein includes an alkyl moiety having at least one carbon-carbon double bond, wherein alkyl is as defined above. Examples of alkenyl groups include, but are not limited to, vinyl 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 wherein 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 (C6H5CH2-) and methylbenzyl (CH3C6H4CH2-).

The term "alkaryl" as used herein is an "alkyl-aryl-" group. Non-limiting examples of alkaryl groups are methylphenyl-, dimethylphenyl-, ethylphenyl-, propylphenyl-, isopropylphenyl-, butylphenyl-, isobutyl Phenyl- 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 foregoing hydrocarbon-derived groups can have from about 1 to about 20 carbon atoms (eg, C1-C20 alkyl, C6-C20 aryl, C7-C20 alkaryl, C7-C20 aralkyl ) or 1 to about 12 carbon atoms (eg, C1-C12 alkyl, C6-C12 aryl, C7-C12 alkaryl, C7-C12 aralkyl), or 1 to about 8 carbon atoms, or 1 to about 6 carbon atoms.

The technical problem to be solved by the present invention is to provide a halogen-free resin composition, a laminate and a printed circuit board with low expansion coefficient, low dielectric loss and high rigidity in view of the deficiencies of the prior art.

In order to solve the above-mentioned technical problems, one of the technical solutions adopted in the present invention 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 o-cresol epoxy resin; (b) 50 to 70 parts by weight of bismaleimide resin; (c) 75 to 105 parts by weight of cyanate hardener; (d) 30 to 45 parts by weight of 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 DOPO flame retardant.

The molecular structure of the o-cresol epoxy resin of the present invention is that each benzene ring is connected with an epoxy group. Compared with the bisphenol A type epoxy resin in the prior art, the epoxy resin of the o-cresol epoxy resin has The value is as high as 0.5 eq/100g or more. When the resin is cured, it can provide 2.5 times more cross-linking points, and it is easy to form a three-dimensional structure with high cross-linking density. It has better thermal stability, mechanical strength, electrical insulation performance, water resistance, resistance Chemical properties, high glass transition temperature (Tg), used in electronic components, and can maintain good electrical insulation performance in high temperature and humid environments. Preferably, the o-cresol epoxy resin can be commercially available NPCN-701, NPCN-702, NPCN-703, NPCN-704 (all trade names) manufactured by Nanya Plastics Industry Co., Ltd.; Changchun Artificial Resin CNE202 manufactured by the factory; N-665, N-670, N-673, N-680, N-690, N-695 manufactured by Dainippon Ink Chemical Industry Co., Ltd.; YDCN-701, YDCN manufactured by Toto Chemical Co., Ltd., Japan -702, YDCN-703, YDCN-704, YDCN-701P, YDCN-702P, YDCN-703P, YDCN-704P, YDCN-701S, YDCN-702S, YDCN-703S; SQCN700-1, SQCN700 manufactured by Shandong Shengquan Chemical Co., Ltd. -2, SQCN700-3, SQCN700-4, SQCN700-4.5, SQCN702, SQCN703, SQCN700-1, SQCN704L, SQCN704ML, SQCN707, SQCN704H.

The bismaleimide resin of the present invention is not particularly limited, and is mainly a compound containing two maleimide groups in the molecule. Prepolymers of bismaleimide compounds, or bismaleimide compounds can also be used. Prepolymers of maleimide compounds and amine compounds. Preferably, bismaleimide is selected from bis(4-maleimidophenyl)methane, 2,2-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 present invention can increase the reactive functional groups in the resin structure and increase the glass transition temperature. 45 to 55 parts by weight of a novolac type cyanate ester hardener, 30 to 50 parts by weight of a bisphenol A type cyanate ester hardener, and 30 to 45 parts by weight of a bisphenol A type DOPO hardener. Phenolic cyanate hardener has the heat resistance and flame retardancy of phenolic resin and the dielectric properties of cyanate. Preferably, the novolac type cyanate hardener includes commercially available Yangzhou Tianqi model CE-05CS, the bisphenol A type cyanate hardener includes commercially available Lonza model ULL-950S, bisphenol A type DOPO Type hardeners include commercially available Olin model number XQ-83006.

For example, the bisphenol A type DOPO type hardener can have the following structure:

A non-DOPO phosphorus-containing flame retardant as defined in the present invention 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 easily hydrolyzed to P-OH, which will increase the dielectric constant and dielectric loss of the material. Therefore, the use of non-DOPO flame retardants can avoid increasing the Dk and DF of the material, where Dk is is the dielectric constant (Dielectric Constant, εr), and DF is the dielectric loss.

In more detail, the non-DOPO flame retardant is selected from resorcinol dixylenylphosphate (resorcinol dixylenylphosphate, RDXP (such as PX-200)), melamine polyphosphate, tris(2-carboxyethyl) tri(2-carboxyethyl)phosphine (TCEP), trimethyl phosphate (TMP), tris(isopropyl chloride) phosphate, dimethyl methyl phosphonate, DMMP), bisphenol diphenyl phosphate, ammonium polyphosphate, hydroquinone bis-(diphenyl phosphate), bisphenol A - A group consisting of bisphenol A bis-(diphenylphosphate) and phosphazene compounds (Phosphazene, such as SPB-100, SPH-100, SPV-100 and other commercial products). Preferably, it can be 20 to 30 parts by weight of resorcinol bis-xylyl phosphate and 5 to 15 parts by weight of a phosphazene compound (such as SPB-100). Preferably, the non-DOPO flame retardant of the present invention is 10 to 20 parts by weight of resorcinol bis-xylyl phosphate (eg PX-200), which can provide excellent halogen-free flame retardant effect.

(I)； On the other hand, the DOPO flame retardant of the present invention is selected from the group consisting of the following chemical formula (I) and chemical formula (II):

(I);

(II)； wherein, R ¹ is C(R ₄ ) ₂ ; R ² and R ³ are each independently hydrogen, C1-C15 alkyl, C6-C12 aryl, C7-C15 aralkyl or C7-C15 alkaryl; or R ² and R ³ may form a C1-C6 alkyl substituted or unsubstituted saturated or unsaturated cyclic ring; each R ⁴ is independently hydrogen, C1-C6 alkyl, C6-C12 aryl or C3-C12 and each m is independently selected from a positive integer from 1 to 4;

(II);

wherein A is a direct bond, C6-C12 aryl, C3-C12 cycloalkyl or C3-C12 cycloalkenyl, and the cycloalkyl or cycloalkenyl may be optionally substituted by C1-C6 alkyl; wherein, R ¹ , R ² , R ³ and R ⁴ are independently hydrogen, C1-C15 alkyl, C6-C12 aryl, C7-C15 aralkyl or C7-C15 alkaryl; or R ¹ and R ² or R ³ and R ⁴ can form a C1-C6 alkyl substituted or unsubstituted saturated or unsaturated cyclic ring; each m is independently selected from a positive integer from 1 to 4, and each R ⁵ and R ⁶ are independently hydrogen or C1 -C6 alkyl; each n is independently selected from a positive integer from 0 to 5.

Specifically, the DOPO flame retardant may be selected from the group consisting of 6H-ibenz[c,e][1,2]oxaphosphines, 6,6'-(1,2-ethanediyl)bis-,6 ,6'-dioxide, 6H-diphenyl[c,e][1,2]oxaphosphine, 6,6'-(1,4-butanediyl)bis-, 6,6' -Dioxide, or 6H-diphenyl[c,e][1,2]oxaphosphazene, 6,6'-(p-xylylenediyl)bis-,6,6'-dioxide formed groups.

In addition, the resin composition of the present invention further comprises: a hardening accelerator, which can make the cyanate ester ring-opening reaction, selected from the group consisting of phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, and guanidine-based hardening accelerators. Hardening accelerator, metal hardening accelerator, peroxide hardening accelerator. Preferably, a metal-based hardening accelerator and a peroxide-based hardening accelerator are mixed.

More specifically, metal-based hardening accelerators include metal organometallic complexes or organometallic salts of cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organocobalt complexes such as cobalt(II) acetylacetonate, cobalt(III) acetylacetonate, and copper(II) acetylacetonate. organo-copper complexes, organo-zinc complexes such as zinc(II) acetylacetonate, organo-iron complexes such as iron(III) acetylacetonate, nickel(II) acetylacetonate etc. organo-nickel complexes, manganese (II) acetylacetonate and other organo-manganese complexes. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. Preferably, the metal-based hardening accelerator is cobalt(III) acetylacetonate (Co(acac) ₃ ).

Peroxide-based curing accelerators include, for example, cyclohexanone peroxide, t-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, and t-butyl isopropyl peroxide. Propylbenzene, di-tert-butyl peroxide, dicumyl hydroperoxide, cumene hydroperoxide, tert-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 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl - The group consisting of 2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole.

More preferably, the hardening accelerator of the present invention can be based on 100 parts by weight of epoxy resin, 1 part by weight of metal-based hardening accelerator, 1 part by weight of 2-ethyl-4-methylimidazole and 1 part by weight of peroxide Department of hardening accelerator.

In addition, the resin composition of the present invention further comprises: inorganic filler, which can increase the thermal conductivity of the halogen-free low-dielectric epoxy resin composition, improve its thermal expansion and mechanical strength, preferably, the inorganic filler is uniform Distributed in halogen-free low-dielectric epoxy resin composition. Preferably, the inorganic filler can be pre-treated with a silane coupling agent. Preferably, the inorganic filler can be spherical, flake, granular, columnar, plate, needle or irregular. Preferably, the inorganic filler is selected from silica (such as molten, non-molten, porous or hollow silica), alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, nitride A group consisting of aluminum, boron nitride, aluminum silicon carbide, silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, barium sulfate, magnesium carbonate, barium carbonate, mica, talc, and graphene. Preferably, the addition amount of the inorganic filler may be 200 to 200 parts by weight based on 100 parts by weight of the epoxy resin. Preferably, NQ-1035I manufactured by Nomoray can be used, which can effectively improve thermal conductivity, mechanical strength and reduce thermal expansion.

In addition, the halogen-free low-dielectric epoxy resin composition of the present invention further includes an appropriate amount of solvent, for example, ketones, esters, ethers, alcohols, etc. More specifically, the solvent of the present invention is selected from From the group consisting of acetone, methyl ethyl ketone, propylene glycol methyl ether, 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 butanone (MEK) and 70 to 80 parts by weight of cyclohexanone or a combination of other solvents and the like.

In order to solve the above-mentioned technical problem, another technical solution adopted by the present invention is to provide a laminated board, which includes: a resin substrate, which includes a plurality of prepreg films, and each of the prepreg films is made of a glass fiber cloth It is made by coating the halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity of the present invention; and a metal foil layer, which is arranged on at least one surface of the resin substrate.

The present invention also provides another technical solution, which is a laminate, which includes: (a) a resin substrate, which includes a plurality of prepreg films, and each of the prepreg films is coated with a glass fiber cloth according to the present invention. and (b) a metal foil layer, which is disposed on at least one surface of the resin substrate, or the resin substrate can be provided with metal foil layers up and down as required.

Besides, the present invention further provides another technical solution, which is a printed circuit board including the laminate of the present invention.

The following will focus on the halogen-free epoxy resin composition of the present invention, as well as several groups of examples and comparative examples, to illustrate that the optimum laminate properties can be achieved by the specific composition ratio of the present invention.

[Example]

The following Examples E1 to E4 are the use of the halogen-free low-dielectric epoxy resin composition of the present invention to manufacture prepreg films in a continuous process. Usually glass fiber cloth is used as the base material. Rolled fiberglass cloth is continuously passed through a series of rollers into a gluing tank containing the halogen-free, low-dielectric epoxy resin composition of the present invention. In the gluing tank, the glass fiber cloth is fully infiltrated with the resin, and then the excess resin is scraped off by the metering roller, and then enters the gluing furnace to bake for a certain period of time, so that the solvent evaporates and the resin is solidified to a certain extent. Curing the film, then the prepreg film obtained in the above batch, take four prepreg films and two 18 μm copper foils from the same batch, and stack them in the order of copper foil, four prepreg films, and copper foil, and then Under vacuum conditions, the copper foil substrate was formed by pressing at 220° C. for 2 hours, in which four pieces of prepreg film were cured to form an insulating layer between the two copper foils.

Table 1 composition E1 E2 E3 E4 epoxy resin Cresol novolac epoxy * 50 50 40 40 General resin Bismaleimides* 50 50 60 60 hardener Cyanate ester* (PN type) 40 55 40 55 BPAN-DOPO* 40 40 40 40 Cyanate ester* (BPA type) 50 30 50 30 flame retardant Resorcinol dixylenylphosphate 10 16 10 16 Dopo flame retardant chemical formula (I) 10 4 - - Dopo flame retardant chemical formula (II) - - 10 4 Inorganic filler spherical silica 220 220 220 220 accelerator Cobaltic acetylacetonate 1 1 1 1 Cobaltic acetylacetonate 1 1 1 1 Dicumyl peroxide 1 1 1 1 solvent MEK (Butanone) 60 60 60 60 Cyclohexanone (cyclohexanone) 70 70 70 70

*Cresol novolac epoxy: CNE-202 cresol novolac epoxy resin manufactured by Changchun Artificial Resin Company.

*Bismaleimides: KI-70 manufactured by KI Corporation.

*Cyanate ester(PN type): CE-05CS manufactured by Yangzhou Tianqi Company.

*BPAN-DOPO*: XQ-83006 manufactured by Olin Corporation.

*Cyanate ester (BPA type): ULL-9505 manufactured by Lonza Corporation.

[Comparative example]

Prepreg films were produced in a continuous process according to the compositions and ratios of Comparative Examples C1 to C7 in Table 2 below. Usually glass fiber cloth is used as the base material. Rolled fiberglass cloth is continuously passed through a series of rollers into a gluing tank containing the halogen-free, low-dielectric epoxy resin composition of the present invention. In the gluing tank, the glass fiber cloth is fully infiltrated with the resin, and then the excess resin is scraped off by the metering roller, and then enters the gluing furnace to bake for a certain period of time, so that the solvent evaporates and the resin is solidified to a certain extent. Curing the film, then the prepreg film obtained in the above batch, take four prepreg films and two 18 μm copper foils from the same batch, and stack them in the order of copper foil, four prepreg films, and copper foil, and then Under vacuum conditions, the copper foil substrate was formed by pressing at 220° C. for 2 hours, in which four pieces of prepreg film were cured to form an insulating layer between the two copper foils.

Table 2 composition C1 C2 C3 C4 C5 epoxy resin HP-7200 40 40 40 40 40 NC-3000 60 60 60 60 60 Maleic anhydride hardener Styrene Maleic Anhydride (SMA) EF60 30 - - Modified maleic anhydride copolymer of formula 1 - - 20 - - Modified maleic anhydride copolymer of formula 2 - - 20 - - Maleic anhydride modified polyimide resin of formula 3 - - - 40 35 benzoxazine resin LZ8280 - 60 - 50 20 flame retardant Formula I flame retardant 36 - - - - Formula II flame retardant - - 60 - - Formula III flame retardant - 62 - - - SAYTEX 8010 - - - 30 - flame retardant compound PX-200 (resorcinol bis-xylyl phosphate) - - - - - TCEP (tris(2-chloroethyl) phosphate) - - - - - TMP - - - - - Inorganic filler Fused silica 28 57 47 41 30 hardening accelerator 2E4MI (2-ethyl-4-methylimidazole) 1 1 1 1 1 solvent MEK (Butanone) 42 80 114 97 56 PMA (propylene glycol methyl ether ethyl ester) 20 - - - -

* HP-7200: DCPD (dicyclopentadiene type) epoxy resin.

* NC-3000: Nippon Kayaku Co., Ltd. biphenyl type epoxy resin.

* Maleic anhydride modified polyimide resins of formulas 1-3 and flame retardants of formulas I-III: refer to Patent No. TWI632190 and Application No. TW109106662.

[physical property test]

The copper foil laminates of the above-mentioned Examples E1 to E4 and Comparative Examples C1 to C7 were respectively tested for physical properties, and the test results were recorded in Table 3:

Glass transition temperature (Tg): Measured by differential scanning calorimetry (DSC) according to the DSC method specified in IPC-TM-650 2.4.25.

Heat resistance of copper foil laminates (T288): also known as "tin bleaching results", the heat resistance test is based on the industry standard IPC-TM-650 2.4.24.1, the time required to soak the copper foil laminates in a tin furnace at 288°C until the board bursts .

Immersion tin test for copper-clad laminates after moisture absorption: use the prepreg containing copper foil for heat resistance (T288) test, according to industry standard IPC-TM-650 2.4.24.1, soak the copper-clad laminates at 288°C The time it takes for the tin furnace to explode.

Copper foil laminate heat resistance (S/D) test: copper-containing substrate dip tin test (solder dip 288 ℃, 10 seconds, measure the number of heat resistance cycles).

Copper foil laminated board heat resistance (PCT) test: PCT without copper substrate absorbs moisture and then dip tin test (pressure cooking at 121 ℃, after 1 hour, measure solder dip 288 ℃, 20 seconds to see whether there is a burst board).

Tensile strength between copper foil and substrate (peeling strength, half ounce copper foil, P/S): measured according to IPC-TM-650 2.4.1 testing specification.

Dielectric constant (Dk): Measured according to IPC-TM-650 2.5.5 testing specifications, the dielectric constant represents the electronic insulation properties of the film made, and the lower the value, the better the electronic insulation properties.

Dielectric loss (Df): Measured according to IPC-TM-650 2.5.5 test specification, dielectric loss indicates the ability of a substance to absorb microwaves of a certain frequency at a certain temperature, usually in the specification of communication products, the dielectric loss The lower the value, the better.

Flame resistance (flaming test, UL94): measured according to the UL94 vertical combustion method, which determines the flame resistance level of plastic materials based on the self-ignition time, self-ignition speed, and dropped particle state of the standard test piece of plastic material after being burned by flame. According to the flame resistance grade, the order is HB, V-2, V-1, V-0, and the highest is 5V. The UL 94 test method refers to the burning of plastic materials on a flame in a vertical manner. Taking every ten seconds as a test cycle, the steps are as follows: Step 1: Put the test piece into the flame for ten seconds and then remove it, and measure the continuous burning time (T1) of the test piece after the removal; Step 2: When the test piece flame After being extinguished, put it into the flame for ten seconds and then remove it, and then measure the continuous burning time (T2) of the test piece after removal; Step 3: Repeat the experiment several times and take the average value; Step 4: Calculate the ratio of T1+T2 total. The requirement of UL 94 V-0 grade is that the average of T1 and T2 of the single burning time of the test piece shall not exceed 10 seconds, and the total of T1 and T2 shall not exceed 50 seconds to meet the requirements of UL 94 V-0 .

X/Y-axis thermal expansion coefficient (CTE): Measured according to IPC-TM-650-2.4.24 test specification.

Z-axis coefficient of thermal expansion (CTE) (50-260°C): Measured according to IPC-TM-650-2.4.24.1 testing specification.

Modulus(X/Y) is determined according to the "IPC-TM-650 2.4.24.4" test specification.

table 3 property test testing method E1 E2 E3 E4 C1 C2 C3 C4 C5 Tg DSC 224 216 230 233 161 168 147 171 174 T288 TMA >60 >60 >60 >60 5 twenty two 32 >70 >70 S/D dip cycles >60 >60 >60 >60 3 18 8 >20 >20 PCT 20s /288℃ qualified qualified qualified qualified Failed qualified Failed qualified qualified P/S Hoz Cu foil 6.6 5.9 6.7 6.3 6.7 5.2 5.8 6.3 6.9 Dk 10GHz 4.07 4.10 4.10 4.11 3.93 4.14 4.25 4.21 4.04 Df 10GHz 0.007 0.008 0.007 0.008 0.015 0.009 0.012 0.013 0.011 Fire resistance UL94 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-2 X/Y CTE IPC-TM-650-2.4.24(ppm/℃) 9.3 9.6 9.8 9.1 14.6 15.0 15.7 15.3 14.8 Z CTE(50-260℃) TMA(IPC-TM-650-2.4.24.1)(%) 0.85 0.88 0.90 0.82 2.90 2.93 2.96 2.95 2.92 Modulus(X/Y) DMA (MPa) 9736 9792 9858 9679 4316 4713 5120 5005 4588 other PP appearance good good good good good Difference Difference good good

[Advantageous effects of the embodiment]

One of the beneficial effects of the present invention is that the halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity, laminated board and printed circuit board provided by the present invention can be provided by specific components and proportions, and at the same time Improve sheet toughness and heat resistance, and reduce costs. Furthermore, the composition can be made into a prepreg or resin film, which can then be applied to copper foil substrates and printed circuit boards. It can fully meet the needs of the current market.

Furthermore, the low expansion coefficient, low dielectric loss, high rigidity halogen-free resin composition provided by the present invention provides a copper foil laminate with a lower expansion coefficient, compared with the prior art X/Y axis Its CTE is lower than 10 ppm/°C, Z-axis CTE (50-260°C) is lower than 1%, and the dielectric loss (Df) is lower than 0.008 at 10GHz, providing better glass transition temperature (Tg), sheet toughness It also has better rigidity, and obviously has better heat resistance effect than the prior art.

The contents disclosed above are only preferred feasible embodiments of the present invention, and are not intended to limit the scope of the present invention. Therefore, any equivalent technical changes made by using the contents of the description and drawings of the present invention are included in the application of the present invention. within the scope of the patent.

Claims (10)

A low-expansion coefficient, low-dielectric loss, high-rigidity halogen-free resin composition, comprising: (a) 30 to 40 parts by weight of o-cresol epoxy resin; (b) 50 to 70 parts by weight of 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 phosphorous-containing flame retardant and (f) 2 to 12 parts by weight of DOPO flame retardant; wherein, the DOPO flame retardant is selected from the group consisting of the following chemical formulae (I) and (II):

(I); wherein, R ₁ is C(R ₄ ) ₂ ; R ₂ and R ₃ are each independently hydrogen, C1-C15 alkyl, C6-C12 aryl, C7-C15 aralkyl or C7-C15 alkane Aryl; or R ₂ and R ₃ can form a saturated or unsaturated cyclic ring substituted or unsubstituted by C1-C6 alkyl; each R ₄ is independently hydrogen, C1-C6 alkyl, C6-C12 aryl or C3-C12 cycloalkyl; and each m is independently selected from a positive integer from 1 to 4;

(II); wherein A is a direct bond, C6-C12 aryl, C3-C12 cycloalkyl or C3-C12 cycloalkenyl, and the cycloalkyl or cycloalkenyl may be optionally substituted by C1-C6 alkyl wherein, R ₁ , R ₂ , R ₃ and R ₄ are independently hydrogen, C1-C15 alkyl, C6-C12 aryl, C7-C15 aralkyl or C7-C15 alkaryl; or R ₁ and R ₂ or R ₃ and R ₄ can form a saturated or unsaturated cyclic ring substituted or unsubstituted by C1-C6 alkyl; each m is independently selected from a positive integer from 1 to 4, and each R ₅ and R ₆ are independently is hydrogen or C1-C6 alkyl; each n is independently selected from a positive integer from 0 to 5. The halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity according to claim 1, wherein the bismaleimide is selected from bis(4-maleimidophenyl)methane, 2,2-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 group. The halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity according to claim 1, wherein the cyanate ester hardener comprises 45 to 55 parts by weight of a novolac type cyanate ester hardener and 30 to 50 parts by weight parts of bisphenol A cyanate hardener. The halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity according to claim 1, wherein the bisphenol A type DOPO hardener has the following structure:

. The halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity according to claim 1, wherein the non-DOPO flame retardant is selected from the group consisting of resorcinol bis-xylyl phosphate, melamine polyphosphate, (2-carboxyethyl) phosphine, trimethyl phosphate, tris(isopropyl chloride) phosphate, dimethyl-methyl phosphate, bisphenol biphenyl phosphate, ammonium polyphosphate, hydroquinone- The group consisting of bis-(biphenyl phosphate), bisphenol A-bis-(biphenyl phosphate), and phosphazene compounds. The halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity according to claim 1, further comprising: a hardening accelerator, the hardening accelerator is selected from phosphorus-based hardening accelerators, amine-based hardening accelerators, A group consisting of an imidazole-based hardening accelerator, a guanidine-based hardening accelerator, a metal-based hardening accelerator, and a peroxide-based hardening accelerator. The halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity 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. The halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity according to claim 1, further comprising: an inorganic filler selected from the group consisting of silicon dioxide, aluminum oxide, aluminum hydroxide, magnesium oxide, Group consisting of magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, barium sulfate, magnesium carbonate, barium carbonate, mica, talc, and graphene . A laminate comprising: A resin substrate comprising a plurality of prepreg films, and each of the prepreg films is made of a glass fiber cloth coated with the halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity as described in claim 1 made; and A metal foil layer is disposed on at least one surface of the resin substrate. A printed circuit board comprising the laminate as claimed in claim 9.