CN114806167A - Low-expansion-coefficient halogen-free resin composition, laminated plate and printed circuit board - Google Patents

Abstract

The present application discloses a halogen-free resin composition with a low expansion coefficient, a laminated board and a printed circuit board. The halogen-free resin composition of the present application comprises: (a) 1 to 10 parts by weight of o-cresol epoxy resin, (b) 50 to 70 parts by weight of bismaleimide resin, (c) 30 to 45 parts by weight parts of polyhydroxy-modified styrene resin, (d) 60 to 90 parts by weight of a cyanate ester hardener, and (e) 1 to 20 parts by weight of a non-DOPO phosphorous-containing flame retardant. The halogen-free resin composition of the present application can provide an epoxy resin composition with low expansion coefficient, low dielectric loss and high rigidity, and provide better material toughness and heat resistance through specific components and proportions.

Description

Low-expansion coefficient halogen-free resin compositions, laminates, and printed circuit boards

technical field

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

Background technique

Under the continuous fever of the communication electronics market, high-frequency and high-speed transmission has become a necessary option, and the circuit board that plays the role of carrying components, power supply and signal transmission has become the key to the development of this field. The existing technology epoxy resin and phenolic The printed circuit board made of resin 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 bonded to the surface at high temperature and high pressure. , 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 for thermosetting resin composition. After combining with epoxy resin, the epoxy group will open the ring to form 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 bromine-based flame retardants), such as tetrabromocyclohexane, hexabromocyclodecane and 2,4,6-tris(tribromo Phenoxy)-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 When discarded, it is easy to cause pollution to the environment. In addition, halogen-containing electronic equipment waste will produce corrosive, toxic gas and smoke when burned, and dioxins, dibenzofurans, etc. will be detected in the products after combustion. carcinogens. 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 proper 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.

SUMMARY OF THE INVENTION

The technical problem to be solved by the present application 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 this application is to provide a halogen-free resin composition with a low expansion coefficient, which includes:

(a) the o-cresol epoxy resin of 1 to 10 parts by weight;

(b) 50 to 70 parts by weight of bismaleimide resin;

(c) 30 to 45 parts by weight of polyvalent hydroxyl modified styrene resin;

(d) 60 to 90 parts by weight of a cyanate ester hardener; and

(e) 1 to 20 parts by weight of a non-DOPO phosphorus-containing flame retardant.

Optionally, 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-maleimido) phenyl)methane and bis(3,5-diethyl-4-maleimidophenyl)methane.

Optionally, the polyvalent hydroxyl modified styrene resin is selected from the group consisting of the following chemical formulae (I) and (II):

所表示的取代基，n为0至20，p为0.1至2.5，X为氢或碳数1至6的烃基。wherein, R ₁ is hydrogen or a hydrocarbon group with 1 to 6 carbon atoms, and R ₂ is

In the represented substituent, n is 0 to 20, p is 0.1 to 2.5, and X is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms.

Optionally, the cyanate ester hardener includes: 30 to 45 parts by weight of a PN type cyanate ester hardener; and 30 to 45 parts by weight of a BPA type cyanate ester hardener.

Optionally, the non-DOPO phosphorus-containing flame retardant is selected from the group consisting of phosphinate, polyphosphate, phosphonium salt, phosphate ester, phosphazene and the group consisting of phosphite esters.

Optionally, the non-DOPO phosphorus-containing flame retardant is 1 to 10 parts by weight of resorcinol bis-xylyl phosphate, and 1 to 10 parts by weight of a phosphazene compound.

Optionally, the low-expansion coefficient halogen-free resin composition further comprises: a hardening accelerator, the hardening accelerator is selected from phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, guanidine-based hardening accelerators A group consisting of a hardening accelerator, a metal-based hardening accelerator, and a peroxide-based hardening accelerator.

Optionally, the low expansion coefficient halogen-free resin composition further comprises: an inorganic filler, the inorganic filler is selected from silica, alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, nitrogen A group consisting of aluminum oxide, boron nitride, aluminum silicon carbide, silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, barium sulfate, magnesium carbonate, barium carbonate, mica, talc, and graphene.

In order to solve the above-mentioned technical problem, another technical solution adopted in this application 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 The fiber cloth is made by coating the low-expansion coefficient halogen-free resin composition of the present application; and a metal foil layer is disposed on at least one surface of the resin substrate.

In order to solve the above-mentioned technical problem, another technical solution adopted by the present application is to provide a printed circuit board, which includes the laminated board of the present application.

One of the beneficial effects of the present application is that the low-expansion coefficient halogen-free resin composition, the laminate and the printed circuit board provided by the present application can be provided by specific components and proportions, and at the same time, the toughness and resistance of the sheet can be improved. heat 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 application, please refer to the following detailed description of the present application, however, the provided contents are only used for reference and description, and are not intended to limit the present application.

Detailed ways

The following are specific specific examples to illustrate the embodiments of the “low expansion coefficient halogen-free resin composition, laminate and printed circuit board” disclosed in the present application. Those skilled in the art can understand the present disclosure from the contents disclosed in this specification. Application advantages and effects. The present application 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 application. The following embodiments will further describe the related technical contents of the present application in detail, but the disclosed contents are not intended to limit the protection scope of the present application. 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 technical problem to be solved by the present application 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 this application is to provide a halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity, which comprises:

(a) the o-cresol epoxy resin of 1 to 10 parts by weight;

(b) 50 to 70 parts by weight of bismaleimide resin;

(c) 30 to 45 parts by weight of polyvalent hydroxyl modified styrene resin;

(d) 60 to 90 parts by weight of a cyanate ester hardener; and

(e) 1 to 20 parts by weight of a non-DOPO phosphorus-containing flame retardant.

The molecular structure of the o-cresol epoxy resin of the present application is that each benzene ring is connected with an epoxy group. Compared with the bisphenol A epoxy resin of the prior art, the ring of the o-cresol epoxy resin is The oxygen value is as high as 0.5eq/100g or more, and the resin can provide 2.5 times more cross-linking points when curing. Chemical resistance, high glass transition temperature (Tg), used in electronic components, can maintain good electrical insulation performance in high temperature and humid environments. Preferably, the o-cresol novolac 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, manufactured by Toto Chemical Co., Ltd., Japan, YDCN-702, YDCN-703, YDCN-704, YDCN-701P, YDCN-702P, YDCN-703P, YDCN-704P, YDCN-701S, YDCN-702S, YDCN-703S; SQCN700-1, SQCN700-2, SQCN700-3, SQCN700-4, SQCN700-4.5, SQCN702, SQCN703, SQCN700-1, SQCN704L, SQCN704ML, SQCN707, SQCN704H.

The bismaleimide resin of the present application 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. A prepolymer of a maleimide compound and an amine compound. 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 the group consisting of bis(3,5-diethyl-4-maleimidophenyl)methane.

The polyvalent hydroxyl modified styrene resin of the present application is obtained by adding a polyvalent hydroxyl compound to a styrene-based resin. The polyhydroxyl modified styrene resin of the present application can effectively reduce electrical properties and provide better hardenability and flammability. Further, the polyhydroxyl modified styrene resin of the present application can be selected from the following chemical formula (I) and (II) Groups consisting of:

所表示的取代基，n为0至20，p为0.1至2.5，X为氢或碳数1至6的烃基。wherein, R ₁ is hydrogen or a hydrocarbon group with 1 to 6 carbon atoms, and R ₂ is

In the represented substituent, n is 0 to 20, p is 0.1 to 2.5, and X is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms.

The cyanate hardener of the present application includes: 30 to 45 parts by weight of a novolac type (PN type) cyanate hardener and 30 to 45 parts by weight of a bisphenol A type (BPA type) cyanate hardener. The specific cyanate resin of the present application can increase the reactive functional groups in the resin structure, increase the glass transition temperature, and reduce the electrical properties. 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, and the bisphenol A type cyanate hardener includes commercially available Lonza model ULL-950S.

In more detail, the cyanate ester hardener has the following structure:

Wherein Ar ₁ and Ar ₂ are each independently phenylene, biphenylene, naphthylene and anthracenyl; X ₁ and X ₂ are each independently C1-C8 alkylene, C1-C8 haloalkenyl, and each R1 is independently hydrogen or C1-C8 alkyl, and n is an integer from 0 to 10.

Among them, the novolac type (PN type) cyanate hardener has the following structure:

Here, R ₁ and R ₂ each independently represent a hydrogen atom, a C1-C5 aliphatic hydrocarbon group, or a phenyl group.

Wherein, the bisphenol A type (BPA type) cyanate hardener has the following structure:

Here, R ₁ and R ₂ each independently represent a hydrogen atom, a C1-C5 aliphatic hydrocarbon group, or a phenyl group.

A non-DOPO phosphorous-containing flame retardant as defined herein, means free of 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. Preferably, the non-DOPO phosphorus-containing flame retardant is selected from the group consisting of phosphinate, polyphosphate, phosphonium salt, phosphate ester, phosphazene, and phosphazene. A group consisting of phosphite esters.

The metal salt of hypophosphite can be selected from dialkylaluminum hypophosphite, tris(diethylhypophosphite)aluminum, tris(methylethylhypophosphite)aluminum, tris(diphenylhypophosphite)aluminum, bis(diethylhypophosphite)aluminum Hypophosphite) zinc, bis (methyl ethyl hypophosphite) zinc, bis (diphenyl hypophosphite) zinc, bis (diethyl hypophosphite) titanyl, bis (methyl ethyl hypophosphite) titanyl and bis(methyl ethyl hypophosphite) (diphenyl hypophosphite) titanyl group. In more detail, the commercially available CLARIANT model is OP-935.

Examples of polyphosphates include, but are not limited to, melamine polyphosphate, melam polyphosphate, and melem polyphosphate. Commercially available polyphosphates include the model Melapur 200 available from BASF. The phosphonium salt may be selected from tetraphenylphosphonium tetraphenylborate. The phosphoric acid ester may be selected from condensed phosphoric acid ester compounds and cyclic phosphoric acid ester compounds.

The condensed phosphate compound can be selected from triphenyl phosphate, tricresyl phosphate, xylenyl-diphenyl phosphate, cresyl-diphenyl phosphate, Resorcinol bis-xylenylphosphate (resorcinoldixylenylphosphate, RDXP), resorcinol bis-diphenylphosphate (resorcinol bis-diphenylphosphate, RDP). Commercially available phosphate esters include the products available from Daha Chemical as PX-200 and PX-202.

The phosphazene compound includes a cyclic phosphazene compound and a linear phosphazene compound. Commercially available phosphazenes include those available from Otsuka Chemical under the model numbers BP-PZ, SPB-100 and SPH-100. The phosphite may be selected from trimethylphosphite and triethylphosphite.

Preferably, the non-DOPO phosphorus-containing flame retardant of the present application is 1 to 10 parts by weight of resorcinol bis-xylyl phosphate (such as PX-200) and 1 to 10 parts by weight of a phosphazene compound (such as SPB). -100), which can provide excellent halogen-free flame retardant effect.

In addition, the resin composition of the present application further comprises: a hardening accelerator, which can make the cyanate ester ring-opening reaction, and is selected from phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, 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 preferably, based on 100 parts by weight of the epoxy resin, 1 part by weight of a metal-based hardening accelerator and 3 parts by weight of a peroxide-based hardening accelerator can be used.

More specifically, metal-based hardening accelerators include metal organometallic complexes or organometallic salts such as 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 organocopper such as copper (II) acetylacetonate. Complexes, organozinc complexes such as zinc acetylacetonate (II), organoiron complexes such as iron (III) acetylacetonate, organonickel complexes such as nickel acetylacetonate (II) Organic manganese complexes 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-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.

In addition, the resin composition of the present application further includes: 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 may be surface-treated in advance via 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 fused, non-fused, porous or hollow silica), alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, nitride The 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 150 to 200 parts by weight based on 100 parts by weight of the epoxy resin. Preferably, NQ-1035I manufactured by Nomoray Company 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 application further includes an appropriate amount of solvent, for example, ketones, esters, ethers, alcohols, etc. More specifically, the solvent of the present application is selected from From the group consisting of acetone, butanone, propylene glycol methyl ether, propylene glycol methyl ether acetate, dimethylacetamide, and cyclohexanone. For example, the solvent may be selected from a combination of 50 to 60 parts by weight of butanone (MEK) and 40 to 50 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 in this application 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 The fiber cloth is made by coating the halogen-free resin composition with low expansion coefficient, low dielectric loss and high rigidity of the present application; and a metal foil layer, which is arranged on at least one surface of the resin substrate.

Another technical solution provided by the present application is a laminated board, 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 as shown in the present invention. and (b) a metal foil layer, which is arranged on at least one surface of the resin substrate, or the metal foil layers are arranged on the upper and lower sides of the resin substrate as required.

In addition, the present application provides yet another technical solution, which is a printed circuit board, which includes the laminate of the present application.

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

Example

The following Examples E1 to E4 are used to manufacture the prepreg in a continuous process using the halogen-free low-dielectric epoxy resin composition of the present application. Usually glass fiber cloth is used as the base material. The roll of 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 application. 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 take four prepreg films and two 18μm copper foils from the same batch of prepreg films prepared in the above batch, and stack them in the order of copper foil, four prepreg films, and copper foil, and then place them in the same batch. 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

*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.

*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. The roll of 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 application. 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 take four prepreg films and two 18μm copper foils from the same batch of prepreg films prepared in the above batch, and stack them in the order of copper foil, four prepreg films, and copper foil, and then place them in the same batch. 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

*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 to 3 and flame retardants of formulas I to 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 "bleaching results", the heat resistance test is based on the industry standard IPC-TM-650 2.4.24.1, the copper foil laminates are immersed in a tin furnace at 288°C until they explode board time.

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

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 is immersed in tin after moisture absorption test (pressurecooking 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 grade of plastic materials based on the self-ignition time, self-ignition speed, and dropped particle state after the standard test piece of plastic material is burned by flame. According to the flame resistance grade, the order is HB, V-2, V-1, V-0, and the highest is 5V. Whereas the UL 94 test method refers to the burning of the plastic material 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 removing it; Step 3: Repeat the experiment several times and take the average value; Step 4: Calculate the value of T1+T2. total. The requirement of UL 94V-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 94V-0.

X/Y-axis thermal expansion coefficient (CTE): Measured according to IPC-TM-650-2.4.24 testing 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) was determined according to the "IPC-TM-650 2.4.24.4" test specification.

table 3

Beneficial Effects of Embodiments

One of the beneficial effects of the present application is that the low-expansion coefficient halogen-free resin composition, the laminate and the printed circuit board provided by the present application can be provided by specific components and proportions, and at the same time, the toughness and resistance of the sheet can be improved. heat 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 of the copper foil laminates provided by the application has a relatively low expansion coefficient, compared with the prior art X / The CTE of the Y-axis is lower than 10ppm/°C, the CTE of the Z-axis (50-260°C) is lower than 2%, and the dielectric loss (Df) is lower than 0.007 at 10GHz, providing a better glass transition temperature (Tg), The plate also has better rigidity in terms of toughness, and obviously has better heat resistance effect than the prior art.

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

Claims (10)

1. A low expansion coefficient halogen-free resin composition, which is characterized by comprising:

(a)1 to 10 parts by weight of an o-cresol formaldehyde epoxy resin;

(b)50 to 70 parts by weight of a bismaleimide resin;

(c)30 to 45 parts by weight of a polyhydric hydroxyl-modified styrene resin;

(d)60 to 90 parts by weight of a cyanate ester hardener; and

(e)1 to 20 parts by weight of a non-DOPO phosphorus containing flame retardant.

2. The low expansion factor 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 halogen-free resin composition with low expansion coefficient as claimed in claim 1, wherein the polyhydroxyl-modified styrene resin is selected from the group consisting of the following formulas (I) and (II):

wherein R is ₁ Is hydrogen or a hydrocarbon group of 1 to 6 carbon atoms, R ₂ Is composed of

The substituent represented by the formula (I), n is 0 to 20, p is 0.1 to 2.5, and X is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms.

4. The low expansion coefficient halogen-free resin composition of claim 1, wherein the cyanate ester hardener comprises: 30 to 45 parts by weight of a PN type cyanate ester hardener; and 30 to 45 parts by weight of a BPA-type cyanate ester hardener.

5. The low expansion factor halogen-free resin composition of claim 1, wherein the non-DOPO phosphorus-containing flame retardant is selected from the group consisting of metal hypophosphite (phosinate), polyphosphate (polyphosphate), phosphonium salt (phosphonium salt), phosphate ester (phosphonite ester), phosphazene (phosphonitrile), and phosphite ester (phosphonite ester).

6. The halogen-free resin composition with low expansion coefficient of claim 1, wherein the non-DOPO phosphorus-containing flame retardant is 1 to 10 parts by weight of resorcinol dixylylphosphate and 1 to 10 parts by weight of phosphazene compound.

7. The low expansion coefficient halogen-free resin composition of claim 1, wherein 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.

8. The low expansion coefficient halogen-free resin composition of claim 1, wherein 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.

9. A laminate panel, comprising:

a resin substrate comprising a plurality of prepreg sheets, wherein each prepreg sheet is made of a glass fiber cloth coated with the halogen-free resin composition with low expansion coefficient according to claim 1; and

and the metal foil layer is arranged on at least one surface of the resin substrate.

10. A printed circuit board comprising the laminate of claim 9.