WO2020047920A1

WO2020047920A1 - Thermosetting resin composition and prepreg, laminate and high frequency circuit substrate containing same

Info

Publication number: WO2020047920A1
Application number: PCT/CN2018/108196
Authority: WO
Inventors: 罗成; 唐国坊
Original assignee: 广东生益科技股份有限公司
Priority date: 2018-09-07
Filing date: 2018-09-28
Publication date: 2020-03-12
Also published as: CN109337289A; CN109337289B

Abstract

Disclosed are a thermosetting resin composition, and a prepreg, a laminate and a high frequency circuit substrate which contain same. The thermosetting resin composition comprises the following components: 12-50 parts by weight of a cyanate ester resin; 30-60 parts by weight of an epoxy resin; and 10-28 parts by weight of a biphenyl phenolic resin. The prepreg and a copper-cladded substrate, which are prepared from the provided thermosetting resin composition, have a high glass transition temperature, excellent dielectric properties, a low water absorption, a high thermal resistance, a high peel strength, and a high interlaminar adhesive force and have a good processability.

Description

Thermosetting resin composition and prepreg, laminate and high-frequency circuit substrate containing the same

Technical field

The invention belongs to the technical field of laminates, and relates to a thermosetting resin composition and a prepreg, a laminate and a high-frequency circuit substrate using the same.

Background technique

Traditional laminates for printed circuits usually use bromine flame retardants to achieve flame retardancy, especially tetrabromobisphenol A epoxy resin. This brominated epoxy resin has good flame retardancy, but it is burning. When hydrogen bromide gas is generated. In addition, in recent years, carcinogens such as dioxin and dibenzofuran have been detected in the combustion products of electronic and electrical equipment wastes containing halogens such as bromine and chlorine, so the application of brominated epoxy resins is limited. On July 1, 2006, the two environmental directives of the European Union, "About the Waste Electrical and Electronic Equipment Directive" and "About the Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment," were formally implemented. The development of flame-retardant copper-clad laminates became Industry hotspots, all copper-clad laminate manufacturers have launched their own flame-retardant copper-clad laminates.

At the same time, with the high-speed and multi-functionalization of consumer electronics product information processing, the application frequency continues to increase. In addition to the increasing environmental protection requirements, the dielectric constant and dielectric loss of printed circuit boards are required to be lower and lower. Reducing Dk / Df has become a hot spot for substrate industry players.

In addition, for the copper-clad substrate material, in order to meet the PCB processing performance and the performance requirements of terminal electronic products, it must have good dielectric properties, heat resistance and mechanical properties. The peel strength, excellent heat and humidity resistance and UL94 V-0 flame retardant grade.

CN103298882A discloses a thermosetting resin composition, a prepreg and a metal foil laminate using the same, by using a specific content of a novolac resin as a curing agent in a BT resin or a mixture of a cyanate resin and an epoxy resin, Therefore, the separation of the resin and the inorganic filler during the process of laminating the prepreg on the metal foil is suppressed, but the flame retardant and dielectric properties are not involved therein. CN102873940A discloses a halogen-free, low-dielectric-constant, high-toughness copper-clad laminate, which is prepared by using bisphenol A cyanate as a main resin in a resin glue formulation, and adding a multifunctional epoxy resin and a phenolic resin at the same time. The obtained board has a lower dielectric constant and good heat and humidity resistance, but the epoxy resin is a curing agent with a small content. CN102127296A discloses a cyanate resin composition and a copper-clad board prepared by using the same. The composition includes a bisphenol A type cyanate resin, a brominated bisphenol A epoxy resin, and a 1-5% phenolic resin. High heat resistance, good dielectric properties, good humidity and heat resistance and flame retardancy. CN104212167A discloses the preparation and application of a low-cost low-dielectric-constant thermosetting resin. The resin is cured by reacting two or three resins among cyanate ester, epoxy resin, and phenol resin containing phenyl ether structure. Copper-clad laminate with good dielectric properties and high impact performance. However, the phenyl ether structure contained in the phenol resin of the phenyl ether structure results in insufficient heat resistance and low T _g , which limits its application. CN101208386A discloses an epoxy resin composition for encapsulating a semiconductor device, which contains a mixture of a phenol resin type phenol compound having a biphenyl-derived group and 4,4′-dihydroxybiphenyl through a glycidyl etherification reaction The prepared modified epoxy resin, curing agent and inorganic filler have good resistance to bending and reflow, but it does not involve its dielectric properties, moisture and heat resistance, and glass transition temperature (T _g ). CN102211984A discloses an epoxy plastic sealing material and an epoxy resin and a preparation method thereof. The epoxy plastic sealing material includes a biphenol aldehyde resin derivative, an epoxy resin, a curing agent and a filler, and has intrinsic flame retardancy and low viscosity. The characteristics are not related to its peel strength and interlayer adhesion.

As we all know, there are many materials with low dielectric constant and dielectric loss tangent properties, such as: polyolefin, fluororesin, polystyrene, polyphenylene ether, modified polyphenylene ether, bismaleimide-tris Although these resins have good dielectric properties, they have the disadvantages of difficult processing, poor heat resistance, etc., and have poor peel strength and interlayer adhesion, which cannot meet high frequency and high speed. Requirements for copper clad substrates.

Therefore, it is desired to develop a thermosetting resin composition with high T _g , excellent dielectric properties and heat resistance, and at the same time, it can take into account performance requirements such as peel strength and interlayer adhesion to prepare laminates and high-frequency circuits. Substrate, etc.

Summary of the Invention

An object of the present invention is to provide a thermosetting resin composition and a prepreg, a laminate, and a high-frequency circuit board containing the same.

To achieve this, the present invention adopts the following technical solutions:

In a first aspect, the present invention provides a thermosetting resin composition. The thermosetting resin composition includes the following components:

Cyanate resin 12-50 parts by weight;

Epoxy resin: 30-60 parts by weight;

Biphenol formaldehyde resin 10-28 parts by weight.

In the present invention, a cyanate resin and a biphenol-formaldehyde resin are used together as a curing agent for the epoxy resin, and each has its own advantages in the system: the cyanate resin can improve the heat resistance of the thermosetting resin composition and reduce the dielectric loss At the same time, the phenolic hydroxyl group contained in the biphenol-formaldehyde resin can effectively promote the curing of cyanate esters and generate a highly symmetrical triazine structure, which brings excellent dielectric properties. The epoxy resin is effectively cured under the action of an acid ester, and the obtained cured product has a high T _g , and has excellent dielectric properties and heat resistance. In addition, the biphenol aldehyde resin itself is a self-extinguishing material, and the content of the flame retardant in the system can be adjusted to achieve the effect of UL94 V-0 flame retardant grade.

In the present invention, epoxy resin, cyanate resin, and biphenol formaldehyde resin are selected and mixed for curing. All three work together to synergize, and can significantly improve the T of prepregs made of the resin composition and laminates for printed circuits. _g and heat resistance, and it has excellent dielectric properties, low water absorption, good humidity and heat resistance, and good processability, but also makes the system have excellent peel strength and interlayer adhesion.

In the present invention, the weight part of the biphenol aldehyde resin is 10-28 weight parts, for example, 12 weight parts, 15 weight parts, 18 weight parts, 20 weight parts, 22 weight parts, 25 weight parts, and the like. When the content of biphenol-formaldehyde resin is too low, the curing cross-linking catalysis effect on cyanate ester is too weak, resulting in a larger amount of cyanate ester resin reacting with epoxy resin instead of homopolymerization to form high symmetry and electrical properties. A good triazine ring results in slightly poor electrical properties of the composition; when the content of biphenol-formaldehyde resin is too high, on the one hand, it will affect the electrical properties of the system, on the other hand, the curing and cross-linking of biphenol-formaldehyde resin to cyanate esters The catalytic effect is too fast, it is easy to form too many cyanate self-polymers, and it is not easy to form a more uniform interpenetrating system, resulting in a low T _{g of the} system, low interlayer bonding force and peel strength, and poor heat and humidity resistance.

In the present invention, the structure of the biphenol-formaldehyde resin is shown in Formula I:

Among them, n is an integer from 1 to 10, such as 2, 3, 4, 5, 6, 7, 8, 9, and the like.

In the present invention, the above-mentioned biphenol-formaldehyde resin is selected, and the value of n is an integer of 1-10. In the present invention, when n is 0, the hydroxyl equivalent is too low, too many hydroxyl groups, and the catalytic effect is too good, which causes the cyanate resin to be cured too quickly, but the heat resistance of the system is deteriorated. The electrical properties are also poor; when the n value is> 10, the solubility of biphenolaldehyde in the solvent is too poor, which affects the preparation of the glue.

In the present invention, the weight part of the cyanate resin is 12-50 parts by weight, for example, 13 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 35 parts by weight, 38 parts by weight, 40 parts by weight, 45 parts by weight, 48 parts by weight, and the like. When the cyanate resin content is too low, the degree of cross-linking of the system is too low; when the cyanate resin content is excessive, the system has poor heat and humidity resistance.

In the present invention, the cyanate resin has a structure of Formula II or Formula III:

Wherein R _{1 is} selected from -CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- ,

or

Any of: R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R _8, and R ₉ are each independently selected from a hydrogen atom, a substituted or unsubstituted linear alkyl group of C1-C4 Or C1-C4 substituted or unsubstituted branched alkyl.

Preferably, the cyanate resin is selected from 2,2-bis (4-cyanoxyphenyl) propane, bis (4-cyanoxyphenyl) ethane, and bis (3,5-dimethyl- 4-cyanooxyphenyl) methane, 2,2-bis (4-cyanooxyphenyl) -1,1,1,3,3,3-hexafluoropropane, α, α′-bis (4- Cyanooxyphenyl) -m-isopropylbenzene, cyclopentadiene-based cyanate, phenol novolac cyanate, cresol novolac cyanate, 2,2-bis (4-cyanoxybenzene Propyl) propane prepolymer, bis (4-cyanooxyphenyl) ethane prepolymer, bis (3,5-dimethyl-4-cyanoxyphenyl) methane prepolymer, 2,2- Bis (4-cyanooxyphenyl) -1,1,1,3,3,3-hexafluoropropane prepolymer, α, α′-bis (4-cyanooxyphenyl) -m-diisopropyl Any one or a mixture of at least two of a benzene prepolymer, a cyclopentadiene cyanate prepolymer, a phenol novolac cyanate prepolymer, or a cresol novolac cyanate prepolymer, More preferred are 2,2-bis (4-cyanooxyphenyl) propane, α, α′-bis (4-cyanoxyphenyl) -m-isopropylbenzene, and bis (3,5-dimethyl) 4-cyanooxyphenyl) methane, 2,2-bis (4-cyanoxyphenyl) propane prepolymer, α Any of α′-bis (4-cyanooxyphenyl) -m-isopropylbenzene prepolymer or bis (3,5-dimethyl-4-cyanoxyphenyl) methane prepolymer Or a combination of at least two.

In the present invention, the weight part of the epoxy resin is 30-60 weight parts, for example, 35 weight parts, 38 weight parts, 40 weight parts, 42 weight parts, 45 weight parts, 48 weight parts, 50 weight parts, 55 Parts by weight, 58 parts by weight, and the like.

In the present invention, the epoxy resin is an epoxy resin having two or more epoxy groups in one molecule.

Preferably, the epoxy resin is selected from a glycidyl ether epoxy resin, a glycidyl ester epoxy resin, a glycidylamine epoxy resin, an alicyclic epoxy resin, an epoxidized olefin epoxy resin, Any one of Hein epoxy resin or imide epoxy resin or a combination of at least two of them.

Preferably, the glycidyl ether epoxy resin includes a bisphenol A type epoxy resin (for example, a bisphenol A type phenolic epoxy resin), a bisphenol F type epoxy resin, an o-cresol novolac epoxy resin, and triphenol Any one or a combination of at least two types of novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin, alkylbenzene novolac epoxy resin, or naphthol novolac epoxy resin .

Further preferably, the epoxy resin is an epoxy resin having a formula IV structure:

Wherein Z ₁ , Z ₂ and Z ₃ are each independently selected from

or

In any one of them, R _{10 is} selected from any one of a hydrogen atom, a C1-C5 substituted or unsubstituted linear alkyl group, or a C1-C5 substituted or unsubstituted branched alkyl group.

Y ₁ and Y ₂ are each independently selected from a single bond, -CH _2- ,

or

In any one of them, R _{11 is} selected from a hydrogen atom, a C1-C5 substituted or unsubstituted linear alkyl group, or a C1-C5 substituted or unsubstituted branched alkyl group.

n ₁ is an integer from 1 to 10, such as 2, 3, 4, 5, 6, 7, 8, 9, and the like.

Preferably, the glycidyl amine epoxy resin includes triglycidyl p-aminophenol, triglycidyl trimeric isocyanate, tetraglycidyl diaminodimethylenebenzene, tetraglycidyl-4,4 ′ -Diaminodiphenylmethane, tetraglycidyl-3,4'-diaminodiphenyl ether, tetraglycidyl-4,4'-diaminodiphenyl ether, or tetraglycidyl-1,3-diamino Any one or a combination of at least two of methylcyclohexane.

The thermosetting resin composition of the present invention adopts the above-mentioned epoxy resin having a specific molecular structure, which has higher functionality and good dielectric properties, has a higher cured product T _g , and has a lower water absorption rate.

In order to further increase the crosslinking density of the thermosetting resin composition to be obtained, the thermosetting resin composition may preferably further include a curing accelerator.

Preferably, based on the total weight of the cyanate resin, the epoxy resin, and the biphenol-formaldehyde resin being 100 parts by weight, the addition amount of the curing accelerator is 0.01-1 part by weight, for example, 0.02 part by weight, 0.05 part by weight, 0.1 parts by weight, 0.5 parts by weight, 0.8 parts by weight, etc., more preferably 0.01-0.2 parts by weight;

Preferably, the curing accelerator includes any one or at least two of an organic metal salt, an imidazole compound, a derivative of an imidazole compound, a piperidine compound, a pyridine compound, a Lewis acid, or triphenylphosphine. combination.

Preferably, the organic metal salt includes any one or at least two of metal octanoate, metal isooctanoate, metal acetylacetonate, metal naphthenate, metal salicylate, or metal stearate. combination.

Preferably, the metal is selected from any one or a combination of at least two of zinc, copper, iron, tin, cobalt, or aluminum.

Preferably, the imidazole compound is any one or a combination of at least two of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, or 2-undecylimidazole .

Preferably, the piperidines are 2,3-diaminopiperidine, 2,5-diaminopiperidine, 2,6-diaminopiperidine, 2-amino-3-methylpiperidine, 2- Any of amino-4-methylpiperidine, 2-amino-3-nitropiperidine, 2-amino-5-nitropiperidine, or 2-amino-4,4-dimethylpiperidine or A combination of at least two.

Preferably, the pyridine compound is any one or a combination of at least two of 4-dimethylaminopyridine, 2-aminopyridine, 3-aminopyridine, and 4-aminopyridine.

Preferably, the thermosetting resin composition further includes a filler.

Preferably, based on the total weight of the cyanate resin, epoxy resin, and biphenol-formaldehyde resin being 100 parts by weight, the filler is added in an amount of 5-300 parts by weight, such as 10 parts by weight, 15 parts by weight, 20 parts by weight Parts, 50 parts by weight, 80 parts by weight, 100 parts by weight, 150 parts by weight, 180 parts by weight, 250 parts by weight, 280 parts by weight, etc., and more preferably 5-200 parts by weight.

Preferably, the median particle diameter of the filler is 0.01-50 μm, for example, 0.02 μm, 0.05 μm, 0.15 μm, 0.2 μm, 0.5 μm, 0.8 μm, 1 μm, 1.5 μm, 2 μm, 5 μm, 8 μm, 10 μm, 15 μm, 25 μm, 30 μm, 40 μm, 45 μm, etc., more preferably 0.01-20 μm, and still more preferably 0.1-10 μm.

Preferably, the filler is selected from organic fillers or inorganic fillers, more preferably inorganic fillers, still more preferably surface-treated inorganic fillers, and most preferably surface-treated silica.

Preferably, the surface-treated surface treatment agent is selected from any one or a combination of at least two of a silane coupling agent, a silicone oligomer, or a titanate coupling agent.

Preferably, based on 100 parts by weight of the inorganic filler, the amount of the surface treatment agent is 0.1-5.0 parts by weight, such as 0.2 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1.0 parts by weight, 1.2 parts by weight, 1.5 parts by weight , 2.0 parts by weight, 2.5 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, etc., more preferably 0.5-3.0 parts by weight, and still more preferably 0.75-2.0 parts by weight.

Preferably, the inorganic filler is selected from any one or a combination of at least two of non-metal oxides, metal nitrides, non-metal nitrides, inorganic hydrates (such as metal hydrates), inorganic salts, or inorganic phosphorus. Further preferred are fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, aluminum oxide, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, and titanic acid. Any one or a combination of at least two of barium, strontium titanate, calcium carbonate, calcium silicate, or mica.

Preferably, the organic filler is selected from any one or a combination of at least two of polytetrafluoroethylene, polyphenylene sulfide, or polyethersulfone.

In the present invention, the thermosetting resin composition further includes a flame retardant.

The present invention does not limit the kind of flame retardant, and any flame retardant that can achieve the flame retardant effect can be used in the present invention.

In a second aspect, the present invention provides a prepreg, which includes a reinforcing material and the thermosetting resin composition according to the first aspect attached to the prepreg after drying by dipping.

In a third aspect, the present invention provides a laminate including at least one prepreg according to the second aspect.

According to a fourth aspect, the present invention provides a high-frequency circuit substrate. The high-frequency circuit substrate includes at least one prepreg according to the second aspect, and one or both sides of the prepreg after being laminated. Metal foil.

Preferably, the metal foil is a copper foil.

Compared with the prior art, the present invention has the following beneficial effects:

(1) In the present invention, a cyanate resin and a biphenol-formaldehyde resin are used together as a curing agent for the epoxy resin. The three are mixed and cured to work together to make the composition have a higher glass transition temperature, excellent dielectric properties, and Heat resistance, at the same time have lower water absorption and higher peel strength and interlayer adhesion;

(2) The T _g of the copper-clad laminate prepared from the thermosetting resin composition provided by the present invention is above 185 ° C, the dielectric constant is below 4.23 (10 GHz), the dielectric loss is below 0.008 (10 GHz), and its peel strength is Above 0.82N / mm, the interlayer bonding force is above 0.65N / mm. When a small amount of flame retardant is added, the flame retardant effect can reach V-0.

detailed description

The technical solutions of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are merely to help understand the present invention and should not be regarded as a specific limitation to the present invention.

Preparation Example 1

In this preparation example, biphenolaldehyde (n = 0, LBPN-1) was synthesized. The preparation method is as follows:

In a 250 mL three-necked flask equipped with a stirring device and a reflux condenser, add 25.1 g of 4,4′-dichloromethylbiphenyl and 3 g of methanol, continue to purge nitrogen, add 75.2 g of phenol and 3 g of 37% hydrochloric acid, at 90 ° C. Under reflux for 5h. During the entire process, the reaction system changed from a milky white suspension to a light yellow solution, and gas was emitted, and the tail gas was passed into water or an alkaline solution for absorption. After the reaction, the temperature was elevated to 180 ° C. to remove the excess phenol under reduced pressure. The product in the bottle was decanted while hot. After cooling, a light yellow solid LBPN-1 was obtained, with a hydroxyl equivalent of 185 and n = 0.

Preparation Example 2

In this preparation example, biphenolaldehyde (n = 5, LBPN-2) was synthesized. The preparation method is as follows:

In a 250 mL three-necked flask equipped with a stirring device and a reflux condenser, 25.1 g of 4,4′-dichloromethylbiphenyl and 3 g of methanol were added. Nitrogen was continuously introduced, and 16.9 g of phenol and 4 g of 37% hydrochloric acid were added. Under reflux for 6h. During the entire process, the reaction system changed from a milky white suspension to a light yellow solution, and gas was emitted, and the tail gas was passed into water or an alkaline solution for absorption. After the reaction, the temperature was raised to 180 ° C. to remove the excess phenol under reduced pressure. The product in the bottle was decanted while hot. After cooling, a light yellow solid LBPN-2 was obtained, with a hydroxyl equivalent of 244 and n = 5.

Preparation Example 3

This preparation example synthesizes biphenol aldehyde (n = 10, LBPN-3). The preparation method is as follows:

In a 250 mL three-necked flask equipped with a stirring device and a reflux condenser, 25.1 g of 4,4′-dichloromethylbiphenyl and 4 g of methanol were added. Nitrogen was continuously introduced, and 12.2 g of phenol and 4 g of 37% hydrochloric acid were added at 90 ° C. Under reflux for 7h. During the entire process, the reaction system changed from a milky white suspension to a light yellow solution, and gas was emitted, and the tail gas was passed into water or an alkaline solution for absorption. After the reaction, the temperature was raised to 180 ° C. to remove the excess phenol under reduced pressure. The product in the flask was decanted while hot. After cooling, a light yellow solid LBPN-3 was obtained, with a hydroxyl equivalent of 254 and n = 10.

Preparation Example 4

This preparation example synthesizes biphenol aldehyde (n = 13, LBPN-4). The preparation method is as follows:

In a 250 mL three-necked flask equipped with a stirring device and a reflux condenser, 25.1 g of 4,4′-dichloromethylbiphenyl and 5 g of methanol were added. Nitrogen was continuously introduced, and 10.8 g of phenol and 5 g of 37% hydrochloric acid were added. The reaction was refluxed for 8 h. During the entire process, the reaction system changed from a milky white suspension to a light yellow solution, and gas was emitted, and the tail gas was passed into water or an alkaline solution for absorption. After the reaction, the temperature was raised to 180 ° C. to remove the excess phenol under reduced pressure. The product in the bottle was decanted while hot. After cooling, a light yellow solid LBPN-4 was obtained, with a hydroxyl equivalent of 257 and n = 13.

The materials and brand information involved in the following examples and comparative examples are as follows:

(A) Cyanate

CY-40: Wuqiao Resin Plant, DCPD type cyanate resin;

PT30S: LONCZ, phenolic cyanate resin;

CE01PS: Jiangsu Tianqi, bisphenol A cyanate resin;

CE01MO: Jiangsu Tianqi, bisphenol A cyanate resin;

(B) Epoxy resin

HP-7200HHH-M57: DIC, DCPD epoxy resin, epoxy equivalent 288;

HP-7200H-75M: DIC, DCPD epoxy resin, epoxy equivalent 280;

HP-6000: DIC, epoxy resin, epoxy equivalent 250;

HP-9900: DIC, naphthol-type epoxy resin, epoxy equivalent 274;

NC-3000H: Nippon Kayaku, biphenyl epoxy resin, epoxy equivalent 294;

SKE-1: Suncote, special epoxy resin, epoxy equivalent 120;

SKE-3: Suncote, special epoxy resin, epoxy equivalent 120;

(C) Phenolic resin

MEH-7851H: Meiwa Chemical, biphenol-formaldehyde resin, hydroxyl equivalent 235, corresponding to n = 3;

BPNH9781: Hunan Jiashengde, biphenol-formaldehyde resin, hydroxyl equivalent 235, corresponding to n = 3;

SH-5120: Shengquan, Jinan, biphenol-formaldehyde resin, hydroxyl equivalent 235, corresponding to n = 3;

LBPN-1: homemade, biphenol aldehyde, hydroxyl equivalent 185, corresponding to n = 0;

LBPN-2: homemade, biphenol aldehyde, hydroxyl equivalent 244, corresponding to n = 5;

LBPN-3: self-made, biphenol aldehyde, hydroxyl equivalent 254, corresponding to n = 10;

LBPN-4: self-made, biphenol aldehyde, hydroxyl equivalent 257, corresponding to n = 13;

2812: MOMENTIVE, phenol novolac, hydroxyl equivalent 105;

DOW-9274: Olin, phenolic phenol, hydroxyl equivalent 340;

(D) Accelerator

2E4MZ: 2-ethyl-4-methylimidazole, Shikoku Chemicals;

Zinc isooctanoate: The Shepherd Chemical Company

(E) Filler

Spherical silicon: fused silica, with an average particle size of 1-10 μm and a purity of 99% or more;

(F) Flame retardant

OP935: Clariant, aluminum diethyl hypophosphite, with a phosphorus content of 23.5%;

FR-245: Israeli chemistry, bromotriazine, bromine content 67%.

Examples 1-8

A thermosetting resin composition was prepared according to the components shown in Table 1, and a copper-clad laminate sample was prepared according to the following method for the production of a copper-clad laminate:

Mix the cyanate ester resin, biphenol aldehyde resin and epoxy resin with optional curing accelerator, flame retardant and filler in the solvent according to the proportion in Table 1 to control the glue liquid-solid content to 65%. Use 2116 glass fiber The cloth is impregnated with the above glue, controlled to a suitable thickness, and then baked in an oven at 115-175 ° C for 2-15 minutes to make a prepreg, and then several prepregs are stacked together, and 18 μm RTF copper is stacked on both sides thereof. The foil is made of a copper-clad laminate under the conditions of a curing temperature of 170-250 ° C, a curing pressure of 25-60 kg / cm ² , and a curing time of 60-300 min.

Comparative Examples 1-8

A thermosetting resin composition was prepared according to the components shown in Table 2. A copper-clad laminate sample was prepared according to the method for manufacturing a copper-clad laminate described in Example 1-8.

Table 1

Table 2

Performance Testing

Performance tests were performed on the copper clad boards provided in Examples 1-8 and Comparative Examples 1-8. The test methods are as follows:

(1) Glass transition temperature (T _g ): Use DMA test to measure according to DMA test method specified in IPC-TM-650 2.4.24;

(2) Dielectric constant (Dk) and dielectric loss factor (Df): tested according to SPDR method;

(3) Moisture and heat resistance (PCT) evaluation: After the copper foil on the surface of the copper-clad laminate is etched, the substrate is evaluated; the substrate is placed in a pressure cooker, treated at 120 ° C and 105KPa for 2 hours, and dipped in a tin furnace at 288 ° C Record the corresponding time when the substrate is delaminated; when the substrate is in the tin furnace for more than 5 minutes without bubbling or delamination, the evaluation can be ended, × is delaminated, and O is delaminated;

(4) Thermal expansion coefficient (CTE): measured in accordance with the CTE test method specified in IPC-TM-650 2.4.24C;

(5) Interlayer bonding force: measured according to the interlayer bonding force test method specified in IPC-TM-650 2.4.8;

(6) Peeling strength: measured in accordance with the peeling strength test method specified in IPC-TM-650 2.4.8;

(7) Thermal cracking time (T288): Use a TMA instrument to measure in accordance with the T288 test method specified in IPC-TM-650 2.4.24.1;

(8) Flame retardancy: According to UL 94 standard method.

The test results of the copper-clad laminates provided for the examples and comparative examples are shown in Table 3-6:

table 3

Table 4

table 5

Table 6

It can be known from the examples and the performance tests that the prepreg made from the thermosetting resin composition provided by the present invention and the obtained copper-clad board have a T _{g of} more than 185 ° C, and can even reach 245 ° C. Its dielectric properties are excellent, and With good moisture and heat resistance, high peel strength and interlayer bonding force, low thermal expansion coefficient and good processability, when a small amount of flame retardant is added, its flame retardant effect can reach V-0.

It can be known from the comparison between Examples 1, 7 and Comparative Examples 1, 4 that the amounts of the cyanate resin and the epoxidized resin provided by the present invention should be within the range provided by the present invention. The amount of resin exceeds the upper limit, the copper-clad laminate produced has low T _g , large CTE, low peel strength and low interlayer bonding force; when excessive cyanate resin is used and the amount of epoxy resin exceeds the lower limit, the moisture-heat resistance of the copper-clad laminate will be poor. . It can be known from the comparison between Examples 2, 6 and Comparative Examples 2 and 3 that the added amount of biphenol-formaldehyde resin used in the present invention is 10-28 parts by weight, and the copper-clad laminates obtained below or exceeding this weight range cannot reach the present application. The technical effect is that when the amount of biphenol-formaldehyde resin is excessively added, the content of phenolic hydroxyl groups in the system is too much, resulting in poor electrical properties of the system, and at the same time, the catalytic effect of excessive biphenol-aldehyde curing and crosslinking of cyanate ester is too fast. , It is not easy to form a more uniform interpenetrating system, which results in a lower T _{g of the} system, low interlayer adhesion and peel strength, and poor heat and humidity resistance. When the amount of biphenol-formaldehyde resin is too low, the The catalytic effect of curing and crosslinking of cyanate esters is too weak, which causes a large amount of cyanate esters to chemically react with epoxy, instead of homopolymerizing to form a highly symmetrical, good electrical performance triazine ring, resulting in slightly poor electrical performance of the system. From the comparison between Example 8 and Comparative Example 5, it can be known that when the conventional phenolic resin is used in place of the biphenolic resin used in the present invention, the conventional phenolic resin has a lower hydroxyl equivalent and a larger hydroxyl content, which catalyzes the cyanate resin. The effect is too rapid, only the self-polymer of the cyanate resin is formed, and a more uniform interpenetrating system cannot be formed. The phenolic resin and the epoxy resin do not react or react less, and cannot be made into a board. From the comparison between Example 8 and Comparative Example 6, it can be known that when the phosphorus-containing phenolic resin is selected, although its hydroxyl equivalent is high, the softening point of the phosphorus-containing phenolic material is too low, even though it can participate in the curing of the system, but the plasticizing effect Too strong, resulting in low T _{g of the} sheet and poor resistance to humidity and heat. It can be seen from the comparison between Example 3 and Comparative Example 7 that when biphenolaldehyde with n = 0 is selected, the hydroxyl equivalent is low, the hydroxyl content is large, the electrical properties are poor, and the catalytic effect on the cyanate resin is too rapid. It is more difficult to form a more uniform interpenetrating system, which has poor resistance to moisture and heat; and this biphenol-formaldehyde resin has a small molecular weight and low self-softening point, which results in poor heat resistance. Its sheet has a low T _g and a T288 layered burst. From the comparison between Example 3 and Comparative Example 8, it can be seen that when biphenolaldehyde with n = 13 is selected, although its hydroxyl equivalent is large and its hydroxyl content is small, its molecular weight is too large, but its solubility is poor. Difficult to make into sheet. Therefore, the thermosetting resin composition of the present invention not only requires the combination of a cyanate resin, an epoxy compound, and a biphenol-formaldehyde resin, etc., but also satisfies the proportion of each component in order to obtain a copper-clad laminate having excellent properties.

The applicant states that the present invention illustrates the thermosetting resin composition of the present invention and the prepreg, laminate, and high-frequency circuit substrate containing the same through the above examples, but the present invention is not limited to the above examples, which does not mean The present invention must be implemented by relying on the above embodiments. Those skilled in the art should know that any improvement to the present invention, equivalent replacement of the raw materials of the products of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the scope of protection and disclosure of the present invention.

Claims

A thermosetting resin composition, characterized in that the thermosetting resin composition includes the following components:

Cyanate resin 12-50 parts by weight;

Epoxy resin: 30-60 parts by weight;

Biphenol resin 10-28 parts by weight.
The thermosetting resin composition according to claim 1, wherein the structure of the biphenol aldehyde resin is as shown in Formula I:

Here, n is an integer of 1-10.
The thermosetting resin composition according to claim 1 or 2, wherein the cyanate resin has a structure of Formula II or Formula III:

Wherein R 1 is selected from -CH 2- , -CH (CH 3 )-, -C (CH 3 ) 2- , -C (CF 3 ) 2- ,

Any of: R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8, and R 9 are each independently selected from a hydrogen atom, a substituted or unsubstituted linear alkyl group of C1-C4 Or C1-C4 substituted or unsubstituted branched alkyl.
The thermosetting resin composition according to any one of claims 1-3, wherein the cyanate resin is selected from the group consisting of 2,2-bis (4-cyanooxyphenyl) propane, and bis (4 -Cyanooxyphenyl) ethane, bis (3,5-dimethyl-4-cyanoxyphenyl) methane, 2,2-bis (4-cyanoxyphenyl) -1,1,1 , 3,3,3-hexafluoropropane, α, α′-bis (4-cyanooxyphenyl) -m-isopropylbenzene, cyclopentadiene type cyanate, phenol novolac type cyanate, Cresol novolac cyanate, 2,2-bis (4-cyanoxyphenyl) propane prepolymer, bis (4-cyanoxyphenyl) ethane prepolymer, bis (3,5-di Methyl-4-cyanooxyphenyl) methane prepolymer, 2,2-bis (4-cyanooxyphenyl) -1,1,1,3,3,3-hexafluoropropane prepolymer, α, α′-bis (4-cyanoxyphenyl) -m-isopropylbenzene prepolymer, cyclopentadiene type cyanate prepolymer, phenol novolac type cyanate prepolymer, or cresol Any one or a mixture of at least two of phenolic cyanate prepolymers, preferably 2,2-bis (4-cyanooxyphenyl) propane, α, α′-bis (4-cyanoxyoxy) Phenyl) -m-isopropylbenzene, bis (3,5-dimethyl-4-cyanooxy Phenyl) methane, 2,2-bis (4-cyanooxyphenyl) propane prepolymer, α, α′-bis (4-cyanoxyphenyl) -m-diisopropylbenzene prepolymer Or any one or a combination of at least two of bis (3,5-dimethyl-4-cyanoxyphenyl) methane prepolymers.
The thermosetting resin composition according to any one of claims 1 to 4, wherein the epoxy resin is an epoxy resin having two or more epoxy groups in one molecule;

Preferably, the epoxy resin is selected from a glycidyl ether epoxy resin, a glycidyl ester epoxy resin, a glycidylamine epoxy resin, an alicyclic epoxy resin, an epoxidized olefin epoxy resin, Any one or a combination of at least two kinds of Hein epoxy resin or imide epoxy resin;

Preferably, the glycidyl ether epoxy resin includes bisphenol A epoxy resin, bisphenol F epoxy resin, o-cresol novolac epoxy resin, triphenol phenolic epoxy resin, and dicyclopentadiene novolac Any one or a combination of at least two of epoxy resin, biphenyl-type phenolic epoxy resin, alkylbenzene-type phenolic epoxy resin, or naphthol-type phenolic epoxy resin;

Further preferably, the epoxy resin is an epoxy resin having a formula IV structure:

Wherein Z 1 , Z 2 and Z 3 are each independently selected from

Any one of R 10 is selected from any one of a hydrogen atom, a C1-C5 substituted or unsubstituted linear alkyl group, or a C1-C5 substituted or unsubstituted branched alkyl group;

Y 1 and Y 2 are each independently selected from a single bond, -CH 2- ,

Any one of R 11 is selected from any one of a hydrogen atom, a C1-C5 substituted or unsubstituted linear alkyl group, or a C1-C5 substituted or unsubstituted branched alkyl group;

n 1 is an integer from 1 to 10;

Preferably, the glycidyl amine epoxy resin includes triglycidyl p-aminophenol, triglycidyl trimeric isocyanate, tetraglycidyl diaminodimethylenebenzene, tetraglycidyl-4,4 ′ -Diaminodiphenylmethane, tetraglycidyl-3,4'-diaminodiphenyl ether, tetraglycidyl-4,4'-diaminodiphenyl ether, or tetraglycidyl-1,3-diamino Any one or a combination of at least two of methylcyclohexane.
The thermosetting resin composition according to any one of claims 1-5, wherein the thermosetting resin composition further comprises a curing accelerator;

Preferably, based on the total weight of the cyanate resin, epoxy resin and biphenol-formaldehyde resin being 100 parts by weight, the amount of the curing accelerator to be added is 0.01-1 part by weight, and more preferably 0.01-0.2 part by weight;

Preferably, the curing accelerator includes any one or at least two of an organic metal salt, an imidazole compound, a derivative of an imidazole compound, a piperidine compound, a pyridine compound, a Lewis acid, or triphenylphosphine. combination;

Preferably, the organic metal salt includes any one or at least two of metal octanoate, metal isooctanoate, metal acetylacetonate, metal naphthenate, metal salicylate, or metal stearate. combination;

Preferably, the metal is selected from any one or a combination of at least two of zinc, copper, iron, tin, cobalt, or aluminum;

Preferably, the imidazole compound is any one or a combination of at least two of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, or 2-undecylimidazole ;

Preferably, the piperidines are 2,3-diaminopiperidine, 2,5-diaminopiperidine, 2,6-diaminopiperidine, 2-amino-3-methylpiperidine, 2- Any of amino-4-methylpiperidine, 2-amino-3-nitropiperidine, 2-amino-5-nitropiperidine, or 2-amino-4,4-dimethylpiperidine or A combination of at least two;

Preferably, the pyridine compound is any one of 4-dimethylaminopyridine, 2-aminopyridine, 3-aminopyridine, and 4-aminopyridine or a combination of at least two of them.
The thermosetting resin composition according to any one of claims 1-6, wherein the thermosetting resin composition further comprises a filler;

Preferably, based on the total weight of the cyanate resin, the epoxy resin, and the biphenol-formaldehyde resin being 100 parts by weight, the filler is added in an amount of 5-300 parts by weight, and more preferably 5-200 parts by weight;

Preferably, the median particle diameter of the filler is 0.01-50 μm, further preferably 0.01-20 μm, and still more preferably 0.1-10 μm;

Preferably, the filler is selected from organic fillers or inorganic fillers, more preferably inorganic fillers, still more preferably surface-treated inorganic fillers, and most preferably surface-treated silica;

Preferably, the surface-treated surface treatment agent is selected from any one or a combination of at least two of a silane coupling agent, a silicone oligomer, or a titanate coupling agent;

Preferably, based on 100 parts by weight of the inorganic filler, the amount of the surface treatment agent is 0.1-5.0 parts by weight, further preferably 0.5-3.0 parts by weight, and still more preferably 0.75-2.0 parts by weight;

Preferably, the inorganic filler is selected from any one or a combination of at least two of non-metal oxides, metal nitrides, non-metal nitrides, inorganic hydrates, inorganic salts, or inorganic phosphorus, and more preferably fused silica. , Crystalline silica, spherical silica, hollow silica, aluminum hydroxide, aluminum oxide, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, Any one or a combination of at least two of calcium carbonate, calcium silicate or mica;

Preferably, the organic filler is selected from any one or a combination of at least two of polytetrafluoroethylene, polyphenylene sulfide, or polyethersulfone.
The thermosetting resin composition according to any one of claims 1 to 7, wherein the thermosetting resin composition further comprises a flame retardant.
A prepreg, characterized in that the prepreg comprises a reinforcing material and the thermosetting resin composition according to any one of claims 1 to 8 attached to the prepreg after being dried by dipping.
A laminate, wherein the laminate comprises at least one prepreg according to claim 9.
A high-frequency circuit substrate, characterized in that the high-frequency circuit substrate comprises at least one prepreg according to claim 9 and metal foils covering one or both sides of the laminated prepreg;

Preferably, the metal foil is a copper foil.