WO2020124673A1 - Thermosetting resin composition and prepreg using same, laminate, and metal foil-clad laminate - Google Patents

Abstract

The present invention provides a thermosetting resin composition and a prepreg using same, a laminate, and a metal foil-clad laminate. The thermosetting resin composition comprises epoxy resin, a styrene maleic anhydride oligomer, and an ester curing agent having a structure represented by formula I. According to the present invention, the ester curing agent having the structure represented by formula I and the styrene maleic anhydride oligomer are used cooperatively for curing the epoxy resin; no secondary hydroxyl or other polar groups are generated in the process of curing; moreover, a cured product contains a large amount of hydrophobic groups; high glass transition temperature of the cured product is guaranteed, and the water absorption rate, coefficient of thermal expansion and dielectric loss factor can be significantly reduced. The laminate and the metal foil-clad laminate prepared by using the thermosetting resin composition have good heat resistance, moisture resistance, peel strength, dielectric properties, and flame retardance.

Description

Thermosetting resin composition and prepreg, laminate and metal foil-clad laminate using the same Technical field

The invention belongs to the technical field of printed circuit boards, and particularly relates to a thermosetting resin composition and a prepreg, a laminate and a metal foil-clad laminate using the same.

Background technique

With the high-speed and multi-functionalization of information processing of electronic products, the application frequency continues to increase, requiring lower and lower dielectric constant (Dk) and dielectric loss value (Df), so reducing Dk/Df has become a pursuit of substrate manufacturers Hot spots. In order to achieve low Dk and low Df, various low-polarity resins such as styrene-maleic anhydride oligomers (SMA) are widely used. SMA can give substrates excellent dielectric properties and heat resistance, but there is water absorption High rate and large coefficient of thermal expansion (CTE) problems.

In addition, under the global trend of strengthening "green" and "environmental protection", the development of halogen-free flame-retardant copper-clad laminates has become a hot spot in the industry, and various copper-clad laminate manufacturers have launched their own halogen-free flame-retardant copper-clad laminates. Foil laminate. At present, the most commonly used halogen-free flame retardants in the industry are still mainly phosphorus-based flame retardants. Phosphorus-based flame retardants are more likely to absorb moisture than bromine-based flame retardants. The disadvantages of high are more obvious.

The high water absorption rate will cause the dielectric properties of the board to deteriorate significantly due to moisture absorption, and may also cause the substrate to explode due to heat after moisture absorption during the processing of the printed circuit board (PCB); a large CTE will directly affect the high multilayer board Reliability. Therefore, on the premise of ensuring a high glass transition temperature (Tg) and excellent dielectric properties, how to reduce the water absorption rate and CTE of the SMA halogen-free system has become a technical problem.

The CCL industry commonly uses benzoxazine resin to reduce the water absorption of cured products. However, the dielectric properties of benzoxazine resin are poor, and the molecular structure contains polar groups, which will seriously deteriorate the dielectric properties of the SMA system. The most effective way to reduce the CTE of the cured product or sheet is to increase the filler ratio in the formulation. However, usually the SMA has a large molecular weight and high initial reactivity, resulting in a high resin melt viscosity, which limits the proportion of fillers added to the formulation.

Therefore, how to reduce the water absorption rate, thermal expansion coefficient, and dielectric loss while ensuring that the CCL has a high glass transition temperature is a problem that needs to be solved in the art.

Summary of the invention

In view of the deficiencies of the prior art, the object of the present invention is to provide a thermosetting resin composition and a prepreg, laminate and metal foil-clad laminate using the same. Laminates and metal-clad laminates prepared with the thermosetting resin composition have high glass transition temperature, high peel strength, low water absorption, low thermal expansion coefficient, low dielectric constant, low dielectric loss factor, and high heat resistance And good chemical resistance.

To achieve this goal, the present invention uses the following technical solutions:

In a first aspect, the present invention provides a thermosetting resin composition, characterized in that the thermosetting resin composition includes the following components: epoxy resin, styrene-maleic anhydride oligomer and ester curing agent;

The ester curing agent has the structure of formula I:

Wherein R ₁ -R ₈ are each independently selected from one of a hydrogen atom, a C ₁ -C ₁₀ aliphatic hydrocarbon group, a C ₃ -C ₁₀ alicyclic hydrocarbon group, or a C ₆ -C ₁₀ aromatic hydrocarbon group, and not all are A hydrogen atom;

X is selected from one of -O-, -S-, -CH ₂ -or -C(CH ₃ ) ₂ -;

Y is selected from one of C ₁ -C ₁₀ aliphatic hydrocarbon groups, C ₃ -C ₁₀ alicyclic hydrocarbon groups or C ₆ -C ₁₀ aromatic hydrocarbon groups;

n is an integer of 1-10.

The present invention uses an ester curing agent with the structure of Formula I and styrene-maleic anhydride oligomers to cure epoxy resins cooperatively, does not generate polar groups such as secondary hydroxyl groups during the curing process, and the cured product contains a large amount of hydrophobic The group, while ensuring that the cured product has a high glass transition temperature, can significantly reduce its water absorption rate, thermal expansion coefficient and dielectric loss factor. The laminate and the metal foil-clad laminate prepared by using the thermosetting resin composition also have the above-mentioned advantages.

In the present invention, the C ₁ -C ₁₀ aliphatic hydrocarbon group refers to containing 1-10 (for example, 1, 2, 3, 4, 5, 6, 6, 7, 8, 9 or 10) aliphatic hydrocarbon group of carbon atom; for example, it may be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl and the like.

The C ₃ -C ₁₀ alicyclic hydrocarbon group refers to an alicyclic group containing 3 to 10 (eg, 3, 4, 5, 6, 7, 8, 8, 9 or 10) carbon atoms Hydrocarbon group; for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.

The C ₆ -C ₁₀ aromatic hydrocarbon group refers to an aliphatic hydrocarbon group containing 6-10 (for example 6, 7, 8, 9, or 10) carbon atoms; for example, it may be phenyl, benzyl , Phenethyl or phenylpropyl, etc.

In formula I, n may be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

As a preferred technical solution of the present invention, based on the total weight parts of the epoxy resin, styrene-maleic anhydride oligomer and ester curing agent being 100 parts, the thermosetting resin composition includes: 40-70 Parts epoxy resin, 10-35 parts styrene-maleic anhydride oligomer and 5-25 parts ester curing agent.

Unless otherwise specified, the "ester curing agent" in the present invention refers to an ester curing agent having the structure of Formula I.

In the present invention, the weight parts of the epoxy resin may be 40 parts, 42 parts, 45 parts, 48 parts, 50 parts, 52 parts, 55 parts, 58 parts, 60 parts, 62 parts, 65 parts, 68 parts Or 70 copies.

The weight parts of the styrene-maleic anhydride oligomer may be 10 parts, 12 parts, 13 parts, 15 parts, 16 parts, 18 parts, 20 parts, 22 parts, 23 parts, 25 parts, 26 parts, 28, 30, 32, 33 or 35 parts.

The weight parts of the ester curing agent may be 5, 6, 8, 10, 12, 13, 15, 15, 18, 20, 22, 23, or 25 parts Wait.

In the present invention, the epoxy resin, the styrene-maleic anhydride oligomer and the ester curing agent are mixed with each other at the above-mentioned specific ratio to further improve the comprehensive performance of the cured product and the laminate prepared therefrom. If the content of epoxy resin is too small, the processing performance of the laminate will be poor; if the amount of epoxy resin is too large, it will lead to a lower glass transition temperature of the cured product and the laminate, and poorer dielectric properties . If the content of styrene-maleic anhydride oligomer is too small, the effect of reducing the dielectric constant and dielectric loss of the cured product is not obvious; if the content of styrene-maleic anhydride oligomer is too large, then Will significantly reduce the adhesion of the cured product, resulting in reduced peel strength of the laminate. If the content of the ester curing agent is too small, the effect of improving the water absorption rate and dielectric properties of the cured product is not obvious. If the content of the ester curing agent is too large, it will cause the brittleness of the cured product and the laminate to be large, processing Poor performance.

As a preferred technical solution of the present invention, the epoxy resin is a halogen-free epoxy resin.

Preferably, the halogen-free epoxy resin is selected from bisphenol A epoxy resin, bisphenol F epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, triphenol novolac ring Oxygen resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin, alkylbenzene novolac epoxy resin or naphthol novolac epoxy resin, or a combination of at least two of them.

Preferably, the halogen-free epoxy resin has the structure of formula II:

Among them, X ₁ , X ₂ and X ₃ are each independently

R _{9 is} selected from a hydrogen atom, a substituted or unsubstituted C ₁ -C ₅ linear alkyl group or a substituted or unsubstituted C ₃ -C ₅ branched alkyl group;

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

One of R _{10 is} selected from a hydrogen atom, a substituted or unsubstituted C ₁ -C ₅ linear alkyl group or a substituted or unsubstituted C ₃ -C ₅ branched alkyl group;

m is an integer of 1-10; for example, it can be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

In the present invention, the C ₁ -C ₅ straight-chain alkyl group refers to a straight-chain alkyl group containing 1 to 5 (eg 1, 2, 3, 4 or 5) carbon atoms; for example, it may be Methyl, ethyl, propyl, butyl or pentyl.

The C ₃ -C ₅ branched alkyl group refers to a branched alkyl group containing 3-5 (eg 3, 4 or 5) carbon atoms; for example, it may be isopropyl, isobutyl, tert-butyl Base or isoamyl, etc.

The halogen-free epoxy resin having the structure of Formula II has higher functionality and good dielectric properties, which helps to further increase the glass transition temperature of the cured product, and reduce dielectric loss and water absorption.

As a preferred technical solution of the present invention, the styrene-maleic anhydride oligomer has the structure of formula III:

Among them, j:k=(3-8):1; for example, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7 : 1, 7.5: 1 or 8: 1 etc.

Preferably, the weight average molecular weight of the styrene-maleic anhydride oligomer is 5000-50000; for example, it may be 5000, 6000, 7000, 8000, 10000, 15000, 20000, 25000, 30000, 35000, 40000, 45000 or 50000 etc.

As a preferred technical solution of the present invention, the thermosetting resin composition further includes a flame retardant.

Preferably, the flame retardant is a phosphorus-containing flame retardant.

Preferably, based on the total weight parts of the epoxy resin, styrene-maleic anhydride oligomer and ester curing agent being 100 parts, the added amount of the phosphorus-containing flame retardant is 1-50 parts, For example, 1 part, 2 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 35 parts, 40 parts, 45 parts Or 50 parts; etc.; more preferably 1-30 parts.

Preferably, the phosphorus-containing flame retardant is selected from tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa -10-phosphinophenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene, 10-phenyl-9,10-dihydro-9-oxa-10- One or a combination of at least two of phosphaphenanthrene-10-oxide, phenoxyphosphazene compound, phosphate, polyphosphate, phosphonate or polyphosphonate.

As a preferred technical solution of the present invention, the thermosetting resin composition further includes a curing accelerator to cure the resin composition and accelerate the curing speed of the resin composition.

Preferably, based on the total weight parts of the epoxy resin, styrene-maleic anhydride oligomer and ester curing agent being 100 parts, the addition amount of the curing accelerator is 0.05-1 part; for example, It is 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1 part.

Preferably, the curing accelerator is selected from one or a combination of at least two of imidazole compounds, triphenylphosphine, dimethylaminopyridine, boron trifluoride monoethylamine, or zinc octoate.

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

Preferably, the thermosetting resin composition further includes a filler to further reduce the coefficient of thermal expansion (CTE) and water absorption of the cured product and the laminate, and improve the thermal conductivity.

Preferably, based on the total weight parts of the epoxy resin, styrene-maleic anhydride oligomer and ester curing agent being 100 parts, the addition amount of the filler is 1-150 parts, for example, it may be 1 1 part, 2 parts, 5 parts, 8 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts or 150 parts, etc.; further preferably 1-100 parts.

Preferably, the filler is an organic filler and/or an inorganic filler.

Preferably, the inorganic filler is selected from silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, silicic acid One or a combination of at least two of calcium, mica, and glass fiber powder.

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

In the present invention, the filler is most preferably silica, which may be, for example, fused silica, crystalline silica, spherical silica or hollow silica; the median particle size is 1-15 μm, For example, it may be 1 μm, 2 μm, 3 μm, 5 μm, 6 μm, 8 μm, 10 μm, 12 μm, 13 μm or 15 μm, etc.; further preferably 1-10 μm. The filler having a particle size distribution within the above range has better dispersibility in the thermosetting resin composition.

In a second aspect, the present invention provides a resin glue, which is obtained by dissolving or dispersing the thermosetting resin composition provided in the first aspect of the invention in a solvent.

In a third aspect, the present invention provides a prepreg including a reinforcing material, and the thermosetting resin composition provided in the first aspect of the present invention adhered to the reinforcing material after being impregnated and dried.

In the present invention, the following methods can be used to prepare the prepreg:

The thermosetting resin composition is dissolved in a solvent to form a glue solution, and then the reinforcement material is impregnated with the glue solution to obtain a prepreg after drying.

Wherein, the solvent is preferably methyl ethyl ketone (MEK), the solid content of the glue solution is preferably 60-70%, the reinforcing material is preferably glass cloth, and the impregnation amount of the glue solution is preferably 200-230g/m ² . The drying temperature is preferably 155°C, and the time is preferably 5-10 min.

In a fourth aspect, the invention provides a laminate comprising one or at least two superposed prepregs provided in the third aspect of the invention.

In a fifth aspect, the present invention provides a metal-clad laminate comprising one or at least two superposed prepregs provided in the third aspect of the present invention and one or both sides covered on the outside of the prepreg Metal foil.

The metal foil-clad laminate is prepared by laminating one or at least two prepregs first, and then cladding metal foil on the outermost side or both sides of the prepreg, and finally heating and pressure curing get.

The heating and pressing operation can be carried out by a laminator, and the lamination must meet the following requirements: ① The temperature increase rate of lamination should be controlled at 1.5-2.5°C/min when the material temperature is 80-120°C; ② Lamination Pressure setting, the outer layer material temperature is applied full pressure at 120-150 ℃, the full pressure is about 350psi; ③ During curing, the material temperature is controlled at 180-220 ℃, and keep warm for 60-120min.

The metal foil may be copper foil, nickel foil, aluminum foil, SUS foil (stainless steel foil), or the like.

In a sixth aspect, the present invention provides a printed circuit board including at least one prepreg provided in the third aspect of the present invention.

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

The present invention uses an ester curing agent with the structure of Formula I and styrene-maleic anhydride oligomers to cure epoxy resins cooperatively, does not generate polar groups such as secondary hydroxyl groups during the curing process, and the cured product contains a large amount of hydrophobic Group, can effectively increase the glass transition temperature of the cured product, and reduce its water absorption rate, thermal expansion coefficient and dielectric loss factor. The laminate prepared using the thermosetting resin composition has a glass transition temperature of 165°C-200°C, a thermal expansion coefficient of 2.1%-2.8%, a water absorption rate of 0.20%-0.32%, and a dielectric constant (10 GHz) of 3.5- 3.8, the dielectric loss factor (10GHz) is 0.0062-0.0079, the dielectric constant after humidity is 3.5-3.9, the dielectric loss factor after humidity is 0.0067-0.0098, the layering foaming time at 288℃>120s, and the peel strength is 1.08- 1.34N/mm, the drop hammer impact crack area is 205-395mm ² , the flame resistance is V-0, and it has good heat resistance, moisture resistance, peel strength, dielectric properties and flame retardancy.

detailed description

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

The sources/preparation methods of the materials involved in the examples and comparative examples of the present invention are as follows:

(A) Halogen-free epoxy resin

(A-1) Dicyclopentadiene novolac epoxy resin HP-7200H (brand name of Dainippon Ink);

(A-2) Biphenyl novolac epoxy resin NC-3000 (Japanese chemical brand name).

(B) anhydride

(B-1) Styrene-maleic anhydride oligomer EF40, with a weight average molecular weight of 10500, and a molar ratio of styrene units to maleic anhydride units of 4:1 (Craywill brand name);

(B-2) Styrene-maleic anhydride oligomer EF60, with a weight average molecular weight of 11500, and a molar ratio of styrene units to maleic anhydride units of 6:1 (Craywell brand name);

(B-3) Methylhexahydrophthalic anhydride, its structure is:

(C) curing agent

(C-1) An ester curing agent having the structure of Formula I, the structure of which is:

The average repeating unit n is 1.25;

The preparation method is as follows:

Into a flask equipped with a thermometer, a dropping funnel, and a stirrer, 2 mol (568.78 g) of tetramethyl bisphenol A and 1500 g of tetrahydrofuran were put in, and nitrogen was bubbled and stirred until completely dissolved. Next, add 1 mol (203.02 g) of terephthaloyl chloride with stirring and dissolve. Then, control the temperature of the system below 20° C., and slowly add (more than 0.5 hours) 2 mol (202.38 g) of triethylamine (formulated as 20% triethylamine) (Ethylamine/tetrahydrofuran solution was added dropwise). Next, the reaction is continued to be stirred for 2 to 3 hours below 20°C. Next, 2mol (381.25g) of 2-naphthoyl chloride was added to control the temperature of the system below 15°C, then 2mol (202.38g) of triethylamine was slowly added dropwise (prepared as a 20% triethylamine/tetrahydrofuran solution) , Continue stirring the reaction below 15 ℃ for 2 to 5 hours. After the reaction was completed, it was allowed to stand, and the solid of triethylamine hydrochloride was removed by filtration. The solution was distilled and concentrated under reduced pressure, and then methanol was added to precipitate the resin product, which was filtered, washed with water until the pH value of the final water layer was 7, and then washed with methanol , And then dried to obtain the product. The ester equivalent of the prepared active ester resin was 252 g/eq according to the charging ratio.

(C-2) An ester curing agent having the structure of Formula I, the structure of which is:

The average repeating unit n is 1.25;

The preparation method is as follows:

Into a flask equipped with a thermometer, a dropping funnel, and a stirrer, 2 mol (568.78 g) of tetramethyl bisphenol A and 1500 g of tetrahydrofuran were put in, and nitrogen was bubbled and stirred until completely dissolved. Next, add 1 mol (203.02 g) of terephthaloyl chloride with stirring and dissolve. Then, control the temperature of the system below 20° C., and slowly add (more than 0.5 hours) 2 mol (202.38 g) of triethylamine (formulated as 20% triethylamine) (Ethylamine/tetrahydrofuran solution was added dropwise). Next, the reaction is continued to be stirred for 2 to 3 hours below 20°C. Next, 2 mol (281.14 g) of benzoyl chloride was added to control the temperature of the system below 15° C., and then 2 mol (202.38 g) of triethylamine (formulated as a 20% triethylamine/tetrahydrofuran solution) was slowly added dropwise. The reaction is continued to be stirred for 2 to 5 hours below 15°C. After the reaction was completed, it was allowed to stand, and the solid of triethylamine hydrochloride was removed by filtration. The solution was distilled and concentrated under reduced pressure, and then methanol was added to precipitate the resin product, which was filtered, washed with water until the pH value of the final water layer was 7, and then washed with methanol , And then dried to obtain the product. The ester equivalent of the prepared active ester resin was 226 g/eq according to the charging ratio.

(C-3) An ester curing agent having the structure of Formula I, the structure of which is:

The average repeating unit n is 1.25;

The preparation method is as follows:

Into a flask equipped with a thermometer, a dropping funnel, and a stirrer, 2 mol (512.66 g) of tetramethyl bisphenol F and 1500 g of tetrahydrofuran were introduced, nitrogen gas was introduced, and the mixture was stirred until completely dissolved. Next, add 1 mol (203.02 g) of terephthaloyl chloride with stirring and dissolve. Then, control the temperature of the system below 20° C., and slowly add (more than 0.5 hours) 2 mol (202.38 g) of triethylamine (formulated as 20% triethylamine) (Ethylamine/tetrahydrofuran solution was added dropwise). Next, the reaction is continued to be stirred for 2 to 3 hours below 20°C. Next, add 2mol (157g) of acetyl chloride to control the temperature of the system below 15°C, then slowly add 2mol (202.38g) of triethylamine (prepared as a 20% triethylamine/tetrahydrofuran solution dropwise) at 15°C The stirring reaction is continued for 2 to 5 hours. After the reaction was completed, it was allowed to stand, and the solid of triethylamine hydrochloride was removed by filtration. The solution was distilled and concentrated under reduced pressure, and then methanol was added to precipitate the resin product, which was filtered, washed with water until the pH value of the final water layer was 7, and then washed with methanol , And then dried to obtain the product. The ester equivalent of the prepared active ester resin was 181 g/eq according to the charging ratio.

(C-4) An ester curing agent V-575 (Japan UNITIKA trade name), the structure is as follows:

The average repeating unit n is 1.25;

(C-5) Dicyclopentadiene phenol type active ester HPC-8000T65 (brand name of Dainippon Ink);

(C-6) Bisphenol A cyanate CE01PS (Yangzhou Tianqi trade name);

(C-7) Dicyclopentadiene type benzoxazine LZ 8260N70 (HUNTSMAN trade name).

(D) flame retardant

(D-1) Phosphorus-containing phenol formaldehyde XZ92741 (US DOW trade name);

(D-2) Phenoxyphosphazene compound SPB-100 (trade name of Mitsubishi of Japan).

(E) curing accelerator

2-phenylimidazole (formed from Shikoku, Japan).

(F) filler

Spherical silicon micropowder (average particle size 1-10 μm, purity 99% or more).

Examples 1-12

Examples 1-12 provide thermosetting resin composition glue, prepreg and copper clad laminate using the same, the preparation method is as follows:

(1) Preparation of glue for thermosetting resin composition:

Using MEK solvent, the components (B) styrene-maleic anhydride oligomer, (C) curing agent and (D-2) phenoxyphosphazene compound SPB-100 were formulated into solid content of 60% and 50%, respectively And 25% solution, add them to a 1000mL beaker in sequence, then add (A) halogen-free epoxy resin, (D-1) phosphorus-containing phenolic XZ92741 and (F) filler, and add an appropriate amount (E) curing accelerator 2- Phenylimidazole, adjust the gelation time (GT) to 200-300s, add MEK solvent to control the solid content to 65%, continue to stir for 2h and ripen to obtain the thermosetting resin composition glue;

Among them, the types and amounts (in parts by weight) of each component are shown in Table 1 and Table 2.

(2) Preparation of prepreg:

Prepare 6 pieces of 2116 glass cloth (manufacturer: Taiwan Hubert Company), size: 320mm×380mm, first apply the above thermosetting resin composition glue to each glass cloth, so that the glue infiltrate the glass cloth on both surfaces Stick the resin, and then smooth the two surfaces through the rolled pinch shaft and remove part of the glue. The total weight of the glass cloth and the resin composition after removing the solvent is controlled at 200-230g/m ² To obtain a prepreg glass cloth, and then put it in a 155 ℃ oven for 6-8min to obtain a prepreg.

(3) Production of copper clad laminate:

Prepare 2 sheets of electrolytic copper foil with a thickness of 35 μm and a size of 410 mm × 410 mm (manufacturer: Suzhou Futian), stack 6 sheets of the above prepregs, keeping the 4 corners aligned, and separate the upper and lower surfaces of the stacked prepregs Cover a prepared electrolytic copper foil, put it into a laminator, and perform lamination according to the following conditions: ①The temperature increase rate of lamination should be controlled at 1.5-2.5℃/min when the material temperature is 80-120℃;② Lamination pressure setting, the outer layer material temperature is applied at 120-150 ℃, full pressure is applied, the full pressure is 350psi; ③ During curing, the material temperature is controlled at 200 ℃, and heat preservation for 90min, to obtain a copper clad laminate.

Examples 13-16

Examples 13-16 provide thermosetting resin composition glue, prepregs and copper clad laminates using the same. The difference from Example 2 is that component (A) halogen-free epoxy resin and (B) styrene-Malay The amount of anhydride oligomer or (C) curing agent is different, as shown in Table 2 below.

Comparative example 1-4

The difference between Comparative Examples 1-4 and Example 2 is that the type of component (C) curing agent is different, as shown in Table 3 below.

Comparative example 5-8

Comparative Examples 5-8 differ from Example 11 in the kind of component (C) curing agent, as shown in Table 3 below.

Comparative Example 9-12

Comparative Examples 9-12 differ from Example 12 in the kind of component (C) curing agent, as shown in Table 4 below.

Comparative Example 13

The difference between Comparative Example 13 and Example 2 is that the type of component (B) anhydride is different, as shown in Table 4 below.

Comparative Example 14

The difference between Comparative Example 14 and Example 11 is that the type (B) of the acid anhydride is different, as shown in Table 4 below.

The performance of the copper clad laminates provided in the above examples and comparative examples was tested respectively. The test standards/methods are as follows:

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

(b) Coefficient of thermal expansion (CTE)

According to the ZC CTE test method specified in IPC-TM-6502.4.24.

(c) Water absorption

After the 100mm×100mm sample was placed in a constant temperature and humidity box with a temperature of 85°C and a humidity of 85% for 168 hours, the water absorption of the treated sample was tested.

(d) Dielectric constant, dielectric loss factor

According to the resonance method using a strip line, the dielectric loss and the dielectric loss factor at 1 GHz were measured according to IPC-TM-650 2.5.5.5.

(e) Dielectric constant, dielectric loss factor (after humidity)

After the sample is placed in a constant temperature and humidity box with a temperature of 85°C and a humidity of 85% for 168 hours, the dielectric loss and dielectric loss factor at 1 GHz are measured according to IPC-TM-650 2.5.5.5.

(f) Resistance to dip soldering

Observe the delamination bubbling time according to IPC-TM-650 2.4.13.1.

(g) Peel strength

According to the experimental conditions of "After Thermal Stress" in the method of IPC-TM-650 2.4.8, test the peel strength of the metal cap layer.

(h) Drop hammer impact crack area

The drop weight impact test machine is used for testing. The test method: the drop weight height is 1 m, the drop weight is 0.75 kg, the drop weight is released, and the crack area of the plate is tested. The size of the crack area of the plate can initially reflect the toughness of the plate. Generally speaking, the smaller the crack area, the better the toughness of the plate.

(i) Difficult to burn

According to UL 94 vertical combustion method.

The performance of the copper clad laminates provided by the above examples and comparative examples is shown in Table 1-4 below:

Table 1

Table 2

table 3

Table 4

It can be seen from the physical property data in Tables 1-4 that Example 1-12 uses 5-25 parts of the ester curing agent having the structure of Formula I and 10-35 parts of styrene-maleic anhydride oligomer to cure 40-70 parts without Halogen epoxy resin, the resulting plate has high Tg, low CTE, low water absorption, excellent dielectric properties, high heat resistance and peel strength, and excellent toughness, while also achieving halogen-free flame retardant V-0 level.

In Example 13, 30 parts of an ester curing agent having the structure of Formula I and a styrene-maleic anhydride oligomer EF40 composite curing dicyclopentadiene phenol epoxy resin HP-7200H are used. The sheet has high Tg, low CTE, and low Water absorption, excellent dielectric properties and heat resistance, but the drop area used to characterize toughness has a large crack area and poor toughness of the plate, which is not conducive to downstream PCB processing.

In Example 14, 3 parts of an ester curing agent having the structure of Formula I and styrene-maleic anhydride oligomer EF40 are used to cure dicyclopentadiene novolac epoxy resin HP-7200H, which has excellent dielectric properties but low Tg , Large CTE, high water absorption rate and obvious deterioration of dielectric properties after moisture absorption.

In Example 15, 40 parts of styrene-maleic anhydride oligomer EF40 and an ester curing agent having the structure of Formula I are used to cure dicyclopentadiene phenol epoxy resin HP-7200H. The sheet has high Tg, low water absorption, Excellent dielectric properties and heat resistance, CTE is not ideal and the peel strength is too low, too low peel strength is easy to cause the copper wire to fall off during subsequent processing.

In Example 16, 8 parts of styrene-maleic anhydride oligomer EF40 and an ester curing agent having the structure of Formula I are used to cure dicyclopentadiene phenol epoxy resin HP-7200H. The sheet has high Tg, low CTE, and low Water absorption and high heat resistance, but due to the low amount of EF40, the dielectric constant of the sheet is too high and the toughness is poor.

As described above, the laminate prepared using the thermosetting resin composition provided by the present invention has higher Tg, lower CTE, lower water absorption, and more excellent dielectric properties compared to the general halogen-free laminate And peel strength, heat resistance, toughness, suitable for high-speed applications. In addition, the halogen content of the present invention can reach the V-0 standard in the flame retardant test UL94 within the range required by the JPCA halogen-free standard, and has the effect of environmental protection.

In Comparative Example 1, the ester curing agent V-575 and styrene-maleic anhydride oligomer EF40 were used to cure dicyclopentadiene novolac epoxy resin HP-7200H. The sheet has high Tg, low CTE, and excellent dielectric properties. And heat resistance, but the water absorption rate is high and the dielectric properties of the board after moisture absorption are poor.

In Comparative Example 2, dicyclopentadiene phenol type active ester HPC-8000T65 and styrene-maleic anhydride oligomer EF40 composite cured dicyclopentadiene novolac epoxy resin HP-7200H were used. The sheet had a lower Tg and a larger CTE. The water absorption rate is high and the dielectric properties of the board after moisture absorption are poor.

In Comparative Example 3, bisphenol A type cyanate CE01PS and styrene-maleic anhydride oligomer EF40 were used to cure dicyclopentadiene phenol epoxy resin HP-7200H. The sheet has high Tg, low CTE, and excellent dielectric properties. Performance and heat resistance, but the water absorption rate is high and the dielectric properties of the board after moisture absorption are poor.

In Comparative Example 4, dicyclopentadiene-type benzoxazine LZ 8260N70 and styrene-maleic anhydride oligomer EF40 composite cured dicyclopentadiene novolac epoxy resin HP-7200H was used. The sheet had low water absorption and excellent dielectric constant. , Good heat resistance, but the plate has low Tg, large CTE and high dielectric loss.

In Comparative Example 5, an ester curing agent V-575 and a styrene-maleic anhydride oligomer EF40 were used to cure biphenyl novolac epoxy resin NC-3000. The sheet has high Tg, low CTE, excellent dielectric properties and Heat resistance, but high water absorption and poor dielectric properties after moisture absorption.

In Comparative Example 6, bicyclopentadiene phenol type active ester HPC-8000T65 and styrene-maleic anhydride oligomer EF40 composite curing biphenyl phenol epoxy resin NC-3000 were used. The sheet had a lower Tg, a larger CTE, and water absorption. The rate is high and the dielectric properties of the sheet after moisture absorption are poor.

In Comparative Example 7, bisphenol A cyanate CE01PS and styrene-maleic anhydride oligomer EF40 were used to cure biphenyl novolac epoxy resin NC-3000. The sheet has high Tg, low CTE, and excellent dielectric properties. And heat resistance, but the water absorption rate is high and the dielectric properties of the board after moisture absorption are poor.

In Comparative Example 8, bicyclopentadiene-type benzoxazine LZ 8260N70 and styrene-maleic anhydride oligomer EF40 composite cured biphenyl novolac epoxy resin NC-3000 was used. The sheet had low water absorption and excellent dielectric constant. The heat resistance is good, but the sheet has a low Tg, a large CTE, and a high dielectric loss.

In Comparative Example 9, an ester curing agent V-575 and a styrene-maleic anhydride oligomer EF60 were used to cure dicyclopentadiene novolac epoxy resin HP-7200H. The sheet has high Tg, low CTE, and excellent dielectric properties. And heat resistance, but the water absorption rate is high and the dielectric properties of the board after moisture absorption are poor.

In Comparative Example 10, dicyclopentadiene phenol type active ester HPC-8000T65 and styrene-maleic anhydride oligomer EF60 composite cured dicyclopentadiene novolac epoxy resin HP-7200H were used. The sheet had a lower Tg and a larger CTE. The water absorption rate is high and the dielectric properties of the board after moisture absorption are poor.

In Comparative Example 11, bisphenol A type cyanate CE01PS and styrene-maleic anhydride oligomer EF60 were used to cure dicyclopentadiene novolac epoxy resin HP-7200H. The sheet has high Tg, low CTE, and excellent dielectric properties. Performance and heat resistance, but the water absorption rate is high and the dielectric properties of the board after moisture absorption are poor.

In Comparative Example 12, dicyclopentadiene-type benzoxazine LZ 8260N70 and styrene-maleic anhydride oligomer EF60 composite cured dicyclopentadiene novolac epoxy resin HP-7200H was used. The sheet had low water absorption and excellent dielectric constant. , Good heat resistance, but the plate has low Tg, large CTE and high dielectric loss.

In Comparative Example 13, an ester curing agent having the structure of Formula I and methyl hexahydrophthalic anhydride were used to cure dicyclopentadiene novolac epoxy resin HP-7200H, and the sheet had poor dielectric properties and heat resistance, and The drop weight impact test used to characterize toughness has a large crack area and poor sheet toughness, which is not conducive to downstream PCB processing.

In Comparative Example 14, an ester curing agent having the structure of Formula I and methylhexahydrophthalic anhydride were used to cure biphenyl novolac epoxy resin NC-3000. The sheet performance was similar to that of Comparative Example 13. The dielectric properties and resistance were The thermal property is poor, and the drop weight impact test used to characterize the toughness has a large crack area and poor toughness of the plate, which is not conducive to downstream PCB processing.

The applicant declares that the above is only a specific embodiment of the present invention, but the scope of protection of the present invention is not limited to this. Those skilled in the art should understand that any person who belongs to the technical field disclosed in the present invention Within the technical scope, changes or replacements that can be easily thought of fall within the protection scope and the disclosure scope of the present invention.

Claims (10)

1. A thermosetting resin composition, characterized in that the thermosetting resin composition includes the following components: epoxy resin, styrene-maleic anhydride oligomer and ester curing agent;

   The ester curing agent has the structure of formula I:

   

   Wherein R ₁ -R ₈ are each independently selected from one of a hydrogen atom, a C ₁ -C ₁₀ aliphatic hydrocarbon group, a C ₃ -C ₁₀ alicyclic hydrocarbon group, or a C ₆ -C ₁₀ aromatic hydrocarbon group, and not all are A hydrogen atom;

   X is selected from one of -O-, -S-, -CH ₂ -or -C(CH ₃ ) ₂ -;

   Y is selected from one of C ₁ -C ₁₀ aliphatic hydrocarbon groups, C ₃ -C ₁₀ alicyclic hydrocarbon groups or C ₆ -C ₁₀ aromatic hydrocarbon groups;

   n is an integer of 1-10.
2. The thermosetting resin composition according to claim 1, characterized in that, based on the total weight parts of the epoxy resin, styrene-maleic anhydride oligomer and ester curing agent being 100 parts, the thermosetting resin composition The resin composition includes: 40-70 parts epoxy resin, 10-35 parts styrene-maleic anhydride oligomer and 5-25 parts ester curing agent.
3. The thermosetting resin composition according to claim 1 or 2, wherein the epoxy resin is a halogen-free epoxy resin;

   Preferably, the halogen-free epoxy resin is selected from bisphenol A epoxy resin, bisphenol F epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, triphenol novolac ring One or a combination of at least two of oxygen resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin, alkylbenzene novolac epoxy resin or naphthol novolac epoxy resin;

   Preferably, the halogen-free epoxy resin has the structure of formula II:

   

   Among them, X ₁ , X ₂ and X ₃ are each independently

   

   R _{9 is} selected from a hydrogen atom, a substituted or unsubstituted C ₁ -C ₅ linear alkyl group or a substituted or unsubstituted C ₃ -C ₅ branched alkyl group, and Y ₁ and Y ₂ are each independently selected From single bond, -CH ₂ -,

   

   

   One of R _{10 is} selected from a hydrogen atom, a substituted or unsubstituted C ₁ -C ₅ linear alkyl group or a substituted or unsubstituted C ₃ -C ₅ branched alkyl group, m is 1- An integer of 10;

   Preferably, the styrene-maleic anhydride oligomer has the structure of formula III:

   

   Among them, j:k=(3-8):1;

   Preferably, the weight average molecular weight of the styrene-maleic anhydride oligomer is 5000-50000.
4. The thermosetting resin composition according to any one of claims 1 to 3, wherein the thermosetting resin composition further comprises a flame retardant;

   Preferably, the flame retardant is a phosphorus-containing flame retardant;

   Preferably, based on the total weight parts of the epoxy resin, styrene-maleic anhydride oligomer and ester curing agent being 100 parts, the added amount of the phosphorus-containing flame retardant is 1-50 parts, It is further preferably 1-30 parts;

   Preferably, the phosphorus-containing flame retardant is selected from tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa -10-phosphinophenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene, 10-phenyl-9,10-dihydro-9-oxa-10- One or a combination of at least two of phosphaphenanthrene-10-oxide, phenoxyphosphazene compound, phosphate, polyphosphate, phosphonate or polyphosphonate.
5. The thermosetting resin composition according to any one of claims 1 to 4, wherein the thermosetting resin composition further comprises a curing accelerator;

   Preferably, based on the total weight parts of the epoxy resin, styrene-maleic anhydride oligomer and ester curing agent being 100 parts, the addition amount of the curing accelerator is 0.05-1 part;

   Preferably, the curing accelerator is selected from one or a combination of at least two of imidazole compounds, triphenylphosphine, dimethylaminopyridine, boron trifluoride monoethylamine or zinc octoate;

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

   Preferably, the thermosetting resin composition further includes a filler;

   Preferably, based on the total weight parts of the epoxy resin, styrene-maleic anhydride oligomer and ester curing agent being 100 parts, the amount of the filler added is 1-150 parts, further preferably 1 -100 copies;

   Preferably, the filler is an organic filler and/or an inorganic filler;

   Preferably, the inorganic filler is selected from silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, silicic acid One or a combination of at least two of calcium, mica and glass fiber powder;

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

   Preferably, the filler is silica with a median particle size of 1-15 µm, further preferably 1-10 µm.
6. A resin glue solution characterized in that the resin glue solution is obtained by dissolving or dispersing the thermosetting resin composition according to any one of claims 1 to 5 in a solvent.
7. A prepreg, characterized in that the prepreg includes a reinforcing material, and the thermosetting resin composition according to any one of claims 1 to 5 attached to the reinforcing material after being impregnated and dried.
8. A laminate, characterized in that the laminate comprises one or at least two superposed prepregs according to claim 7.
9. A metal-foil-clad laminate, characterized in that the metal-foil-clad laminate comprises one or at least two superposed prepregs according to claim 7 and one covering the outside of the prepreg Metal foil on one or both sides.
10. A printed circuit board, characterized in that the printed circuit board includes at least one prepreg according to claim 7.