CN112852104A

CN112852104A - Thermosetting resin composition and application thereof

Info

Publication number: CN112852104A
Application number: CN202110030685.4A
Authority: CN
Inventors: 陈振文; 王碧武
Original assignee: Shengyi Technology Co Ltd
Current assignee: Shengyi Technology Co Ltd
Priority date: 2021-01-11
Filing date: 2021-01-11
Publication date: 2021-05-28
Anticipated expiration: 2041-01-11
Also published as: CN112852104B

Abstract

The invention relates to a thermosetting resin composition and application thereof, wherein the thermosetting resin composition comprises the following components: the epoxy resin comprises epoxy resin, active ester, benzoxazine resin and filler, wherein the epoxy resin is crystalline epoxy resin; the structure of the crystalline epoxy resin contains a benzene ring and at least one C1-C4 alkyl substituted on the benzene ring, and the melting point of the crystalline epoxy resin is 80-150 ℃. The copper-clad plate prepared from the thermosetting resin composition has low dielectric constant and dielectric loss factor, low XY axis thermal expansion coefficient, and excellent filling performance, and can meet the application requirements of multilayer plates.

Description

Thermosetting resin composition and application thereof

Technical Field

The invention relates to the technical field of copper-clad plates, in particular to a thermosetting resin composition and application thereof.

Background

In recent years, with the development of high performance, high functionality, and networking of computers and information communication devices, operating signals tend to be high frequency for high-speed transmission and processing of large-capacity information, and thus demands have been made on materials for circuit substrates, particularly those using broadband, such as mobile communication devices.

Generally, it is relatively difficult to simultaneously achieve a low dielectric constant (Dk), a low dielectric dissipation factor (Df), and a low XY axis thermal expansion coefficient (XY-CTE), such as a combination of hydrocarbon and a hollow filler, and although a low Dk and a low Df are achieved, the XY-CTE is significantly large because hydrocarbon is a long chain structure. The typical epoxy, active ester, benzoxazine combination, while achieving low Df and CTE by adding silica, has a significantly higher Dk and an XY-CTE that is generally difficult to lower to 12 ppm/deg.C. The general packaging substrate can easily realize low XY-CTE, but has the problems of high Dk and Df, poor adhesive filling performance, incapability of manufacturing a multilayer board and the like. It can be seen that it is relatively difficult to achieve low Dk, Df and low XY-CTE simultaneously in the prior art.

CN109825081A discloses a thermosetting resin composition, a prepreg containing the same, a metal foil-clad laminate and a printed circuit board, wherein the resin composition comprises the following components: a combination of bismaleimide resin and benzoxazine resin or a prepolymer of bismaleimide resin and benzoxazine resin, an epoxy resin, and an active ester. The metal-clad laminate prepared by the resin composition has high glass transition temperature, low thermal expansion coefficient, higher high-temperature modulus, high peeling strength, low dielectric constant and low dielectric loss factor, and has good heat resistance and good process processability. Although the resin composition has lower Z-axis thermal expansion coefficient, dielectric constant and dielectric dissipation factor, the problem of generally higher XY-CTE is not improved.

CN111500249A discloses a low-dielectric-property low-water-absorption halogen-free copper-clad plate, wherein copper foils are arranged on two sides of the low-dielectric-property low-water-absorption halogen-free copper-clad plate, 3-5 reinforcing material-based prepregs are arranged in the middle of the low-dielectric-property low-water-absorption low-halogen-free copper-clad plate, all layers are: 30-40 parts of bismaleimide modified cyanate ester, 15-20 parts of active ester, 14-18 parts of reactive phosphate, 20-25 parts of phosphorus-containing epoxy resin, 10-15 parts of benzoxazine resin, 0.1-0.1 part of accelerator A, 0.04-0.1 part of accelerator B, 50-100 parts of solvent and 30-50 parts of filler. The method is characterized in that a specific glue solution is prepared according to the characteristics of the copper-clad plate, the glue solution adopts reactive phosphate to replace an additive phosphorus-containing filler and phosphorus-containing phenolic aldehyde, and is matched with various resins such as bismaleimide modified cyanate ester and the like, so that a prepreg and a copper foil can be bonded more firmly, and the prepared copper-clad plate has various characteristics of low water absorption, high Tg, low loss, low CET, halogen-free flame retardance, CAF resistance and the like. Similarly, the problem of high XY-CTE in the prior art is not solved by the halogen-free glue solution.

Therefore, the development of a resin composition for copper clad laminate with low Dk, low Df and low XY-CTE is urgently needed in the field, and the resin composition has excellent adhesive filling performance.

Disclosure of Invention

The invention aims to provide a thermosetting resin composition, and a plate prepared from the thermosetting resin composition has low dielectric constant and dielectric loss factor, low XY-axis thermal expansion coefficient and excellent filling performance, and can meet the application requirements of a multilayer plate.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides a thermosetting resin composition, which comprises the following components: the epoxy resin comprises epoxy resin, active ester, benzoxazine resin and filler, wherein the epoxy resin is crystalline epoxy resin;

the crystalline epoxy resin has a structure containing a benzene ring and at least one C1-C4 (e.g., C2, C3, etc.) alkyl group substituted on the benzene ring, and has a melting point of 80-150 ℃, e.g., 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 148 ℃, etc.

According to the invention, the crystalline epoxy resin with a specific structure and a melting point is added into the thermosetting resin composition, and is combined with the active ester, the benzoxazine and the filler, so that the performances of low Dk, low Df and low XY-CTE can be realized simultaneously, wherein the XY-CTE can be reduced to 12 ppm/DEG C, even below 11 ppm/DEG C, and the prepreg prepared by the resin composition has good flow property, has an excellent adhesive filling function, can meet the application requirement of a multilayer board, and can be applied in the fields of packaging, high speed and the like.

Compared with the structure of unsubstituted C1-C4 alkyl, the invention selects the crystalline epoxy resin substituted with at least one C1-C4 alkyl, is more beneficial to reducing Dk and Df of the sheet material, and compared with the crystalline epoxy resin of other structures, the prepreg prepared by the composition has more excellent fluidity and better filling performance. Further, by selecting a crystalline epoxy resin having a specific melting point, not only Dk and Df can be further reduced, but also the XY-CTE can be further reduced by increasing the filler loading amount due to the lower melt viscosity above the melting point of the crystalline epoxy resin. If the melting point of the crystalline epoxy resin is too low, the crystalline epoxy resin is easy to melt at a lower temperature, the viscosity is too low too early, and the sizing process is obviously influenced, such as the single weight is low, and meanwhile, the fluidity of the resin is too high at a low temperature, the control of a lamination curing process is not facilitated, the high-proportion filling and the thickness control of a filler are not facilitated, and the XY-CTE is influenced; if the melting point is too high, the melting can be carried out at a relatively high temperature, the process control difficulty is obviously increased, and meanwhile, because the temperature is higher, the reaction crosslinking density is obviously increased, although the resin is melted, the melting viscosity is obviously increased, the fluidity is obviously poor, the problems of resin shortage or uneven filler dispersion and the like are easily caused during prepreg or lamination curing, the peeling strength of the plate is influenced, and the XY-CTE is also obviously influenced. Therefore, the present invention's selection of a crystalline epoxy of a particular structure and melting point range is critical to lowering Dk, Df, and XY-CTE.

The crystalline epoxy resin means an epoxy resin having a crystalline moiety at room temperature (25 ℃) and is characterized by having a crystal structure regularly arranged on a part of a polymer chain. Generally, it is an epoxy resin in a state where molecules adversely affecting crystallization are crosslinked, branched little, and have no bulky substituent, or even if any, these form a regular steric configuration. The crystalline epoxy resin generally exists as a solid at a temperature lower than the crystallization temperature at which the resin component is solidified, and becomes a liquid at a temperature higher than the crystallization temperature. Namely, the characteristics are: the crystalline epoxy resin exists as a stable substance in a crystalline state, but the crystalline state is rapidly dissolved to become a liquid with extremely low viscosity as the melting point is reached. The epoxy resin of the present invention contains only a crystalline epoxy resin, may be one or more of crystalline epoxy resins, and does not contain a non-crystalline epoxy resin.

Preferably, the crystalline epoxy resin has a melting point of 100-140 ℃.

The invention preferably selects the crystalline epoxy resin with the melting point of 100-140 ℃ according to the influence on the resin fluidity, has good fluidity in the range, is beneficial to filling glue during application, and can further reduce the XY-CTE of the plate on the premise of ensuring low Dk and low Df.

Preferably, the preparation monomer of the crystalline epoxy resin comprises any one or at least two of the following compounds:

the invention preferably selects the four crystalline epoxy resins with specific structures, has better matching effect with active ester, benzoxazine resin and filler compared with other structures, and is beneficial to further reducing Dk, Df and XY-CTE of the copper-clad plate.

In a preferred embodiment of the present invention, the structure of the crystalline epoxy resin monomer is provided, and the structure of the crystalline epoxy resin can be known without any doubt according to the prior art grasped by those skilled in the art, and a method for preparing the crystalline epoxy resin from the monomer is also known in the art, and those skilled in the art can make the crystalline epoxy resin by self-made or commercially available according to actual conditions.

Preferably, the preparation monomer of the crystalline epoxy resin is

And/or

The melting point of the polymerized crystalline epoxy resin is 108-130 ℃, the side group contains tert-butyl, the moisture absorption is lower than that of the common methyl, the dielectric property is better, and simultaneously, the peeling strength of the plate is more favorably improved due to the S between two benzene rings.

Comprises

The melting point of the polymerized crystalline epoxy resin is 136-150 ℃, the side group contains tert-butyl, the moisture absorption is lower than that of the common methyl, the dielectric property is better, and simultaneously, because only one benzene ring is provided, the epoxy equivalent is relatively small, the crosslinking density is relatively high, and the XY-CTE of the plate is more favorably reduced.

The melting point of the polymerized crystalline epoxy resin is 100-110 ℃, and the biphenyl-structure crystalline epoxy resin is matched with active ester, benzoxazine and a filler, so that compared with the three epoxy resins, the polymerized crystalline epoxy resin has better effect of reducing Dk, Df and XY-CTE.

Preferably, the number average molecular weight of the crystalline epoxy resin is 256-482, such as 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, and the like. Unless otherwise specified, the molecular weight test method of the present invention is GB/T21863-2008, determined by gel permeation chromatography based on polystyrene calibration.

Preferably, the active ester comprises a DCPD-type active ester and/or a naphthalene-type active ester, preferably a DCPD-type active ester.

The DCPD type active ester is preferable in the invention, and is more beneficial to improving the peeling strength of the plate compared with the naphthalene type active ester.

Preferably, the benzoxazine resin includes any one or a combination of at least two of allyl group-containing benzoxazine resin, bisphenol a type benzoxazine resin, bisphenol F type benzoxazine resin, diamine type benzoxazine resin, phenolphthalein type benzoxazine resin, dicyclopentadiene type benzoxazine resin or bisphenol fluorene type benzoxazine resin, preferably dicyclopentadiene type benzoxazine resin and/or bisphenol fluorene type benzoxazine resin.

Preferably, the filler comprises hollow filler and/or non-hollow silica, preferably a combination of hollow filler and non-hollow silica.

In the preferred technical scheme of the invention, the filler combined by hollow filler and non-hollow silica is adopted, and the combination of the hollow filler and the non-hollow silica is matched with the crystalline epoxy resin, the active ester and the benzoxazine resin with the specific structure and the specific melting point, so that the filling amount of the filler can be further improved, and the XY-CTE of the plate can be more effectively reduced.

Preferably, the mass of the hollow filler accounts for 0 to 40% of the total mass of the thermosetting resin composition, such as 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, etc., preferably 10 wt% to 30 wt%. The mass percentage is the filling amount of the hollow filler. The filling amount of the hollow filler is too low, the effect of reducing Dk is not obvious, the filling amount is increased, although Dk is smaller, the process control difficulty is increased because the density of the hollow filler is small, the hollow filler is easy to float, the process control requirement is higher, the filling amount is too high, and the uniform distribution of the hollow filler is difficult to control.

Preferably, the particle size of the hollow filler is 0.1-40um, such as 1um, 2um, 3um, 4um, 5um, 6um, 7um, 8um, 9um, 10um, 11um, 12um, 13um, 14um, 15um, 16um, 17um, 18um, 19um, 20um, 21um, 22um, 23um, 24um, 25um, 26um, 27um, 28um, 29um, 30um, 31um, 32um, 33um, 34um, 35um, 36um, 37um, 38um, 39um, etc. The particle size of the hollow filler is too large, the difficulty in controlling glue filling and drilling during the processing of the multilayer board is high, and the thinner prepreg smaller than 80um is not easy to manufacture; the particle size is too small, the filler is easy to agglomerate, and meanwhile, the fluidity of a resin system is poor, so that the filling glue cannot meet the application requirement of a multilayer board.

Preferably, the particle size of the non-hollow silica is 0.01-40um, such as 0.05um, 0.08um, 0.1um, 0.5um, 0.8um, 1um, 2um, 3um, 4um, 5um, 6um, 7um, 8um, 9um, 10um, 11um, 12um, 13um, 14um, 15um, 16um, 17um, 18um, 19um, 20um, 21um, 22um, 23um, 24um, 25um, 26um, 27um, 28um, 29um, 30um, 31um, 32um, 33um, 34um, 35um, 36um, 37um, 38um, 39um, etc., preferably 0.1-20 um.

Unless otherwise specified, the particle size of the filler of the present invention was measured using a malvern 2000 laser particle size analyzer.

According to the invention, the particle size of the silicon dioxide is optimized, so that the prepreg prepared from the thermosetting resin composition has good fluidity and the capability of applying the filling glue, and the XY-CTE is further reduced.

Preferably, the filler comprises a combination of hollow filler and non-hollow silica, and the total mass of the hollow filler and non-hollow silica comprises 30 wt% to 85 wt% of the total mass of the thermosetting resin composition, such as 32 wt%, 34 wt%, 36 wt%, 38 wt%, 40 wt%, 42 wt%, 44 wt%, 46 wt%, 48 wt%, 50 wt%, 52 wt%, 54 wt%, 56 wt%, 58 wt%, 60 wt%, 62 wt%, 64 wt%, 66 wt%, 68 wt%, 70 wt%, 72 wt%, 74 wt%, 76 wt%, 78 wt%, and the like, preferably 45 wt% to 70 wt%.

Preferably, the thermosetting resin composition comprises the following components in percentage by mass based on 100 wt% of the total mass of the thermosetting resin composition:

further preferably, the thermosetting resin composition comprises the following components in percentage by mass based on 100 wt% of the total mass of the thermosetting resin composition:

according to the invention, the crystalline epoxy resin, the active ester and the benzoxazine resin with specific structures and melting points are preferably compounded with the two fillers according to the addition amount of the formula, so that the components are mutually promoted, and the Dk, the Df and the XY-CTE of the copper-clad plate can be further reduced.

The amount of the above crystalline epoxy resin added is 7 wt% to 30 wt%, for example, 8 wt%, 10 wt%, 12 wt%, 14 wt%, 16 wt%, 18 wt%, 20 wt%, 22 wt%, 24 wt%, 26 wt%, 28 wt%, etc.; the amount of the active ester added is 2 wt% to 25 wt%, such as 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, etc.; the amount of benzoxazine resin added is 6 wt% to 30 wt%, such as 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, etc.; the amount of the hollow filler added is 0 wt% to 40 wt%, for example, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, etc.; the amount of non-hollow silica added is 15 wt% to 85 wt%, such as 16 wt%, 18 wt%, 20 wt%, 22 wt%, 24 wt%, 26 wt%, 28 wt%, 30 wt%, 32 wt%, 34 wt%, 36 wt%, 38 wt%, 40 wt%, 42 wt%, 44 wt%, 46 wt%, 48 wt%, 50 wt%, 52 wt%, 54 wt%, 56 wt%, 58 wt%, 60 wt%, 62 wt%, 64 wt%, 66 wt%, 68 wt%, 70 wt%, 72 wt%, 74 wt%, 76 wt%, 78 wt%, 80 wt%, 82 wt%, 84 wt%, and the like.

Preferably, the thermosetting resin composition further comprises a flame retardant.

The crystalline epoxy resin composition has certain flame retardance due to the fact that the crystalline epoxy resin composition can be filled with a filler with a high content, and UL 94V 0 flame retardance can be achieved without adding or adding a small amount of flame retardant.

Preferably, the flame retardant comprises a bromine-containing flame retardant and/or a halogen-free flame retardant.

Preferably, the halogen-free flame retardant comprises any one or at least two of a phosphorus-containing flame retardant, a nitrogen-containing flame retardant or a silicon-containing flame retardant.

Preferably, the bromine-containing flame retardant comprises any one or a combination of at least two of decabromodiphenyl ether, decabromodiphenylethane, ethylenebistetrabromophthalimide, or brominated polycarbonate. Examples of commercially available brominated flame retardants include, but are not limited to, BT-93W, HP-8010 and HP-3010.

Preferably, the halogen-free flame retardant comprises any one or at least two of tri (2, 6-dimethylphenyl) phosphine, 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2, 6-bis (2, 6-dimethylphenyl) phosphinobenzene, 10-phenyl-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phenoxyphosphazene compound, phosphate ester or polyphosphate ester. Alternative commercially available halogen-free flame retardants include, but are not limited to, SPB-100, PX-200, PX-202, LR-700, OP-930, OP-935, LP-2200, and XP-7866.

The flame retardant may be added in an amount of 1 to 20 wt% based on the resin composition, as required.

Preferably, a curing accelerator is further included in the thermosetting resin composition.

Preferably, the curing accelerator comprises any one or a combination of at least two of imidazole accelerators and derivatives thereof, Lewis acid, triphenylphosphine or piperidine accelerators;

preferably, the imidazole-based accelerator comprises any one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole or 2-undecylimidazole or a combination of at least two of the same.

The curing accelerator may be added in an amount of 0.01 to 5 wt% based on the resin composition, as required.

Another object of the present invention is to provide a resin coating solution obtained by dissolving or dispersing the thermosetting resin composition according to the first object in a solvent.

The conventional preparation method of the resin glue solution comprises the following steps: firstly, adding the solid matter, then adding the liquid solvent, stirring until the solid matter is completely dissolved, then adding the liquid resin and the accelerator, and continuously stirring uniformly.

The solvent in the present invention is not particularly limited, and alcohols such as methanol, ethanol and butanol, alcohols such as ethyl cellosolve, butyl cellosolve, ethylene glycol methyl ether, carbitol and butyl carbitol, ketones such as acetone, butanone, methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and ethoxyethyl acetate, and nitrogen-containing solvents such as N, N-dimethylformamide and N, N-dimethylacetamide can be used. The above solvents may be used alone or in combination of two or more. Ketones such as acetone, methyl ethyl ketone, and cyclohexanone are preferable. The addition amount of the solvent is selected by the skilled person according to the experience of the person in the art, so that the resin glue solution can reach the viscosity suitable for use.

It is a further object of the present invention to provide a prepreg comprising a reinforcing material and the thermosetting resin composition for one of the objects of being impregnated and dried and then adhering thereto.

In the invention, the reinforcing material can be organic fiber cloth, inorganic fiber woven cloth or non-woven cloth; wherein the organic fiber is aramid non-woven fabric; the inorganic fiber woven cloth is E-glass fiber cloth, D-glass fiber cloth, S-glass fiber cloth, T-glass fiber cloth, NE-glass fiber cloth or quartz cloth. The thickness of the reinforcing material is 0.01-0.2mm, such as 0.02mm, 0.05mm, 0.08mm, 0.1mm, 0.12mm, 0.15mm, 0.18mm, and the like. And the reinforcing material is preferably subjected to fiber opening treatment and silane coupling agent surface treatment; the silane coupling agent is any one or a mixture of at least two of epoxy silane coupling agent, amino silane coupling agent or vinyl silane coupling agent.

It is a fourth object of the present invention to provide a laminate comprising at least one third of the prepregs.

Preferably, the laminate is produced by bonding one or more sheets of prepreg together by heating and pressing.

The fifth purpose of the invention is to provide a copper-clad plate, which contains at least one third of the prepreg and metal foils coated on one side or two sides of the laminated prepreg.

Preferably, the metal foil is a copper foil, a nickel foil, an aluminum foil, or a SUS foil, etc.

The sixth purpose of the invention is to provide a printed circuit board, which comprises the laminated board of the fourth purpose or the copper-clad plate of the fifth purpose.

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

Detailed Description

The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

The purchase information of the raw materials used in the following examples and comparative examples is as follows:

(A) epoxy resin

A-1: biphenyl type crystalline epoxy resin, BES1-1100A, melting point: at 100-110 ℃, Ruyimna, the preparation monomer is

A-2: non-biphenyl type crystalline epoxy resin, YNC-502, the melting point is 137-148 ℃, a new material is obtained by wetting, and the preparation monomer is

A-3: novolac type epoxy (non-crystalline epoxy), BNE200, taiwan vinpocetine;

a-4: crystalline epoxy resin with the melting point of 69-75 ℃, the trade name of YNC-504, purchased from Rundah nova, and the preparation monomer is

(B) Active ester

B-1: DCPD-type active esters, 8000, japan DIC;

b-2: naphthalene ring-containing active esters, 8150, japan DIC;

(C) benzoxazine resins

C-1: DCPD-type benzoxazine resin, 8260, Huntsman;

(D) phosphorus-containing flame retardants

D-1: addition type phosphate ester, PX-100, Daba Japan;

(E) curing accelerator:

e: 2-methylimidazole, 2-MI, Japan four kingdoms;

(F) non-hollow silica filler

F-1: spherical silicon dioxide with the particle size of D100 less than 5um, SC2050, Japan admateches;

f-2: angle silica having a particle size D100 of less than 20um, 525, Pedioidae;

(G) hollow filler;

g-1: hollow microspheres, iM30K, 90 wt% particle size <25um, 3M company;

g-2: hollow microspheres, S60HS, 90 wt% particle size <50um, 3M company.

Examples 1 to 11 and comparative examples 1 to 6

Thermosetting resin compositions (the amount of the raw materials was in parts by weight) were prepared as the components shown in table 1, and metal-clad laminate samples were produced according to the following laminate production method:

(1) mixing and stirring the filler and a Methyl Ethyl Ketone (MEK) solvent uniformly, then respectively adding the epoxy resin, the active ester, the benzoxazine resin and other materials, and mixing uniformly to obtain a resin glue solution;

(2) soaking 2116 or 1078 electronic-grade glass fiber cloth (two different reinforcing materials are respectively used for different tests, and the details are shown below) in the resin glue solution, drying the solvent and drying to a semi-cured state to obtain a prepreg, then stacking 8 pieces of 2116 prepreg, respectively placing a special electrolytic copper foil for a copper-clad plate on each of the upper and lower parts, and then carrying out curing lamination at 210 ℃/90min by using a high-temperature press to obtain the copper-clad plate.

Performance testing

The copper-clad laminates obtained in the above examples and comparative examples were subjected to a performance test by the following method:

(1) glass transition temperature (T)_g): using DMA test, the DMA test method specified by IPC-TM-6502.4.24 is measured;

(2) coefficient of thermal expansion (XY, Z-CTE): the CTE test method specified by IPC-TM-6502.4.24C was used for the determination;

(3) dielectric constant (Dk) and dielectric loss factor (Df): the dielectric constant and dielectric dissipation factor at 1GHz were measured by IPC-TM-6502.5.5.9 using a plate capacitance method;

(4) peel Strength (PS): the peel strength is measured according to the test method of IPC-TM-6502.4.8;

(5) thermal crack resistance time (T-288): the test is carried out by using a TMA instrument according to the T-288 test method specified by IPC-TM-6502.4.24.1;

(6) PCT: according to the IPC standard method, the test conditions are 105KPa/60min, the 288 ℃ limit is reached, pass represents pass, and failed represents fail;

(7)1078PP appearance: when the appearance of the prepreg is observed, the resin deficiency or the scratch is obviously poor, the resin deficiency with a small amount and the scratch with a small amount are common, and the prepreg is excellent in that the resin deficiency and the scratch are basically absent.

(8) Testing the fluidity: four pieces of PP of 100 square centimeters were stacked together, placed in a fluidity press and hot-pressed at 171 degrees for 10 minutes, and then a sample of 50 square centimeters was punched out by multiplying the weight by 2 times, and the percentage of weight reduction was calculated as fluidity.

Remarking: the items were tested on 2116PP plaques with an XY-CTE of 8X 2116RC 59% gauge and a DK/Df of 5X 2116RC 59% gauge, except 1078PP was used for appearance with 1078 cloth.

The results of the above performance tests are shown in table 2.

TABLE 1

TABLE 2

As can be seen from the data in Table 2, the copper-clad plate prepared from the thermosetting resin composition provided by the invention not only has lower dielectric constant and dielectric loss factor, but also has lower XY axis thermal expansion coefficient, and meanwhile, the prepreg prepared from the resin composition has better flow property and excellent adhesive filling function, can meet the application requirements of multilayer plates, and can be applied in the fields of packaging, high speed and the like. Wherein, Dk of the copper-clad plate is generally less than 4.25, Df is generally less than 0.0100, XY-CTE is generally less than 13 ppm/DEG C, and the comprehensive performances such as Tg, T-288, PCT, PS, 1078PP appearance, fluidity and the like are better.

Compared with example 1, comparative example 1 adopts phenolic epoxy resin instead of the crystalline epoxy resin with a specific structure and a specific melting point, comparative example 2 does not add benzoxazine resin, and comparative example 3 does not add active ester, the Dk, Df and XY-CTE of the prepreg are all obviously higher than those of example 1, and the flowability of the prepreg is poor, so that the underfill performance is poor. Dk is generally 4.3 or more, or XY-CTE is generally more than 14 ppm/DEG C or more, Df is generally 0.01 or more, and problems such as poor heat resistance, poor PCT or poor PS are presented.

Comparative example 4, which used a crystalline epoxy resin having a melting point not in the range of 80-150 c, showed a significant increase in XY-CTE and poor prepreg flowability, resulting in poor underfill performance, as compared to example 1. Comparative examples 5 and 6 are those in which amorphous epoxy or crystalline epoxy having a melting point out of a specific range is added to the crystalline epoxy defined in the present invention, the fluidity process control is poor, and the XY-CTE is relatively high.

It is understood from the comparison between examples 1 and 7 that when the particle size of the hollow filler is too large (example 7), the XY-CTE is also increased, and the PCT test and 1078PP appearance test results are deteriorated; it can be seen from comparing example 1 with example 8 that the use of a hollow filler in combination with silica (example 1) is more beneficial in reducing Dk, Df and XY-CTE than the use of only one (example 8).

The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims

1. A thermosetting resin composition characterized by comprising the following components: the epoxy resin comprises epoxy resin, active ester, benzoxazine resin and filler, wherein the epoxy resin is crystalline epoxy resin;

the structure of the crystalline epoxy resin contains a benzene ring and at least one C1-C4 alkyl substituted on the benzene ring, and the melting point of the crystalline epoxy resin is 80-150 ℃.

2. The thermosetting resin composition as claimed in claim 1, wherein the crystalline epoxy resin has a melting point of 100-140 ℃;

preferably, the preparation monomer of the crystalline epoxy resin is

And/or

3. Thermosetting resin composition according to claim 1 or 2, characterized in that the active ester comprises a DCPD-type active ester and/or a naphthalene-type active ester, preferably a DCPD-type active ester;

4. Thermosetting resin composition according to any of claims 1-3, characterized in that the filler comprises hollow fillers and/or non-hollow silica, preferably a combination of hollow fillers and non-hollow silica;

preferably, the particle size of the hollow filler is 0.1-40 um;

preferably, the particle size of the non-hollow silica is 0.01-40um, preferably 0.1-20 um;

preferably, the filler comprises a combination of hollow filler and non-hollow silica, and the total mass of the hollow filler and non-hollow silica accounts for 30 wt% to 85 wt%, preferably 45 wt% to 70 wt%, of the total mass of the thermosetting resin composition.

5. The thermosetting resin composition according to any one of claims 1 to 4, characterized by comprising the following components in mass percent, based on 100 wt% of the total mass of the thermosetting resin composition:

6. a resin cement obtained by dissolving or dispersing the thermosetting resin composition according to any one of claims 1 to 5 in a solvent.

7. A prepreg comprising a reinforcing material and a thermosetting resin composition according to any one of claims 1 to 5 attached thereto by impregnation and drying.

8. A laminate comprising at least one prepreg according to claim 7.

9. A copper-clad plate, characterized in that, the copper-clad plate contains at least one prepreg of claim 7 and metal foils coated on one side or both sides of the prepreg after lamination.

10. A printed circuit board comprising the laminate of claim 8 or the copper clad laminate of claim 9.