CN114685991A

CN114685991A - Resin composition and article thereof

Info

Publication number: CN114685991A
Application number: CN202110081577.XA
Authority: CN
Inventors: 明耀强; 胡志龙
Original assignee: ELITE ELECTRONIC MATERIAL (ZHONGSHAN) CO Ltd
Current assignee: ELITE ELECTRONIC MATERIAL (ZHONGSHAN) CO Ltd
Priority date: 2020-12-28
Filing date: 2021-01-21
Publication date: 2022-07-01
Anticipated expiration: 2041-01-21
Also published as: CN114685991B

Abstract

The invention discloses a resin composition, comprising 100 parts by weight of maleimide resin; 20 to 60 parts by weight of a benzoxazine resin; 5 to 40 parts by weight of an epoxy resin; 120 to 240 parts by weight of silica, wherein the silica comprises spherical silica having a settled volume of less than or equal to 0.4 ml/g and a particle size distribution D50 of less than or equal to 1.0 micron; and 0.5 to 1.6 parts by weight of a long-chain alkyl imidazole compound comprising octyl imidazole, undecyl imidazole, heptadecyl imidazole, or a combination thereof. The resin composition can be made into a prepreg, a resin film, a laminate or a printed circuit board, and is improved in at least one of glass transition temperature, thermal expansion rate, copper foil tension, heat resistance after moisture absorption, dielectric loss, the number of resin agglomeration points, surface appearance of a copper-free circuit board, and the like.

Description

Resin composition and product thereof

Technical Field

The present invention relates generally to a resin composition, and more particularly, to a resin composition including a maleimide resin, which can be used to prepare products such as prepregs, resin films, laminates, or printed circuit boards.

Background

In recent years, electronic technology is moving toward higher integration, lower power consumption, and higher performance, and thus higher demands are being made on high-performance electronic materials.

With the high integration of electronic components per unit area, demands are also made on the processability of circuit boards, and not only is good surface appearance of circuit boards required, but also the moisture absorption and heat resistance of resin materials are required to be higher. Therefore, in order to improve the yield of the circuit board, the peel strength of the substrate, the thermal expansion coefficient, and other properties, an inorganic filler is added to the resin composition. However, resin agglomeration points are easy to appear in the circuit board after the circuit board is pressed and filled with glue by the conventional resin composition containing the inorganic filler, and patterns are easy to appear on the surface appearance of the circuit board, so that the quality of the substrate is unstable; therefore, it is also an interest in the industry to solve the problems of resin agglomeration points and surface appearance patterns, etc. to ensure the stability of material quality. Meanwhile, in order to realize the transmission of mass data, the transmission speed of electronic information is required to be high, and the information transmission is also required to be complete, so that the material is required to have low dielectric loss so as to meet the increasing requirements of electronic information data.

Disclosure of Invention

In view of the problems encountered in the prior art, and in particular the inability of the prior art materials to meet one or more of the above-mentioned technical problems, it is a primary object of the present invention to provide a resin composition that overcomes at least one of the above-mentioned technical problems, and articles made using the resin composition.

Specifically, the resin composition or the product thereof provided by the present invention can achieve improvement in at least one of characteristics such as glass transition temperature, thermal expansion coefficient, peel strength (copper foil tension), heat resistance test after moisture absorption, dielectric loss, the number of resin aggregation points, and surface appearance of a copper-free circuit board.

In one aspect, the present invention discloses a resin composition comprising 100 parts by weight of a maleimide resin; 20 to 60 parts by weight of a benzoxazine resin; 5 to 40 parts by weight of an epoxy resin; 120 to 240 parts by weight of silica comprising silica having a settled volume of less than or equal to 0.4 ml/g and a particle size distribution D50 of less than or equal to 1.0 micron; and 0.5 to 1.6 parts by weight of a long-chain alkyl imidazole compound comprising octyl imidazole, undecyl imidazole, heptadecyl imidazole, or a combination thereof.

In one embodiment, the maleimide resin comprises 4,4 '-diphenylmethane bismaleimide, phenylmethane maleimide oligomer, m-phenylene maleimide resin, bisphenol A diphenylether bismaleimide, 3' -dimethyl-5, 5 '-diethyl-4, 4' -diphenylmethane bismaleimide resin, 4-methyl-1, 3-phenylene bismaleimide, 1, 6-bismaleimide- (2,2, 4-trimethyl) hexane, 2, 3-dimethylphenylmaleimide, 2, 6-dimethylphenylmaleimide, N-phenylmaleimide, a maleimide resin containing an aliphatic long chain structure, or a combination thereof.

In one embodiment, the benzoxazine resin includes diaminodiphenyl ether type benzoxazine resin, alkenyl-containing benzoxazine resin, bisphenol a type benzoxazine resin, bisphenol F type benzoxazine resin, dicyclopentadiene benzoxazine resin, phenolphthalein type benzoxazine resin, phosphorus-containing benzoxazine resin, diamine type benzoxazine resin, or a combination thereof.

In one embodiment, the sedimentation volume is determined by using the following solvent measurements: butanone (also known as methyl ethyl ketone), toluene, dimethylacetamide, methanol, ethanol, ethylene glycol monomethyl ether, acetone, methyl isobutyl ketone, cyclohexanone, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide, propylene glycol methyl ether, or combinations thereof.

In one embodiment, the silica comprises spherical silica having a settled volume equal to 0 ml/g and a particle size distribution D50 of less than or equal to 1.0 micron in the resin composition.

In one embodiment, the resin composition includes 100 parts by weight of a maleimide resin; 30 to 60 parts by weight of a benzoxazine resin; 5 to 40 parts by weight of an epoxy resin; 120 to 240 parts by weight of silica, wherein the silica comprises spherical silica having a settled volume equal to 0 ml/g and a particle size distribution D50 of less than or equal to 1.0 micron; and 0.5 to 1.6 parts by weight of a long-chain alkyl imidazole compound comprising octyl imidazole, undecyl imidazole, heptadecyl imidazole, or a combination thereof.

In one embodiment, the ratio of the weight of silica to the weight of total resin is between 0.75:1 and 1.5:1, the weight of total resin being the sum of the weights of all resins in the resin composition except silica and the long chain alkyl imidazole compound. For example, the total resin weight is the sum of the weight of the components of the resin composition except for the inorganic filler (e.g., silica), the curing accelerator (e.g., a long-chain alkyl imidazole compound), the polymerization inhibitor, the coloring agent, the solvent, the toughening agent, and the silane coupling agent.

In one embodiment, the resin composition further comprises cyanate ester, polyolefin resin, small molecule vinyl compound, acrylate resin, phenol resin, polyphenylene ether resin, styrene maleic anhydride resin, polyester resin, amine curing agent, polyamide resin, polyimide resin, or a combination thereof.

In one embodiment, the resin composition further includes a flame retardant, an inorganic filler (e.g., other inorganic fillers than silica), a curing accelerator (e.g., other curing accelerators than long-chain alkyl imidazole compounds), a polymerization inhibitor, a coloring agent, a solvent, a toughening agent, a silane coupling agent, or a combination thereof.

In one embodiment, the spherical silica having a settled volume of less than or equal to 0.4 ml/g and a particle size distribution D50 of less than or equal to 1.0 micron comprises silica sold under the trade name HM031BNJ, silica sold under the trade name HM052BNJ, silica sold under the trade name HM072BNJ, silica sold under the trade name HM102BNJ, or a combination thereof available from Jiangsui glow Powder Technology Ltd.

In one aspect, the present invention provides an article made from the resin composition, which comprises a prepreg, a resin film, a laminate or a printed circuit board.

In one embodiment, the aforementioned article has one, more, or all of the following characteristics:

a dielectric loss of 0.0075 or less as measured at a frequency of 10GHz with reference to the method described in JIS C2565;

the heat resistance test does not generate board explosion after moisture absorption by referring to the methods described in IPC-TM-6502.6.16.1 and IPC-TM-6502.4.23;

the product is prepared into a1 cm long strip sample without a copper circuit board, and the number of resin agglomeration points with the length less than 20 microns in the sample is measured by a scanning electron microscope and is less than or equal to 8;

the product is prepared into a1 cm long strip sample without a copper circuit board, and the number of resin agglomeration points with the length between 20 micrometers and 75 micrometers in the sample is measured by a scanning electron microscope to be less than or equal to 1;

the product is prepared into a1 cm long strip sample without a copper circuit board, and the number of resin agglomeration points with the length of more than 75 microns in the sample is measured by a scanning electron microscope to be 0; and

the article was made into a copper-free circuit board and visually observed for a non-textured surface appearance.

Drawings

FIG. 1 is a plain graphic representation of the surface appearance of a circuit board without copper.

Fig. 2 is a textured representation of the surface appearance of a circuit board without copper.

Fig. 3 is an SEM photograph of resin-free agglomerated spots in the copper-free circuit board of the example.

Fig. 4 is an SEM photograph showing resin agglomeration points in the copper-free circuit board of the comparative example.

Detailed Description

To enable those skilled in the art to understand the features and effects of the present invention, the general description and definitions will be made with respect to terms and phrases used in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

In this document, the terms "comprising," "including," "having," "containing," or any other similar term, are intended to refer to an open-ended franslational phrase (open-ended franslational phrase) that is intended to cover non-exclusive inclusions. For example, a composition or article comprising a plurality of elements is not limited to only those elements recited herein, but may include other elements not expressly listed but generally inherent to such composition or article. In addition, unless expressly stated to the contrary, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or". For example, the condition "a or B" is satisfied in any of the following cases: a is true (or present) and B is false (or not present), a is false (or not present) and B is true (or present), both a and B are true (or present). Moreover, in this document, the terms "comprising," "including," "having," "containing," and "containing" are to be construed as specifically disclosed and cover both the closed conjunctions "consisting of … and the conjunctions" consisting essentially of ….

All features or conditions defined herein as numerical ranges or percentage ranges are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to have covered and specifically disclosed all possible subranges and individual numerical values within the ranges, particularly integer numerical values. For example, a description of a range of "1 to 8" should be considered to have specifically disclosed all subranges such as 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, etc., particularly the subranges bounded by all integer values, and should be considered to have specifically disclosed individual values such as 1, 2,3, 4, 5, 6, 7, 8, etc. within the range. Similarly, a description of a range of "between 1 and 8" should be read as specifically disclosing all ranges disclosed as 1 to 8, 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, and the like, including the endpoints. Unless otherwise indicated, the foregoing explanatory methods apply to all matters contained in the entire disclosure, whether broad or not.

If an amount or other value or parameter is expressed as a range, preferred range, or a list of upper and lower limits, then it is to be understood that all ranges subsumed therein as either the upper or preferred value for that range and the lower or preferred value for that range are specifically disclosed herein, regardless of whether ranges are separately disclosed. Further, when a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.

In this context, a numerical value should be understood to have the precision with which the numerical value is significant, provided that the resulting improved visual appearance is achieved. For example, the number 40.0 should be understood to encompass a range from 39.50 to 40.49.

In this document, where Markush group (Markush group) or Option language is used to describe features or examples of the invention, those skilled in the art will recognize that subgroups of all members of the Markush group or Option list, or any individual member, may also be used to describe the invention. For example, if X is described as being "selected from the group consisting of X1, X2, and X3," it is also meant that claims where X is X1 have been fully described as well as claims where X is X1 and/or X2 and/or X3. Furthermore, to the extent that markush group or option language is used to describe features or examples of the invention, those skilled in the art will recognize that any combination of sub-groups of all members or individual members of the markush group or option list can also be used to describe the invention. Accordingly, for example, if X is described as "selected from the group consisting of X1, X2, and X3," and Y is described as "selected from the group consisting of Y1, Y2, and Y3," then a claim that X is X1 or X2 or X3 and Y is Y1 or Y2 or Y3 has been fully described.

Herein, parts by weight represent parts by weight, which can be any weight unit such as, but not limited to, kilograms, grams, pounds, and the like. For example, 100 parts by weight of maleimide resin, which may represent 100 kilograms of maleimide resin or 100 pounds of maleimide resin.

The following detailed description is merely exemplary in nature and is not intended to limit the invention or the application thereof. Furthermore, there is no intention to be bound by any theory presented in the preceding prior art or the summary of the invention or the following detailed description or examples.

Herein, "or a combination thereof" means "or any combination thereof.

In the present invention, the resin may include compounds and mixtures, unless otherwise specified. The compound comprises a monomer or a polymer. The mixture contains two or more compounds, and the mixture may also contain a copolymer or other auxiliaries, and the like, without being limited thereto.

For example, the compound refers to a chemical substance formed by two or more elements connected by a chemical bond, and may include a monomer, a polymer, and the like, without being limited thereto. Monomer means a compound which can be polymerized or prepolymerized to form a polymer compound. The homopolymer refers to a chemical substance formed by a single compound through polymerization, addition polymerization, or condensation polymerization, and the copolymer refers to a chemical substance formed by two or more compounds through polymerization, addition polymerization, or condensation polymerization, but is not limited thereto. In addition, in the present invention, the polymer of course includes an oligomer, and is not limited thereto. Oligomers, also known as oligomers, are polymers composed of 2 to 20 repeating units, usually 2 to 5 repeating units.

As described above, the main object of the present invention is to provide a resin composition comprising 100 parts by weight of maleimide; 20 to 60 parts by weight of a benzoxazine resin; 5 to 40 parts by weight of an epoxy resin; 120 to 240 parts by weight of silica comprising spherical silica having a settled volume of less than or equal to 0.4 ml/g and a particle size distribution D50 of less than or equal to 1.0 micron; and 0.5 to 1.6 parts by weight of a long-chain alkyl imidazole compound comprising octyl imidazole, undecyl imidazole, heptadecyl imidazole, or a combination thereof.

For example, unless otherwise specified, the long-chain alkyl group in the long-chain alkyl imidazole compound may be substituted for any hydrogen atom in imidazole, and for example, octyl imidazole may include 1-octyl imidazole, 2-octyl imidazole, and the like, and is not limited thereto. Also, for example, the undecylimidazole may include 1-undecylimidazole, 2-undecylimidazole, and the like, without being limited thereto. Also, for example, the heptadecylimidazole may include 1-heptadecylimidazole, 2-heptadecylimidazole, and the like, without being limited thereto.

For example, the long chain alkyl imidazole compounds may include, but are not limited to, 2-octyl imidazole (C8Z), 2-undecylimidazole (C11Z), 2-heptadecyl imidazole (C17Z) which are commercially available from four countries.

In one embodiment, the resin composition of the present invention comprises 120 to 240 parts by weight of silica, for example 120, 160 or 240 parts by weight of silica, compared to 100 parts by weight of maleimide resin.

The silica comprises spherical silica having a sediment volume of less than or equal to 0.4 ml/g and a particle size distribution D50 of less than or equal to 1.0 micron. For example, the sedimentation volume may be 0 ml/g, 0.1 ml/g, 0.2 ml/g, 0.3 ml/g, or 0.4 ml/g, etc., and is not limited thereto. In one embodiment, the silica has a particle size distribution D50 value that is within a tolerance of ± 0.2, unless otherwise specified. For example, the particle size distribution D50 is equal to 1.0 micron, indicating that the particle size distribution D50 may be equal to 1.0 ± 0.2 microns, i.e. the particle size distribution D50 may be 0.8 microns, or the particle size distribution D50 may be 1.0 microns, or the particle size distribution D50 may be 1.2 microns.

Unless otherwise specified, the aforementioned sedimentation volume refers to the volume of a unit mass of filler (such as, but not limited to, silica) sedimented in a solvent, and a smaller sedimentation volume indicates less sedimentation of a unit mass of filler in a solvent, indicating better dispersibility and fluidity of the filler in a solvent. For example, to determine the sedimentation volume, 10g of filler is weighed by an electronic balance (with a precision of 0.01 g) and placed in a 50 ml graduated cylinder with a ground plug (with a precision of 1 ml), then the cylinder wall of the graduated cylinder is washed by a solvent until the filler is sufficiently wetted, then the solvent is added to the measuring range of the graduated cylinder, then the plug is plugged, the graduated cylinder is shaken up and down for 3 minutes at 100 to 110 times per minute, then the graduated cylinder is placed at room temperature for standing for 3 hours, the volume occupied by the sedimentation filler is recorded, each filler is tested for three times, when the error between the test values is less than or equal to 0.10 ml/g, the test value is selected, and the average sedimentation volume of each gram of sedimentation filler in the solvent is calculated.

For example, the sedimentation volume per gram of the sedimented filler in the solvent can be calculated according to the following formula (I):

x is V/m type (I)

In the formula: x represents the settled volume per gram of settled filler in solvent, milliliters per gram (mL/g);

v represents the volume occupied by settled fill, milliliters (mL);

m represents the mass of the filler, in grams (g).

In one embodiment, for example, the solvent used in the method for determining the sedimentation volume may include, but is not limited to, butanone (also called methyl ethyl ketone), toluene, dimethylacetamide, methanol, ethanol, ethylene glycol monomethyl ether, acetone, methyl isobutyl ketone, cyclohexanone, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide, propylene glycol methyl ether, and the like, or a mixture thereof.

For example, the solvent used in the method for measuring the sedimentation volume may be a mixed solvent of butanone and dimethylacetamide mixed in an arbitrary ratio. For example, the mixing ratio of butanone and dimethylacetamide may be 1:9, 9:1, 1:2, 2:1, 3:2, 4:5, 7:6, 8:9, etc., and is not limited.

In one embodiment, for example, and unless otherwise specified, the particle size distribution D50 refers to the particle size corresponding to a cumulative volume distribution of 50% of the filler (e.g., without limitation, spherical silica) as determined by laser light scattering. For example, the spherical silica having a sedimentation volume of 0.4 ml/g or less and a particle size distribution D50 of 1.0 μm or less, preferably a particle size distribution D50 of 1.0 μm or less.

In one embodiment, the spherical silica having a sediment volume of less than or equal to 0.4 ml/g and a particle size distribution D50 of less than or equal to 1.0 micron can be characterized, for example and without limitation, by a specific surface area of 4m²G to 20m²Between/g, the purity is that the content of silicon dioxide is more than or equal to 99.99 percent, and the sphericity is more than or equal to 95 percent.

For example, the spherical silica surface having a sedimentation volume of 0.4 ml/g or less and a particle size distribution D50 of 1.0 μm or less may be modified with a silane coupling agent. For example, the silane coupling agent may include, but is not limited to, one or more of an alkyl silane coupling agent, an unsaturated double bond-containing silane coupling agent, an epoxy silane coupling agent, a phenyl silane coupling agent, an amino silane coupling agent, and an acrylate silane coupling agent.

For example, spherical silicas having a settled volume of less than or equal to 0.4 ml/g and a particle size distribution D50 of less than or equal to 1.0 micron may be obtained from, but not limited to, silicas sold by Jiangsui Himmer powder technology Co., Ltd under the trade names HM031BNJ, HM052BNJ, HM072BNJ, HM102BNJ or HM102BNJ, wherein Jiangsui Himmer powder technology Co., Ltd is located at the website

http://www.jshuimai.com/index.aspx。

In one embodiment, the silica may further comprise other silica in addition to spherical silica having a sediment volume of less than or equal to 0.4 ml/g and a particle size distribution D50 of less than or equal to 1.0 micron, such as, but not limited to, silica having a sediment volume of greater than 0.4 ml/g, a particle size distribution D50 of greater than 1.0 micron, spherical or nonspherical.

In one embodiment, in the resin composition disclosed in the present invention, the resin composition comprises 120 parts by weight to 240 parts by weight of silica, preferably spherical silica having a sedimentation volume of 0 ml/g or more and a particle size distribution D50 of 1.0 μm or less, compared to 100 parts by weight of the maleimide resin.

In one embodiment, for example, the maleimide resin of the present invention refers to a compound or mixture having more than one maleimide functional group in the molecule. The maleimide resin employed in the present invention is not particularly limited, if not specifically indicated, and may be any one or more maleimide resins suitable for use in the production of prepregs, resin films, build-up sheets or printed wiring boards. Specific examples include, but are not limited to, 4 '-diphenylmethane bismaleimide, phenylmethane maleimide oligomer, m-phenylene bismaleimide, bisphenol a diphenylether bismaleimide, 3' -dimethyl-5, 5 '-diethyl-4, 4' -diphenylmethane bismaleimide, 4-methyl-1, 3-phenylene bismaleimide, 1, 6-bismaleimide- (2,2, 4-trimethyl) hexane, 2, 3-dimethylbenzylmaleimide, 2, 6-dimethylbenzylmaleimide, N-phenylmaleimide, maleimide resins containing aliphatic long chain structures, or combinations thereof. In addition, unless otherwise specified, the maleimide resin of the present invention also encompasses prepolymers of the aforementioned resins, such as, for example, a prepolymer of a diallyl compound and a maleimide resin, a prepolymer of a diamine and a maleimide resin, a prepolymer of a polyfunctional amine and a maleimide resin, or a prepolymer of an acidic phenol compound and a maleimide resin, and the like, and is not limited thereto.

For example, the maleimide resin may be a maleimide resin produced by Daiwakasei Corp, such as BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000H, BMI-4000H, BMI-5000, BMI-5100, BMI-7000 and BMI-7000H, or a maleimide resin produced by K.I Chemicals, such as BMI-70, BMI-80.

For example, the maleimide resin containing an aliphatic long chain structure may be a maleimide resin produced by designer molecular companies under the trade names BMI-689, BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI-5000, and BMI-6000.

For example, if not specifically indicated, the benzoxazine resin used in the present invention is not particularly limited, and may be any one or more benzoxazine resins suitable for prepreg, resin film, laminate or printed circuit board fabrication. Specific examples include, but are not limited to, diaminodiphenyl ether type benzoxazine resins, alkenyl-containing benzoxazine resins, bisphenol a type benzoxazine resins, bisphenol F type benzoxazine resins, dicyclopentadiene benzoxazine resins, phenolphthalein type benzoxazine resins, phosphorus-containing benzoxazine resins, diamine type benzoxazine resins. Among them, the alkenyl-containing benzoxazine resin refers to a benzoxazine resin having a carbon-carbon unsaturated double bond (C ═ C) or a derivative functional group thereof, and examples of the aforementioned carbon-carbon unsaturated double bond (C ═ C) or a derivative functional group thereof may include, but are not limited to, functional groups containing a carbon-carbon unsaturated double bond such as a vinyl group, an allyl group, a vinylbenzyl group, and the like in the structure. For example, the alkenyl-containing benzoxazine resin may be allyl-modified benzoxazine resin selected from any one of allyl-modified bisphenol a benzoxazine resin, allyl-modified bisphenol F benzoxazine resin, allyl-modified dicyclopentadiene phenol benzoxazine resin, allyl-modified bisphenol S benzoxazine resin, or diamine benzoxazine resin, or a mixture of at least two thereof. The mixture may be, for example, a mixture of allyl-modified bisphenol a-type benzoxazine resin and allyl-modified bisphenol F-type benzoxazine resin; a mixture of allyl-modified dicyclopentadiene phenol-type benzoxazine resin and allyl-modified bisphenol S-type benzoxazine resin; a mixture of allyl-modified dicyclopentadiene phenol-type benzoxazine resin and allyl-modified bisphenol F-type benzoxazine resin; a mixture of allyl-modified dicyclopentadiene phenol-type benzoxazine resin and allyl-modified bisphenol a-type benzoxazine resin. Wherein, the diamine benzoxazine resin can be diaminodiphenyl methane benzoxazine resin, diaminodiphenyl sulfone benzoxazine resin, diaminodiphenyl sulfide benzoxazine resin or the combination thereof.

For example, the benzoxazine resin may be a benzoxazine resin produced by Huntsman corporation under the trade name LZ-8270 (phenolphthalein type benzoxazine resin), LZ-8280 (bisphenol F type benzoxazine resin), LZ-8290 (bisphenol a type benzoxazine resin), or PF-3500 (diaminodiphenyl ether type benzoxazine resin) produced by vinpocetine or HFB-2006M (phosphorus-containing benzoxazine resin) produced by showa high molecular weight corporation.

In one embodiment, the resin composition of the present invention includes 20 to 60 parts by weight of the benzoxazine resin, for example, 30, 40 or 50 parts by weight of the benzoxazine resin, compared to 100 parts by weight of the maleimide resin. In one embodiment, in the resin composition disclosed in the present invention, the benzoxazine resin is preferably 30 to 60 parts by weight, compared to 100 parts by weight of the maleimide resin.

For example, the epoxy resin of the present invention may be any one or more of various types of epoxy resins known in the art, including, but not limited to, bisphenol a epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, bisphenol AD epoxy resins, novolac epoxy resins, trifunctional epoxy resins, tetrafunctional epoxy resins, polyfunctional epoxy resins, dicyclopentadiene epoxy resins, DCPD epoxy resins, phosphorous epoxy resins, p-xylene epoxy resins, naphthalene epoxy resins (e.g., naphthol epoxy resins), benzofuran epoxy resins, isocyanate-modified epoxy resins. Wherein the novolac epoxy resin can be phenol novolac epoxy resin, bisphenol a novolac epoxy resin, bisphenol F novolac epoxy resin, biphenyl novolac epoxy resin, phenol benzaldehyde (phenol benzaldehide) epoxy resin, phenol aralkyl novolac epoxy resin or o-cresol novolac (o-cresol novolac) epoxy resin; wherein the phosphorus-containing epoxy resin can be DOPO (9, 10-dihydro-9-oxa-10-phosphoanthrene-10-oxide) epoxy resin, DOPO-HQ epoxy resin or the combination thereof. The DOPO epoxy resin may be one or more selected from DOPO-containing phenol novolac epoxy resin (DOPO-containing phenolic novolac epoxy resin), DOPO-containing cresol novolac epoxy resin (DOPO-containing cresol novolac epoxy resin), and DOPO-containing bisphenol A novolac epoxy resin (DOPO-containing bisphenol-A novolac epoxy resin); the DOPO-HQ epoxy resin may be one or more selected from DOPO-HQ-containing phenol novolac epoxy resin (DOPO-HQ-containing phenolic novolac epoxy resin), DOPO-HQ-containing ortho-methyl phenol novolac epoxy resin (DOPO-HQ-containing cresol novolac epoxy resin) and DOPO-HQ-containing bisphenol A novolac epoxy resin (DOPO-HQ-containing bisphenol-A novolac epoxy resin).

For example, the epoxy resin may be purchased from, for example, but not limited to, an epoxy resin having a trade name of NC-3000H (biphenyl type epoxy resin) manufactured by Nippon chemical company, or an epoxy resin having a trade name of HP-7200HH (dicyclopentadiene epoxy resin) manufactured by DIC company, or an epoxy resin having a trade name of NPPN260 (2, 6-dimethylphenol novolac epoxy resin) manufactured by Nanasia Plastic industries, Ltd.

In one embodiment, the resin composition of the present invention comprises 5 to 40 parts by weight of the epoxy resin, for example 10, 20 or 30 parts by weight of the epoxy resin, compared to 100 parts by weight of the maleimide resin.

In one embodiment, the weight ratio of silica to total resin is between 0.75:1 and 1.5: 1. For example, the weight ratio of silica to total resin may be 0.75:1, 0.8:1, 0.9:1, 1:1, 1.2:1, or 1.5:1, and is not limited thereto.

In one embodiment, the total resin weight includes the weight of all resins in the resin composition. For example, the total resin weight is the sum of the weights of all resins in the resin composition except for silica and the long-chain alkyl imidazole compound. For example, the total resin weight is the sum of the weights of the components of the resin composition except for the inorganic filler (e.g., silica), the curing accelerator (e.g., a long-chain alkyl imidazole compound), the polymerization inhibitor, the coloring agent, the solvent, the toughening agent, and the silane coupling agent.

For example, the total resin weight includes, for example and without limitation, the sum of the parts by weight of the maleimide resin, the epoxy resin, and the benzoxazine resin. For example, the total resin weight may further comprise the sum of parts by weight of cyanate ester, polyolefin resin, flame retardant, or a combination thereof. For example, in one embodiment, the total resin weight is the sum of the parts by weight of the maleimide resin, the epoxy resin, and the benzoxazine resin, excluding silica and long-chain alkyl imidazole compounds; for example, in one embodiment, the total resin weight parts include the sum of the weight parts of the maleimide resin, the epoxy resin, the benzoxazine resin, and the cyanate ester, in addition to the inorganic filler (e.g., silica), the curing accelerator (e.g., a long-chain alkyl imidazole compound), the polymerization inhibitor, the toughening agent, the coloring agent, the silane coupling agent, and the solvent.

In one embodiment, for example, the resin composition disclosed herein may further comprise cyanate ester, polyolefin resin, small molecule vinyl compound, acrylate resin, phenol resin, polyphenylene ether resin, styrene maleic anhydride resin, polyester resin, amine curing agent, polyamide resin, polyimide resin, or a combination thereof, as necessary.

The cyanate ester resin employed in the present invention can be various cyanate ester resins known in the art, wherein the cyanate ester resin includes, but is not limited to, cyanate ester resins having an Ar-O-C ≡ N structure (wherein Ar is an aromatic group, such as benzene, naphthalene, or anthracene), phenol novolac type cyanate ester resins, bisphenol a novolac type cyanate ester resins, bisphenol F novolac type cyanate ester resins, dicyclopentadiene structure-containing cyanate ester resins, naphthalene ring structure-containing cyanate ester resins, phenolphthalein type cyanate ester resins, or combinations thereof. For example, examples of cyanate resins include, but are not limited to, cyanate resins produced by Lonza under the trade names Primaset PT-15, PT-30S, PT-60S, BA-200, BA-230S, BA-3000S, BTP-2500, BTP-6020S, DT-4000, DT-7000, ULL950S, HTL-300, CE-320, LVT-50, LeCy, and the like.

For example, the polyolefin resin used in the present invention may be any one or more of those suitable for prepreg, resin film, laminate or printed circuit board fabrication. Specific examples include, but are not limited to, at least one of styrene-butadiene-divinylbenzene terpolymer, styrene-butadiene-maleic anhydride terpolymer, vinyl-polybutadiene-urethane oligomer (vinyl-polybutadiene-urethane oligomer), styrene-butadiene copolymer, hydrogenated styrene-butadiene copolymer, styrene-isoprene copolymer, hydrogenated styrene-isoprene copolymer, methyl styrene homopolymer, petroleum resin, and cyclic olefin copolymer, or a combination thereof.

For example, the small molecular weight vinyl compound used in the present invention refers to a vinyl compound having a molecular weight of 1000 or less, preferably a molecular weight between 100 and 900, and more preferably a molecular weight between 100 and 800. In one embodiment, the small molecule vinyl compound includes, but is not limited to, any one of Divinylbenzene (DVB), bis (vinylbenzyl) ether (bis (vinylbenzyl) ether, BVBE), bis (vinylphenyl) ethane (bis (vinylphenyl) ethane, BVPE), Triallylisocyanurate (TAIC), Triallylcyanurate (TAC), 1, 2, 4-Trivinylcyclohexane (TVCH), or a combination thereof.

For example, acrylate resins useful in the present invention include, but are not limited to, tricyclodecane di (meth) acrylate, tri (meth) acrylate, 1' - [ (octahydro-4, 7-methano-1H-indene-5, 6-diyl) bis (methylene) ] ester (e.g., SR833S, available from Sartomer), or combinations thereof.

For example, the phenol resin employed in the present invention may be a monofunctional, bifunctional or polyfunctional phenol resin. The type of the phenol resin is not particularly limited, and various phenol resins currently used in the industry are within the range of the phenol resin to which the present invention is applicable. Preferably, the phenol resin is selected from phenoxy resin (phenol resin), phenolic resin or a combination thereof.

For example, the polyphenylene ether resin employed in the present invention is not particularly limited, and may be any one or more commercially available products or combinations thereof, specific examples include, but are not limited to, bishydroxypolyphenylene ether resins (e.g., SA90, available from Sabic), bisvinylbenzylpolyphenylene ether resins (e.g., OPE-2st, including vinylbenzylpolyphenylene ether resins having a number average molecular weight of about 1200 (e.g., OPE-2st 1200, available from Mitsubishi gas chemical), vinylbenzylpolyphenylene ether resins having a number average molecular weight of about 2200 (e.g., OPE-2st 2200, available from Mitsubishi gas chemical)), vinylbenzylated modified bisphenol A polyphenylene ethers, methacrylic polyphenylene ether resins (e.g., SA9000, available from Sabic), aminoterminated polyphenylene ether resins or maleimide or maleic anhydride modified polyphenylene ether resins, vinyl chain extended polyphenylene ether resins having a number average molecular weight of about 2200 to 3000, or combinations thereof. Among other things, the vinyl-extended polyphenylene ether resins may include the respective polyphenylene ether resins disclosed in U.S. patent application publication No. 2016/0185904 a1, the contents of which are incorporated herein by reference in their entirety.

For example, in the styrene maleic anhydride resin used in the present invention, the ratio of styrene (S) to Maleic Anhydride (MA) may be 1:1, 2:1, 3:1, 4:1, 6:1 or 8:1, such as but not limited to styrene maleic anhydride copolymer sold under the trade names SMA-1000, SMA-2000, SMA-3000, EF-30, EF-40, EF-60 and EF-80 by Cray Valley, or styrene maleic anhydride copolymer sold under the trade names C400, C500, C700 and C900 by Polyscope. In addition, the styrene maleic anhydride resin may also be an esterified styrene maleic anhydride copolymer, such as those available from Cray Valley under the trade names SMA1440, SMA17352, SMA2625, SMA3840, and SMA 31890. The above-mentioned styrene maleic anhydride resin may be added independently or in combination to the resin composition of the present invention, unless otherwise specified.

For example, the polyester resin used in the present invention is prepared by esterifying an aromatic compound having a dicarboxylic acid group with an aromatic compound having a dihydroxy group, such as but not limited to HPC-8000, HPC-8150 or HPC-8200, which are commercially available from Dainippon ink Chemicals.

For example, the amine curing agent used in the present invention may be dicyandiamide, diaminodiphenyl sulfone, diaminodiphenyl methane, diaminodiphenyl ether, diaminodiphenyl sulfide, or a combination thereof, but is not limited thereto.

For example, the polyamide resins employed in the present invention can be any of a variety of polyamide resins known in the art, including, but not limited to, various commercially available polyamide resin products.

For example, the polyimide resin employed in the present invention can be any of various polyimide resins known in the art, including, but not limited to, various commercially available polyimide resin products.

In one embodiment, for example, the resin composition of the present disclosure may further include a flame retardant, an inorganic filler, a curing accelerator, a polymerization inhibitor, a coloring agent, a solvent, a toughening agent, a silane coupling agent, or a combination thereof, as necessary.

For example, in one embodiment, the flame retardant of the present invention may be any one or more flame retardants suitable for use in prepreg, resin film, laminate or printed circuit board fabrication, and specific examples include, but are not limited to, phosphorus-containing flame retardants, such as at least one, two or more combinations selected from the following group: ammonium polyphosphate (ammonium polyphosphate), hydroquinone-bis- (diphenylphosphate) (hydroquinone bis- (diphenylphosphate)), tris (2-carboxyethyl) phosphine (tri (2-carboxyethyl) phosphine, TCEP), tris (chloroisopropyl) phosphate, trimethyl phosphate (TMP), dimethyl methylphosphonate (DMMP), resorcinol bis- (dimethylphenyl phosphate) (resorcinol bis (dihydroxyphenyl phosphate), RDXP, such as commercially available products like PX-200, PX-201, PX-202), phosphazene compounds (phosphazene, such as SPB-100, SPH-100, SPV-100, melamine products like polyphosphoric acid, polyphosphate, DOPO derivatives (diphenyl phosphate), and diphenyl phosphate resins, DPPO) and derivatives or resins thereof, melamine cyanurate (melamine cyanurate), tris-hydroxy ethyl isocyanurate (tris-hydroxy isocyanurate), aluminum phosphinate salts (e.g., products OP-930, OP-935, and the like), or combinations thereof.

For example, the flame retardant used in the present invention may be a DPPO (diphenyl phosphine oxide) compound (e.g., a double DPPO compound), DOPO (9, 10-dihydro-9-oxa-10-phenylphenanthrene-10-oxide, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) compound (e.g., a double DOPO compound), DOPO resin (e.g., DOPO-HQ, DOPO-NQ, DOPO-PN, DOPO-BPN), DOPO-bonded epoxy resin, etc., wherein the DOPO-PN is a DOPO phenol novolac compound, and the DOPO-BPN may be a DOPO-BPAN (DOPO-bisphenol A novolac), DOPO-BPFN (DOPO-bisphenol F novolac), or DOPO-BPSN (DOPO-bisphenol S novolac) compound.

For example, in one embodiment, the inorganic filler according to the present invention other than spherical silica having a sedimentation volume of 0.4 ml/g or less and a particle size distribution D50 of 1.0 μm or less may be any one or more inorganic fillers suitable for use in resin film, prepreg, laminate or printed circuit board fabrication, and specific examples include, but are not limited to: silica (molten, non-molten, porous or hollow, settled volume may be greater than 0.4 ml/g, particle size distribution D50 may be greater than 1.0 micron), alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, mica, boehmite (boehmite, AlOOH), calcined talc, silicon nitride or calcined kaolin. In addition, the inorganic filler may be in the form of spheres, fibers, plates, granules, flakes or whiskers, and may optionally be pretreated with a silane coupling agent.

In one embodiment, for example, the cure accelerators (including cure initiators) described herein other than long chain alkyl imidazole compounds may include lewis bases or lewis acids and like catalysts. The lewis base may include one or more of imidazole (imidazole, for example, other imidazole compounds than long-chain alkyl imidazole compounds), boron trifluoride amine complex, ethyltriphenylphosphonium chloride (ethyltriphenylphosphonium chloride), 2-methylimidazole (2-methylimidazole, 2MI), 2-phenylimidazole (2-phenyl-1H-imidazole,2PZ), 2-ethyl-4-methylimidazole (2-ethyl-4-methylimidazole,2E4MI), Triphenylphosphine (TPP), and 4-dimethylaminopyridine (4-dimethylaminopyridine, DMAP). The lewis acid may include a metal salt compound, such as a manganese, iron, cobalt, nickel, copper, zinc, etc., and a metal catalyst, such as zinc octoate, cobalt octoate, etc. Cure accelerators also include cure initiators, such as free-radical generating peroxides, including but not limited to: dicumyl peroxide, t-butyl peroxybenzoate, dibenzoyl peroxide (BPO), 2, 5-dimethyl-2, 5-di (t-butylperoxy) -3-hexyne (25B), bis (t-butylperoxyisopropyl) benzene, or combinations thereof.

In one embodiment, for example, the polymerization inhibitor of the present invention is not particularly limited, and may be, for example, various types of polymerization inhibitors known in the art, including, but not limited to, various commercially available polymerization inhibitor products. For example, the polymerization inhibitor may include, but is not limited to, 1-diphenyl-2-trinitrophenylhydrazine, methacrylonitrile, bis-thioesters, nitroxide stable free radicals, triphenylmethyl free radicals, metal ion free radicals, sulfur free radicals, hydroquinone, p-methoxyphenol, p-benzoquinone, phenothiazine, β -phenylnaphthylamine, p-tert-butylcatechol, methylene blue, 4 '-butylidenebis (6-tert-butyl-3-methylphenol), 2' -methylenebis (4-ethyl-6-tert-butylphenol), or a combination thereof.

For example, the nitroxide stable free radical can include, but is not limited to, nitroxide radicals derived from cyclic hydroxylamines, such as 2,2,6, 6-substituted-1-piperidinyloxy radical or 2,2, 5, 5-substituted-1-pyrrolidinyloxy radical. The substituent is preferably an alkyl group having 4 or less carbon atoms such as a methyl group or an ethyl group. Specific examples of the nitroxide radical compound include 2,2,6, 6-tetramethyl-1-piperidinyloxy radical, 2,6, 6-tetraethyl-1-piperidinyloxy radical, 2,6, 6-tetramethyl-4-oxo-1-piperidinyloxy radical, 2, 5, 5-tetramethyl-1-pyrrolidinyloxy radical, 1,3, 3-tetramethyl-2-isoindolinyloxy radical, and N, N-di-tert-butylaminoxy radical. Instead of the nitroxide radical, a stable radical such as a galvinoxyl (galvinoxyl) radical may be used.

The polymerization inhibitor suitable for use in the resin composition of the present invention may also be a product derived by substituting a hydrogen atom or atomic group in the polymerization inhibitor with another atom or atomic group. For example, a product derived by substituting a hydrogen atom in the polymerization inhibitor with an atomic group such as an amino group, a hydroxyl group, or a ketocarbonyl group.

In one embodiment, for example, colorants suitable for use in the present invention may include, but are not limited to, dyes (dye) or pigments (pigment).

In one embodiment, for example, the primary function of the added solvent is to change the solids content of the resin composition and adjust the viscosity of the resin composition. For example, the solvent may include, but is not limited to, methanol, ethanol, ethylene glycol monomethyl ether, acetone, methyl ethyl ketone (also known as methyl ethyl ketone), methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide, dimethylacetamide, propylene glycol methyl ether, and the like, or a mixture thereof.

In one embodiment, for example, the primary function of the addition of the toughening agent is to improve the toughness of the resin composition. Among them, the toughening agent may include, but is not limited to, carboxyl-terminated butadiene nitrile rubber (CTBN), core-shell rubber (core-shell rubber), and the like, or a combination thereof.

In one embodiment, for example, the silane coupling agent used in the present invention may include silane compounds (silanes, such as but not limited to siloxane compounds (siloxanes)), which may be classified according to the type of functional group into aminosilane compounds (amino silanes), epoxysilane compounds (epoxy silanes), vinylsilane compounds, acrylsilane compounds, methacrylsilane compounds, hydroxysilane compounds, isocyanatosilane compounds, methacryloxysilane compounds, and acryloxysilane compounds.

The resin composition of the foregoing embodiments can be made into various articles, such as components suitable for use in various electronic products, including but not limited to prepregs, resin films, laminates, or printed circuit boards.

For example, the resin composition of various embodiments of the present disclosure may be formed into a prepreg that includes a reinforcing material and a layer disposed on the reinforcing material. The layered product is prepared by heating the resin composition at high temperature to form a semi-cured state (B-stage). The baking temperature for preparing the prepreg is between 165 ℃ and 200 ℃. The reinforcing material may be any one of a fiber material, a woven fabric, and a non-woven fabric, and the woven fabric preferably includes a glass fiber cloth. The type of the glass cloth is not particularly limited, and may be commercially available glass cloth for various printed circuit boards, such as E-type glass cloth, D-type glass cloth, S-type glass cloth, T-type glass cloth, L-type glass cloth, or Q-type glass cloth, wherein the type of the fiber includes yarn, roving, and the like, and the form may include open fiber or non-open fiber. The aforementioned nonwoven fabric preferably includes a liquid crystal resin nonwoven fabric, such as a polyester nonwoven fabric, a polyurethane nonwoven fabric, and the like, without being limited thereto. The fabric may also include a liquid crystal resin fabric, such as a polyester fabric or a polyurethane fabric, and is not limited thereto. The reinforcing material can increase the mechanical strength of the prepreg. In a preferred embodiment, the reinforcing material may also optionally be pretreated with a silane coupling agent. The prepreg forms an insulating layer after being subsequently heated and cured (C-stage).

For example, the resin composition of the embodiments of the present invention can be made into a resin film, which is obtained by post-curing the resin composition after baking and heating. The resin composition can be selectively coated on a polyethylene terephthalate film (PET film), a polyimide film (PI film), a copper foil or a copper foil with back glue, and then is formed into a semi-solidified state after being baked and heated, so that the resin composition forms a resin film.

For example, the resin composition of the embodiments of the present invention may be made into a laminate including two metal foils and an insulating layer disposed between the metal foils, wherein the insulating layer may be prepared by curing the resin composition under high temperature and high pressure (C-stage), and the curing temperature may be between 180 ℃ and 220 ℃, preferably between 200 ℃ and 210 ℃, and the curing time is between 60 minutes and 180 minutes, preferably between 80 minutes and 100 minutes. The insulating layer may be formed by curing (C-stage) the prepreg or the resin film. The metal foil may comprise copper, aluminum, nickel, platinum, silver, gold, or alloys thereof, for example the metal foil may be copper foil.

Preferably, the laminate is a Copper Clad Laminate (CCL).

In addition, the laminate can be further processed by a circuit process to form a circuit board, such as a printed circuit board.

For example, the resin composition or the product thereof provided by the invention can be improved in one or more aspects of glass transition temperature, Z-axis thermal expansion rate, copper foil tension, heat resistance after moisture absorption, dielectric loss, resin agglomeration point number, appearance of a circuit board surface without copper, and the like.

For example, the resin composition or article thereof provided by the present invention may satisfy one, more or all of the following characteristics:

a relatively high glass transition temperature, e.g., a glass transition temperature Tg of greater than or equal to 301 deg.C, e.g., between 301 deg.C and 333 deg.C, as measured by the method described with IPC-TM-6502.4.24.4;

a Z-axis thermal expansion of less than or equal to 1.33%, for example between 1.08% and 1.33%, measured by the method described with reference to IPC-TM-6502.4.24.5;

the copper foil tension measured by the method described with reference to IPC-TM-6502.4.8 is high, for example Hoz reversed copper foil, the copper foil tension is greater than or equal to 4.7lb/in, for example, between 4.7lb/in and 5.3lb/in, and for example, between 4.8lb/in and 5.3 lb/in; for example, an ultra-thin copper foil with a thickness of less than or equal to 2 microns is adopted, and the tensile force of the copper foil is greater than or equal to 4.3lb/in, such as between 4.3lb/in and 4.9lb/in, and also such as between 4.4lb/in and 4.9 lb/in;

the method is referred to IPC-TM-6502.6.16.1 and IPC-TM-6502.4.23, and no board explosion occurs in the heat resistance test after moisture absorption;

a dielectric loss of 0.0075 or less, for example, 0.0068 to 0.0075, measured at a frequency of 10GHz with reference to the method described in JIS C2565;

the product is prepared into a1 cm long strip sample without the copper circuit board, and the resin aggregation points in the sample are measured to be less by a scanning electron microscope, for example, the number of the resin aggregation points with the length of less than 20 microns in the sample measured by the scanning electron microscope is less than or equal to 8, for example, between 0 and 8, and for example, between 0 and 6; the number of resin agglomeration points in the sample having a length of between 20 and 75 microns, measured for example by scanning electron microscopy, is less than or equal to 1, for example equal to 0; and the number of resin agglomeration points with a length of more than 75 micrometers in the sample is 0, for example, by scanning electron microscopy; and

the article is formed into a copper-free circuit board and has a visually observable, unpatterned surface appearance.

The resin compositions of examples of the present invention and comparative examples of the present invention were prepared from the following raw materials in the amounts shown in tables 7 to 12, respectively, and further prepared into test specimens or articles. The test results of examples and comparative examples are shown in tables 13 to 18 below.

BMI-2300: phenylmethaneimide oligomers, available from Dazawa Chemicals.

BMI-70: aromatic bismaleimide resin available from K.I chemistry.

BMI-3000: maleimide resins containing aliphatic long chain structures are available from Designer molecules.

BMI-80: aromatic bismaleimide resin available from K.I chemistry.

PF-3500: diaminodiphenyl ether type benzoxazine resin, available from vinpocetine.

LZ 8290: bisphenol a benzoxazine resin, available from Huntsman.

LZ 8280: bisphenol F benzoxazine resin, available from Huntsman.

KZH-5031: allyl modified dicyclopentadiene phenol type benzoxazine resin: made by or purchased from Kolon.

NC-3000H: biphenyl type epoxy resins, available from Nippon Kayaku.

NPPN 260: 2, 6-dimethylphenol novolac epoxy resin, available from south Asia plastics industries, Inc.

HP-7200 HH: dicyclopentadiene epoxy resin, available from great japan ink chemistry (d.i.c.).

HM031 BNJ: the spherical silica treated with the aminosilane coupling agent had a sedimentation volume of 0 ml/g and a particle size distribution D50 of 0.3 μm, and was purchased from Jiangsu Huimei powder science and technology Co.

HM052 BNJ: the spherical silica treated with the aminosilane coupling agent had a sedimentation volume of 0 ml/g and a particle size distribution D50 of 0.5 μm, and was purchased from Jiangsu Huimei powder science and technology Co.

HM052 BYJ: the spherical silica treated with the acrylate silane coupling agent has a sedimentation volume of 0 ml/g and a particle size distribution D50 of 0.5 μm, and is available from Jiangsu Huimei powder science and technology Co.

HM072 BNJ: the spherical silica treated with the aminosilane coupling agent had a sedimentation volume of 0 ml/g and a particle size distribution D50 of 0.7 μm, and was purchased from Jiangsu Huimei powder science and technology Co.

HM102 BNJ: the spherical silica treated with the aminosilane coupling agent had a sediment volume of 0.39 ml/g and a particle size distribution D50 of 1.0 μm, and was purchased from Jiangsu Huimei powder technology Ltd.

Spherical silica A: the spherical silica treated with the aminosilane coupling agent had a sediment volume of 0.60 ml/g and a particle size distribution D50 of 0.5 microns and was purchased from brocade silicon material.

Spherical silica B: the spherical silica treated with the acrylate silane coupling agent had a settled volume of 1.09 ml/g and a particle size distribution D50 of 0.5 microns and was purchased from brocade silicon material.

SC 2050-KNK: spherical silica treated with an aminosilane coupling agent, having a sediment volume of 0.89 ml/g and a particle size distribution D50 of 0.5 microns, was purchased from Admatechs.

Spherical silica C: the particle size distribution D50 was 2 micron spherical silica, purchased from brocade silicon material.

DL 0110: the particle size distribution D50 was 2 micron non-spherical fused silica, available from brocade silicon materials.

D70: particle size distribution D50 was a 7 micron nonspherical fused silica, available from brocade silicon material.

KB-01D: boehmite (AlOOH), available from hexa chemical corporation.

C8Z: 2-octyl imidazole, purchased from four nations.

C11Z: 2-undecylimidazole, available from four nations.

C17Z: 2-heptadecylimidazole, purchased from four nations.

2 MZ: dimethylimidazole, purchased from four nations.

2E4 MZ: diethyl tetramethyl imidazole, available from four nations.

2 PZ: diphenylimidazoles, available from four nations.

25B: peroxide, 100% solids, was purchased from Nichigan oil Co.

MEK: butanone, unlimited sources.

DMAC: dimethylacetamide available from mesopetrochemicals.

Toluene: purchased from a strong place.

Method for measuring and calculating sedimentation volume of silicon dioxide

Method for measuring sedimentation volume

Weighing 10g of filler by an electronic balance (the precision is 0.01 g), placing the filler into a 50 ml graduated cylinder (the precision is 1 ml) with a ground plug, then washing the wall of the graduated cylinder by using a solvent until the filler is fully wetted, then adding the solvent to the measuring range of the graduated cylinder, plugging a plug, shaking up and down for 3 minutes at 100-110 times per minute, placing the graduated cylinder at room temperature for standing for 3 hours, recording the volume occupied by the settled filler, testing each filler for three times, selecting a test value when the error between the measured values is less than or equal to 0.10 ml/g each time, and calculating the average value of the settled volume of each gram of settled filler in the solvent.

Method for calculating sedimentation volume

The sedimentation volume per gram of the sedimented filler in the solvent can be calculated according to the following formula (I):

x is V/m type (I)

In the formula: x represents the settled volume per gram of settled fill in solvent, milliliters per gram (mL/g);

v represents the volume occupied by settled fill, milliliters (mL);

m represents the mass of the filler, in grams (g).

The sedimentation volumes of the above silica raw materials in different solvents or mixed solvents were measured and calculated according to the above measurement methods and calculation methods of sedimentation volumes, and the results of the measurement and calculation are shown in tables 1 to 6 below.

TABLE 1 sedimentation volume of silica in MEK

TABLE 2 sedimentation volume of silica in DMAC

[ Table 3] sedimentation volume of silica in toluene

TABLE 4 sedimentation volume of silica in a mixed solvent (MEK and DMAC mixed at a 1:1 mass ratio)

TABLE 5 sedimentation volume of silica in a mixed solvent (MEK and DMAC mixed at a 9:1 mass ratio)

TABLE 6 sedimentation volume of silica in a mixed solvent (MEK and DMAC mixed at a 1:9 mass ratio)

The compositions of the resin compositions of the examples and comparative examples and the test results are shown in the following table (units are in parts by weight):

TABLE 7 composition of resin compositions of examples (unit: parts by weight)

TABLE 8 composition of resin compositions of examples (unit: parts by weight)

TABLE 9 composition of resin compositions of examples (unit: parts by weight)

TABLE 10 composition of resin compositions for comparative examples (unit: parts by weight)

TABLE 11 composition of resin compositions for comparative examples (unit: parts by weight)

TABLE 12 composition of resin compositions for comparative examples (unit: parts by weight)

The respective resin compositions of tables 7 to 12 were prepared by making varnishes and respective test pieces (samples) in the following manner, and property measurements were made according to specific test conditions to obtain the test results of tables 13 to 18.

Varnish (or glue forming, varnish)

The resin compositions obtained by adding the respective components in the respective examples (represented by E, e.g., E1 to E22) or comparative examples (represented by C, e.g., C1 to C22) in the amounts shown in tables 7 to 12 to a stirring tank and stirring the respective components, and uniformly mixing the respective components are referred to as resin varnishes.

Using example E1 as an example, 100 parts by weight of a maleimide resin (BMI-2300), 40 parts by weight of a benzoxazine resin (PF-3500) and 20 parts by weight of an epoxy resin (NC-3000H) were added to a stirrer containing 100 parts by weight of Methyl Ethyl Ketone (MEK) and 30 parts by weight of Dimethylacetamide (DMAC), and the mixture was stirred until the solid content was dissolved to a homogeneous state in a liquid state. Then, 160 parts by weight of spherical silica (HM031BNJ) having a sedimentation volume of 0 ml/g and a particle size distribution D50 of 1.0 μm or less was added thereto and stirred until completely dispersed, and then 0.8 part by weight of a long-chain alkyl imidazole compound (C11Z, dissolved in solution with an appropriate amount of solvent) was added thereto and stirred for 1 hour, to obtain a varnish of the resin composition E1.

Further, varnishes of other examples E2 to E22 and comparative examples C1 to C22 were prepared in accordance with the amounts of the components listed in tables 7 to 12 above with reference to the method for preparing the varnish of example E1.

Prepreg (use 2116E-glass cloth)

The resin compositions of examples (E1 to E22) and comparative examples (C1 to C22) listed in tables 7 to 12 were added in portions to a stirring tank, respectively, mixed uniformly and stirred until completely dissolved as a varnish (varnish), and the resin compositions were put into an impregnation tank. A glass fiber cloth (e.g., 2116E-glass fiber cloth) is passed through the impregnation tank to adhere the resin composition to the glass fiber cloth, and the resultant is heated at 120 to 150 ℃ to a semi-cured state (B-Stage) to obtain a prepreg (resin content: about 52%).

Prepreg (use 1080E-glass fiber cloth)

The resin compositions of examples (E1 to E22) and comparative examples (C1 to C22) listed in tables 7 to 12 were added in portions to a stirring tank, respectively, mixed uniformly and stirred until completely dissolved as a varnish (varnish), and the resin compositions were put into an impregnation tank. A glass fiber cloth (e.g., 1080-size E-glass fiber cloth) is passed through the impregnation tank to adhere the resin composition to the glass fiber cloth, and the resultant is heated at 120 to 150 ℃ to a semi-cured state (B-Stage) to obtain a prepreg (resin content: about 70%).

Prepreg (using 1017E-glass fiber cloth)

The resin compositions of examples (E1 to E22) and comparative examples (C1 to C22) listed in tables 7 to 12 were added in portions to a stirring tank, respectively, mixed uniformly and stirred until completely dissolved as a varnish (varnish), and the resin compositions were put into an impregnation tank. A glass fiber cloth (e.g., 1017-standard E-glass fiber cloth) is passed through the impregnation tank to adhere the resin composition to the glass fiber cloth, and the resin composition is heated at 120 to 150 ℃ to a semi-cured state (B-Stage) to obtain a prepreg (about 76% resin content).

Copper foil base plate (eight sheets pressed together)

Two reverse-wound (RTF) copper foils having a thickness of 18 μm and eight prepregs (using 2116E-glass cloth) made of each resin composition were prepared in batches. The resin content of each prepreg was about 52%. And laminating the copper foil, the eight prepregs and the copper foil in sequence, and pressing for 2 hours at 200 ℃ under a vacuum condition to form each copper foil substrate. Wherein eight mutually laminated prepregs are cured (C-stage) to form an insulating layer between two copper foils, and the resin content of the insulating layer is about 52%.

Copper-free substrate (eight prepregs laminated)

And etching the copper foil substrate to remove the copper foils on the two sides to obtain a copper-free substrate which is formed by pressing eight prepregs and has the resin content of about 52 percent.

Without copper base (laminated with two prepregs)

Two reversed-Received (RTF) copper foils with a thickness of 18 μm and two prepregs (using 1080E-glass cloth) made of each resin composition were prepared in batches. The resin content of each prepreg was about 70%. And (3) laminating the copper foil, the two prepregs and the copper foil in sequence, pressing for 2 hours at 200 ℃ under vacuum conditions to form each copper foil substrate, and etching and removing the copper foils on two surfaces of each copper foil substrate to obtain the copper-free substrate. Wherein two prepregs stacked on each other are cured (C-stage) to form an insulating layer between the two copper foils, the resin content of the insulating layer being about 70%.

Four-layer circuit board

Firstly, a core plate (core) is manufactured by the following method: four prepregs (e.g., EM-827 available from optoelectronics, 7628E-glass fiber cloth, RC 42%) were prepared, and copper foils were laminated on both sides of the four prepregs, followed by press-curing under vacuum, high temperature (195 ℃) and high pressure (360psi) for 2 hours to obtain a copper-containing core sheet. The core plate is processed by a browning preparation process to obtain a browned core plate. Then, a prepreg (using 2116E-glass cloth) of each example or comparative example and a2 μm ultra-thin copper foil with a carrier were stacked on each of both sides of the outer layer of the browned core sheet, and then laminated under vacuum at 195 ℃ for 2 hours to form a laminate including the ultra-thin copper foil. And stripping the carrier copper foil on the ultrathin copper surface of the outer layer of the laminated board, and carrying out whole-board electroplating by omitting a cleaning procedure to ensure that the thickness of a copper layer is 35 microns to form the four-layer circuit board.

Non-copper circuit board (two layers)

The core board (core) is manufactured by the following method: 1 prepreg (for example, product EM-390, available from optoelectronics, using 1078E-glass fiber cloth, RC 57%) was prepared, and copper foils were laminated on both sides of each of the 1 laminated prepregs, followed by press-curing under vacuum, high temperature (195 ℃) and high pressure (360psi) for 2 hours to obtain a copper-containing core sheet. The core plate is subjected to browning preparation and etching process treatment to obtain the brown core plate of the circuit. Next, prepregs (using 1017E-glass cloth) of each example or comparative example and a 0.5 oz (oz) (18 μm thick) Reversed (RTF) copper foil were stacked on both sides of the outer layer of the wire-browned core board, and then laminated under vacuum at 195 ℃ for 2 hours to form a circuit board including the copper foil. Then, the copper foils on both sides of the circuit board were etched away to obtain a copper-free circuit board (two layers).

The respective test methods and their characteristic analysis items are described below.

1. Glass transition temperature (Tg)

In the glass transition temperature test, a copper-free substrate (formed by pressing eight prepregs) is selected as a sample to be tested for Dynamic Mechanical Analysis (DMA). The samples were heated at a rate of 2 ℃ per minute from 35 ℃ to 350 ℃ and the glass transition temperature (in units) of each sample was measured as described in IPC-TM-6502.4.24.4.

For example, articles made from the resin compositions disclosed herein have a high glass transition temperature, e.g., a glass transition temperature Tg of greater than or equal to 301 deg.C, e.g., between 301 deg.C and 333 deg.C, as measured by the method described in IPC-TM-6502.4.24.4.

2. Thermal expansion rate (ratio of thermal expansion)

In the measurement of the thermal expansion rate (also called dimensional change rate), a copper-free substrate (formed by pressing eight prepregs) is selected as a sample to be measured, and Thermal Mechanical Analysis (TMA) is performed. Heating the sample at a temperature rise rate of 10 ℃ per minute, heating the sample from 35 ℃ to 265 ℃, and measuring the Z-axis dimension change rate (the temperature range of 50-260 ℃ in unit percent) of each sample to be measured by referring to the method described by IPC-TM-6502.4.24.5, wherein the lower the percentage of the dimension change rate is, the better the sample is.

In general, a substrate has a high Z-axis thermal expansion rate, and a copper foil substrate has a large dimensional change rate, which easily causes reliability problems such as board breakage during processing of a printed circuit board. For the art, lower percentages of thermal expansion are preferred, and differences in thermal expansion greater than or equal to 0.1% are significant differences.

For example, articles made from the disclosed resin compositions have a thermal expansion rate of less than or equal to 1.33%, e.g., such as less than or equal to 1.08%, 1.12%, 1.14%, 1.15%, 1.16%, 1.18%, 1.19%, 1.20%, 1.21%, 1.25%, 1.26%, 1.27%, 1.29%, 1.30%, or 1.33%, e.g., between 1.08% and 1.33%, as measured by the method described with reference to IPC-TM-6502.4.24.5.

3. Conventional copper foil tension (or peel strength, peel Strength, P/S)

The copper foil substrate (formed by pressing eight prepregs) is cut into a rectangular sample with the width of 24mm and the length of more than 60mm, and the surface copper foil is etched to only leave a strip-shaped copper foil with the width of 3.18mm and the length of more than 60 mm. The amount of force (lb/in) required to pull the copper foil off the surface of the substrate was measured by the method described in IPC-TM-6502.4.8 at room temperature (about 25 ℃ C.) using a universal tensile strength tester. The higher the copper foil tension is, the better the copper foil tension is, and the difference of the copper foil tension values is more than or equal to 0.1lb/in is a remarkable difference.

For example, the tensile strength of the copper foil measured by the method described in IPC-TM-6502.4.8 for the product made of the resin composition disclosed in the present invention is greater than or equal to 4.7lb/in, preferably greater than or equal to 4.8lb/in, 4.9lb/in, 5.0lb/in, 5.1lb/in, 5.2lb/in or 5.3lb/in, for example, between 4.7lb/in and 5.3lb/in, or between 4.8lb/in and 5.3 lb/in.

4. Ultra-thin copper foil pulling force (or Peel Strength, Peel Strength, P/S)

The four-layer circuit board is cut into a rectangular sample with the width of 24mm and the length of more than 60mm, and the surface copper foil is etched, so that only strip-shaped copper foils with the width of 3.18mm and the length of more than 60mm are left. The amount of force (lb/in) required to pull the copper foil off the surface of the substrate was measured by the method described in IPC-TM-6502.4.8 at room temperature (about 25 ℃ C.) using a universal tensile strength tester. The higher the copper foil tension is, the better the copper foil tension is, and the difference of the copper foil tension values is more than or equal to 0.1lb/in is a remarkable difference.

For example, the tensile strength of the copper foil, measured by the method described in IPC-TM-6502.4.8, of an article made from the disclosed resin composition is greater than or equal to 4.3lb/in, preferably greater than or equal to

4.4lb/in, 4.5lb/in, 4.6lb/in, 4.7lb/in, 4.8lb/in or 4.9lb/in, for example between 4.3lb/in and 4.9lb/in or between 4.4lb/in and 4.9 lb/in.

5. Heat resistance test after moisture absorption (PCT)

The copper-free substrate (formed by pressing eight prepregs) is selected, moisture absorption is carried out for 168 hours (the test temperature is 121 ℃, and the relative humidity is 100%) by the method of IPC-TM-6502.6.16.1 through Pressure Cooking Test (PCT), then the copper-free substrate is immersed into a tin furnace with the constant temperature of 288 ℃ by the method of IPC-TM-6502.4.23, and the copper-free substrate is taken out after being immersed for 20 seconds to observe whether the board explosion occurs, for example, interlayer peeling occurs between the insulating layer and the insulating layer, namely, the board explosion occurs. Delamination can cause blistering separation between any layers of the substrate.

For example, articles made from the resin compositions disclosed herein do not burst after moisture absorption as described in IPC-TM-6502.6.16.1 and IPC-TM-6502.4.23. The no-pop result is recorded as "Pass" to represent Pass, and the pop result is recorded as "Fail" to represent Fail.

6. Dielectric loss (Df)

In the measurement of dielectric loss, the above copper-free substrate (formed by laminating two prepregs) was selected as a sample to be measured, and each sample to be measured was measured at a frequency of 10GHz by a microwave dielectric analyzer (available from AET corporation, japan) according to the method described in JIS C2565. Lower dielectric loss represents better dielectric properties of the sample to be tested.

At a measurement frequency of 10GHz, in the case that the Df value is between 0.0050 and 0.0100, a difference of the Df value less than 0.0003 represents no significant difference in dielectric loss of the substrates, and a difference of the Df value greater than or equal to 0.0003 represents a significant difference in dielectric loss between different substrates (significant technical difficulty).

For example, the dielectric loss of an article made of the resin composition disclosed by the invention is less than or equal to 0.0075, such as between 0.0068 and 0.0075, measured at a frequency of 10GHz according to the method described in JIS C2565.

7. Surface appearance of copper-free circuit boards

The appearance of the surface of the copper-free circuit board (two layers) is visually observed by a person, and if the copper-free circuit board has pattern distribution, the compatibility between the resin and the filler in the resin composition is poor or the phenomenon of non-uniformity caused by large difference of fluidity is represented. The non-copper-containing circuit board may have a pattern that causes poor heat resistance, poor dielectric loss, or large variation in dielectric loss. The surface of the circuit board without copper is marked with 'Y' when the pattern appears at least one position, and the surface of the circuit board without copper is marked with 'N' when the pattern appears no. The surface appearance of the circuit board without copper is shown in fig. 1 without patterns, and the surface appearance of the circuit board without copper is shown in fig. 2 with more pronounced pattern areas indicated by arrows. Reference numeral 6 in fig. 1 and 2 represents the surface appearance of the different copper-free circuit board samples divided into 20 regions, but the different samples were all compared to the 6 th region at the same time.

8. Copper-free circuit board resin agglomerate point

The method comprises the following steps of cutting a sample of a1 cm long strip-shaped copper-free circuit board (two layers) (the 1 cm long strip-shaped copper-free circuit board (two layers) sample should contain a hollow area and a copper surface area), then carrying out glue pouring on the 1 cm long strip-shaped copper-free circuit board (two layers) sample to prepare a slice, and observing the slice through a Scanning Electron Microscope (SEM) (namely observing the resin agglomeration condition of the sample cross section of the 1 cm long strip-shaped copper-free circuit board (two layers)). Then counting the number of resin agglomeration points according to the following steps: firstly, finding out resin agglomeration points at 300 times, then magnifying the resin agglomeration points at 1000 times, and then measuring the size of the resin agglomeration points through an SEM (scanning Electron microscope), wherein for example, 1 resin agglomeration point measured by the SEM is less than 20 micrometers (less than 20 micrometers), and the length of the 1 resin agglomeration point is recorded as 1 resin agglomeration point less than 20 micrometers; for example, when the length of 1 resin aggregation point measured by SEM is 20 micrometers to 75 micrometers, the length is recorded as 1 resin aggregation point of 20 micrometers to 75 micrometers; as another example, 1 resin agglomerate point taken by SEM having a length greater than 75 microns is recorded as 1 resin agglomerate point greater than 75 microns. Repeating the steps until each position of the 1 cm long-strip copper-free circuit board (two layers) sample is observed, and counting the total number of the resin agglomeration points which are less than 20 micrometers (less than 20 micrometers), between 20 micrometers and 75 micrometers (20 micrometers-75 micrometers) and more than 75 micrometers (more than 75 micrometers) in the 1 cm long-strip copper-free circuit board (two layers).

For example, FIG. 3 is an SEM photograph of a sample of a1 cm long copper-free circuit board (two layers) without resin agglomeration points; fig. 4 is an SEM photograph of resin agglomerate points in a1 cm long sample of copper-free circuit board (two layers), where the three black circles in the SEM photograph represent the resin agglomerate points.

The smaller the resin aggregation point or the shorter the length of the resin aggregation point in a1 cm strip-shaped sample without a copper circuit board (two layers), the better the compatibility or fluidity between the resin and the filler of the sample to be measured.

For example, when 1 resin agglomeration point of 20 to 75 μm occurs, it is considered that the resin agglomeration phenomenon is more serious than that when 1 resin agglomeration point of less than 20 μm occurs; similarly, when 1 resin agglomeration point larger than 75 μm occurs, it is considered that the resin agglomeration phenomenon is more serious than that when 1 resin agglomeration point smaller than 20 μm to 75 μm occurs.

For resin agglomerate points less than 20 microns in length, the difference between the values is less than or equal to 1, indicating no significant difference in resin agglomerate points less than 20 microns in length for a copper-free circuit board; the difference between the values is greater than 1, representing a significant difference (with significant technical difficulty) between the values of the resin agglomeration point for lengths less than 20 microns.

For resin agglomeration points between 20 and 75 microns in length, more than 1 is considered unacceptable, with a difference between the values of 1 or greater, representing a significant difference (with significant technical difficulties) between the values of the resin agglomeration points between 20 and 75 microns in length.

Resin agglomeration points greater than 75 microns must not occur, and the difference in value is greater than or equal to 1, indicating a significant difference (significant technical difficulty) between resin agglomeration point values greater than 75 microns in length.

The test results of examples and comparative examples according to the above method are as follows:

TABLE 13 results of characteristic test of the resin compositions of examples and articles thereof

TABLE 14 results of characteristic test of the resin compositions of examples and articles thereof

TABLE 15 characteristic test results of the resin compositions of examples and articles thereof

TABLE 16 results of characteristic test of the resin compositions of comparative examples and articles thereof

TABLE 17 results of characteristic tests of the resin compositions of comparative examples and articles thereof

TABLE 18 results of characteristic test of comparative example resin compositions and articles thereof

From the above test results, the following phenomenon can be observed.

By respectively comparing examples E1-E22 with comparative examples C1-C10 and C19-C20 in parallel, it can be confirmed that the substrate prepared by the invention can simultaneously achieve one, more or all of the technical effects of lower dielectric loss, better heat resistance after moisture absorption, less resin cluster aggregation points with the length of less than 20 micrometers, less resin cluster aggregation points with the length of 20 micrometers to 75 micrometers, more resin cluster aggregation points with the length of more than 75 micrometers, normal appearance of the surface of the copper-free circuit board and the like by using the combination of spherical silica with the long-chain alkyl imidazole compound, the sedimentation volume of which is less than or equal to 0.4 ml/g, and the particle size distribution D50 of which is less than or equal to 1.0 micrometer compared with the use of other silica, other fillers or other imidazole compounds.

By respectively comparing examples E1 to E22 with comparative examples C11 to C18 and C21 to C22 in parallel, it can be confirmed that, when the weight of the benzoxazine resin is 20 to 60 parts by weight, the weight of the epoxy resin is 5 to 40 parts by weight, the weight of the spherical silica having a sedimentation volume of 0.4 ml/g or less and a particle size distribution D50 of 1.0 μm or less is 120 to 240 parts by weight, and the weight of the long-chain alkyl imidazole compound is 0.5 to 1.6 parts by weight, the resin agglomeration problem due to the flowability or compatibility of the resin and silica or other fillers is not observed compared to 100 parts by weight of the maleimide resin, the resin is out of the numerical range compared to the technical solution in which the weight of each component is out of the numerical range (in which no silica or other fillers are added in comparative example C22), the substrate prepared by the invention can simultaneously achieve one, more or all technical effects of lower dielectric loss, better heat resistance after moisture absorption, higher tension of copper foil, less resin aggregation points with the length of less than 20 micrometers in a non-copper-containing circuit board, less resin aggregation points with the length of between 20 micrometers and 75 micrometers, less resin aggregation points with the length of more than 75 micrometers, normal appearance of the surface of the non-copper-containing circuit board and the like.

By comparing the embodiments E1 to E22 shown in the present invention with all the comparative examples C1 to C22, it can be confirmed that the substrate manufactured by the technical solution of the present invention can simultaneously achieve one, more or all of the technical effects of the heat resistance after moisture absorption, the number of the resin clusters having a length of less than 20 micrometers in the copper-free circuit board being less than or equal to 8, the number of the resin clusters having a length of 20 micrometers to 75 micrometers being less than or equal to 1, and the number of the resin clusters having a length of more than 75 micrometers being 0. On the contrary, the comparative examples C1 to C22, which did not use the technical solution of the present invention, could not achieve the above technical effects.

Further, it was confirmed that the copper-free circuit boards obtained in the other examples (E1 to E4, E6 to E22) can further simultaneously achieve heat resistance after moisture absorption, and that the number of resin clusters having a length of less than 20 μm in the copper-free circuit boards was 6 or less and the number of resin clusters having a length of 20 μm to 75 μm was 0, as compared with examples E5 and comparative examples C1 to C22. On the contrary, the above-mentioned technical effects cannot be achieved in the examples E5 and comparative examples C1 to C22.

In addition, it can be confirmed that the substrates obtained in the other examples (E1 to E4, E6 to E17, and E19 to E22) can further achieve the ultra-thin copper foil tensile force (2 micrometers) of 4.4lb/in or more, the heat resistance passing or dielectric loss after moisture absorption of 0.0075 or less, the resin cluster points of less than 20 micrometers in length of the copper-free circuit board of 6 or less, and the resin cluster points of between 20 micrometers and 75 micrometers in length of 0 simultaneously, by comparing the examples E5 and E18 with the comparative examples C1 to C22. On the contrary, the examples E5 and E18 and the comparative examples C1 to C22 could not achieve the above-mentioned technical effects.

The above embodiments are merely exemplary in nature and are not intended to limit the claimed embodiments or the application or uses of such embodiments. In this document, the term "exemplary" represents "as an example, instance, or illustration. Any exemplary embodiment herein is not necessarily to be construed as preferred or advantageous over other embodiments.

In addition, while at least one exemplary embodiment or comparative example has been presented in the foregoing detailed description, it should be appreciated that a vast number of variations are possible. It should also be appreciated that the embodiments described herein are not intended to limit the scope, applicability, or configuration of the claimed subject matter in any way. Rather, the foregoing implementations will provide those skilled in the art with a convenient road map for implementing the described embodiment or embodiments. Rather, various changes may be made in the function and arrangement of elements without departing from the scope defined in the claims, which includes known equivalents and all foreseeable equivalents at the time of filing this patent application.

Claims

1. A resin composition, comprising:

(A)100 parts by weight of a maleimide resin;

(B)20 to 60 parts by weight of a benzoxazine resin;

(C)5 to 40 parts by weight of an epoxy resin;

(D)120 to 240 parts by weight of silica, wherein the silica comprises spherical silica having a sedimentation volume of less than or equal to 0.4 ml/g and a particle size distribution D50 of less than or equal to 1.0 micron; and

(E)0.5 to 1.6 parts by weight of a long chain alkyl imidazole compound comprising octyl imidazole, undecyl imidazole, heptadecyl imidazole, or a combination thereof.

2. The resin composition according to claim 1, the maleimide resin includes 4,4 '-diphenylmethane bismaleimide, phenylmethane maleimide oligomer, m-phenylene bismaleimide, bisphenol a diphenylether bismaleimide, 3' -dimethyl-5, 5 '-diethyl-4, 4' -diphenylmethane bismaleimide, 4-methyl-1, 3-phenylene bismaleimide, 1, 6-bismaleimide- (2,2, 4-trimethyl) hexane, 2, 3-dimethyl-phenylmaleimide, 2, 6-dimethyl-phenylmaleimide, N-phenylmaleimide, maleimide resins containing aliphatic long chain structures, or combinations thereof.

3. The resin composition according to claim 1, wherein the benzoxazine resin comprises diaminodiphenyl ether type benzoxazine resin, alkenyl-containing benzoxazine resin, bisphenol a type benzoxazine resin, bisphenol F type benzoxazine resin, dicyclopentadiene benzoxazine resin, phenolphthalein type benzoxazine resin, phosphorus-containing benzoxazine resin, diamine type benzoxazine resin, or a combination thereof.

4. The resin composition of claim 1, wherein the settled volume is measured using the following solvents: butanone, toluene, dimethylacetamide, methanol, ethanol, ethylene glycol monomethyl ether, acetone, methyl isobutyl ketone, cyclohexanone, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide, propylene glycol methyl ether, or combinations thereof.

5. The resin composition according to claim 1, wherein the silica comprises spherical silica having a settled volume equal to 0 ml/g and a particle size distribution D50 of less than or equal to 1.0 μm.

6. The resin composition according to claim 1, wherein the benzoxazine resin is contained in an amount of 30 to 60 parts by weight, compared to 100 parts by weight of the maleimide resin.

7. The resin composition of claim 1, wherein the weight ratio of silica to total resin is between 0.75:1 and 1.5:1, and the total resin weight is the sum of the weight of all resins in the resin composition except silica and the long chain alkyl imidazole compound.

8. The resin composition of claim 1, further comprising a cyanate ester resin, a polyolefin resin, a small molecule vinyl compound, an acrylate resin, a phenol resin, a polyphenylene ether resin, a styrene maleic anhydride resin, a polyester resin, an amine curing agent, a polyamide resin, a polyimide resin, or a combination thereof.

9. The resin composition of claim 1, further comprising a flame retardant, an inorganic filler, a curing accelerator, a polymerization inhibitor, a coloring agent, a solvent, a toughening agent, a silane coupling agent, or a combination thereof.

10. The resin composition of claim 1, wherein the spherical silica having a settled volume of less than or equal to 0.4 ml/g and a particle size distribution D50 of less than or equal to 1.0 μm comprises silica available from Jiangsu-Gimmer powder technology GmbH under the trade name HM031BNJ, silica available from Jiangsu-Gimmer powder technology GmbH under the trade name HM052BYJ, silica available from HM072BNJ, silica available from HM102BNJ, or a combination thereof.

11. An article made from the resin composition according to any one of claims 1 to 10, wherein the article comprises a prepreg, a resin film, a laminate, or a printed circuit board.

12. The article according to claim 11, wherein the article has a dielectric loss of 0.0075 or less as measured at a frequency of 10GHz in accordance with the method of JIS C2565.

13. The article of claim 11, wherein the article does not burst when subjected to post-moisture pick-up heat resistance testing as described in IPC-TM-6502.6.16.1 and IPC-TM-6502.4.23.

14. The article of claim 11, wherein the article is prepared as a1 cm long strip sample without a copper circuit board, and wherein the number of resin agglomeration points in the sample having a length of less than 20 micrometers is less than or equal to 8 as measured by scanning electron microscopy.

15. The article of claim 11, wherein the article is prepared as a1 cm long strip sample without a copper circuit board, and wherein the number of resin agglomeration points between 20 and 75 microns in length in the sample is less than or equal to 1 as measured by scanning electron microscopy.

16. The article of claim 11, wherein the article is formed into a1 cm long sample without a copper circuit board and the number of resin agglomeration points greater than 75 microns in length in the sample is 0 as measured by scanning electron microscopy.

17. The article of claim 11, wherein the article is formed into a copper-free circuit board and visually observed for a surface appearance with no detail.