High-heat-resistance low-dielectric non-flowing prepreg and application thereof

Abstract

The invention discloses a high-heat-resistance low-dielectric non-flowing prepreg and application thereof. The prepreg comprises a curable resin insulating layer and a reinforcing material, the curable resin insulating layer comprises the following components in parts by weight: 10-50 parts of epoxy resin I; 20 to 80 parts of cyanate ester resin; 20 to 60 parts of a core-shell rubber premixed solution; 5 to 40 parts of cyclic polyolefin; the core-shell rubber premixed liquid is a mixed dispersion liquid of epoxy resin II, an organic solvent and core-shell rubber, and the content of the core-shell rubber is 10-50% in percentage by mass; the epoxy resin, the cyanate ester, the core-shell rubber premixed liquid and the cyclic polyolefin are matched, and the cyclic polyolefin is introduced to adjust the compatibility among the components and greatly improve the dielectric property, so that the resin composition with excellent low dielectric property, heat resistance, non-flowability and low water absorption is obtained; the method is used in the field of non-flowing prepregs with high heat resistance and low dielectric requirements.

Description

Technical Field

[0001] The invention relates to the technical field of electronic materials, and in particular to a high-heat-resistant and low-dielectric no-flow prepreg and application thereof. Background Art

[0002] With the rapid development of consumer electronic products, the requirements of electronic products for circuit boards are getting higher and higher, and a special circuit board-rigid-flex board came into being. Rigid-flex board has the advantages of both rigid board and flexible board. It can not only weld complex electronic components on rigid board, but also has the characteristics of flexible board that it is thin, foldable, bendable, and takes up little space, effectively reducing the volume of electronic products. No-Flow Prepreg for Rigid-Flex Board is a special adhesive material used in the preparation process of Rigid-Flex Board to tightly connect the rigid board and the flexible board through a specific pressing process. No-Flow Prepreg for Rigid-Flex Board usually refers to a semi-cured solid film prepared by impregnating epoxy resin adhesive with glass fiber cloth as a carrier, and then semi-curing treatment. It is characterized by the resin not flowing or having very low fluidity, and having certain adhesive characteristics, which meets the process requirements of rigid-flex printed circuit boards.

[0003] Prior art JP6354884 discloses a cyanate resin composition and a prepreg, which include a cyanate, a curing agent or a curing accelerator, silicon dioxide, and a core-shell rubber; Prior art CN102311614 discloses a resin composition and a semi-cured sheet made using the same, which include a biphenyl epoxy resin, a phenolic resin, and a core-shell rubber; Prior art CN102775734 discloses a halogen-free resin composition and a semi-cured sheet made using the same, which include a phosphorus-containing epoxy resin, a phenolic resin, a core-shell rubber, a macromolecular epoxy resin, a high thermal conductive filler, a curing agent, and an accelerator; In combination with the above-mentioned disclosed technologies, in order to reduce the fluidity of the resin, the prior art often uses a thermoplastic resin with high polarity, low glass transition temperature and high molecular weight in combination with a thermosetting epoxy resin, resulting in poor compatibility of the resin composition, deviation in dielectric properties and low glass transition temperature, and low heat resistance and adhesion.

[0004] Therefore, the present invention provides a high heat-resistant and low dielectric no-flow prepreg and its application to realize a low-flow prepreg material with high heat resistance, low dielectric, high adhesion and excellent processability. Summary of the invention

[0005] The object of the present invention is to provide a high heat-resistant and low dielectric no-flow prepreg and its application, so as to realize a low-flow prepreg material with high heat resistance, low dielectric, high adhesion and excellent processability.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] A high heat-resistant and low dielectric no-flow prepreg, comprising: a curable resin insulating layer and a reinforcing material;

[0008] In parts by weight, the curable resin insulation layer is a curable resin composition layer, and the curable resin composition includes the following components:

[0009] (A) epoxy resin I: 10-50 parts;

[0010] (B) cyanate resin: 20-80 parts;

[0011] (C) core-shell rubber premix: 20-60 parts;

[0012] (D) cyclic polyolefin: 5-40 parts;

[0013] The core-shell rubber premix is ​​a mixed dispersion of epoxy resin II, organic solvent and core-shell rubber, wherein the content of the core-shell rubber is 10%-50% by mass percentage.

[0014] Preferably, the content of the core-shell rubber in the core-shell rubber premix is ​​20%-40%.

[0015] For example, the content of the core-shell rubber in the core-shell rubber premix is ​​20%, 25%, 30%, 35% or 40%.

[0016] For example, the core-shell rubber premix is ​​MX-217 manufactured by KANEKA.

[0017] Preferably, the epoxy resin I and the epoxy resin II both contain at least two epoxy groups in one molecular structure.

[0018] Preferably, the epoxy resin I and the epoxy resin II are the same or different.

[0019] Further preferably, the epoxy resin I and the epoxy resin II are the same. When the two have the same components, the core-shell rubber is better dispersed in the matrix epoxy resin and cyanate resin system, further reducing the resin fluidity and achieving more excellent comprehensive performance.

[0020] The epoxy resin I and epoxy resin II are respectively selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, tetraphenylethane epoxy resin, triphenylmethane epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, dicyclopentadiene epoxy resin, isocyanate epoxy resin, aralkyl linear phenolic epoxy resin, bisphenol A phenolic epoxy resin, polyphenylene ether modified epoxy resin, alicyclic epoxy resin, glycidyl amine epoxy resin, glycidyl ester epoxy resin, phosphorus-containing epoxy resin, nitrogen-containing epoxy resin, and multifunctional epoxy resin.

[0021] Further preferably, the epoxy resin I and the epoxy resin II are selected from at least one of biphenyl epoxy resin, naphthalene epoxy resin, dicyclopentadiene epoxy resin, polyphenylene ether modified epoxy resin and phosphorus-containing epoxy resin.

[0022] For example, the epoxy resin I and the epoxy resin II are selected from NC-3000, NC-2000, EPPN-500, NC-7000, NC-3500, XD-1000, etc. manufactured by Nippon Kayaku, and HP-4032SS, HP-4770, EXA-4750, HP-4700, HP-4710, HP-6000, HP-9500, HP-9540, HP-9900 or EXA-7311, etc. manufactured by DIC.

[0023] Preferably, the cyanate resin is selected from at least one of bisphenol A cyanate resin, bisphenol F cyanate resin, bisphenol E cyanate resin, bisphenol M cyanate resin, DCPD cyanate resin, naphthalene cyanate resin, phenolic cyanate resin and biphenyl cyanate resin.

[0024] Preferably, the cyanate ester resin is a mixture of a monomer and a prepolymer or a prepolymer.

[0025] Preferably, the shell part of the core-shell rubber is selected from at least one of methacrylates, acrylates, and styrenes; the core part is selected from at least one of butadiene rubber, acrylate rubber, silicone rubber, NBR rubber, and SBR rubber.

[0026] Preferably, the average particle size of the core-shell rubber is 0.1 micrometer to 3 micrometers.

[0027] Preferably, the curable resin insulation layer does not contain phenoloxy resin.

[0028] Preferably, the cyclic polyolefin is selected from one of unmodified cyclic polyolefin and modified cyclic polyolefin.

[0029] The modified cyclic polyolefin is selected from at least one of epoxy-modified cyclic polyolefin, hydroxy-modified cyclic polyolefin, anhydride-modified cyclic polyolefin and ester-modified cyclic polyolefin.

[0030] More preferably, the cyclic polyolefin is a norbornene compound or a modified product thereof.

[0031] For example, the cyclic polyolefin is TOPAS6013, TOPAS8007, TOPAS6015 or TOPAS5013 manufactured by Polyplastics.

[0032] In the above technical solution, the curable resin insulating layer also includes inorganic fillers, and the content of inorganic fillers is 30-150 parts.

[0033] The inorganic filler is selected from at least one of silicon dioxide, aluminum hydroxide, aluminum oxide, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, boehmite, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder.

[0034] More preferably, the inorganic filler is spherical silica that has been surface treated with an aniline silane coupling agent.

[0035] Preferably, the structural formula of the phenylaminosilane coupling agent is: Wherein, R is a C1-C6 straight chain alkylene group, and X is a methoxy group or an ethoxy group.

[0036] In the above technical solution, the curable resin insulation layer further includes a catalyst, and the catalyst is 0.01-5 parts.

[0037] The catalyst is at least one of an imidazole catalyst, a pyridine catalyst, and an organic metal salt catalyst.

[0038] Further preferably, the catalyst is selected from at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, modified imidazole and zinc octoate.

[0039] Preferably, the reinforcing material is glass fiber cloth, and the glass fiber cloth is surface treated with a silane coupling agent.

[0040] Preferably, the glass fiber cloth is a spread cloth or a flat cloth; more preferably, the glass fiber cloth is an E glass fiber cloth, an S glass fiber cloth or a Q glass fiber cloth.

[0041] In addition, when the reinforcing material is glass fiber cloth, the glass fiber cloth generally needs to be chemically treated to improve the bonding between the resin composition and the interface of the glass fiber cloth. The main method of the chemical treatment is coupling agent treatment. The coupling agent used is preferably an epoxy silane coupling agent or an amino silane coupling agent, so that the reinforcing material has good water resistance and heat resistance.

[0042] The present application also claims to protect the use of the above-mentioned high heat-resistant and low dielectric no-flow prepreg in rigid-flexible printed circuit boards.

[0043] The specific preparation method of the above-mentioned semi-cured sheet is as follows: add the curable resin composition into a mixing kettle, add a diluent to adjust the solid content to 40-70%, stir evenly to form a glue solution, immerse the reinforcing material in the glue solution, and then bake the impregnated reinforcing material at 100-200°C for 3-10 minutes to obtain the high heat-resistant and low dielectric non-flowing semi-cured sheet provided by the present invention.

[0044] Due to the application of the above technical solution, the present invention has the following beneficial effects compared with the prior art:

[0045] The present invention combines epoxy resin, cyanate ester and core-shell rubber premix and cyclic polyolefin, wherein the cyclic polyolefin is introduced to adjust the compatibility between the components and greatly improve the dielectric properties, thereby obtaining a resin composition with excellent low dielectric, heat resistance, non-flowability and low water absorption, which is used in the field of non-flowable prepregs with high heat resistance and low dielectric requirements. DETAILED DESCRIPTION

[0046] In order to have a clearer understanding of the technical features, purposes and effects of the present invention, a specific implementation scheme is now described in detail.

[0047] The present invention is further described below in conjunction with the examples, but the present invention is not limited to the following examples. The implementation conditions used in the examples can be further adjusted according to the different requirements of specific use, and the implementation conditions not indicated are conventional conditions in the industry. The technical features involved in each embodiment of the present invention can be combined with each other as long as they do not conflict with each other.

[0048] Example 1

[0049] The present embodiment is a curable resin composition, which includes, by weight: 40 parts of epoxy resin, 70 parts of cyanate resin, 30 parts of core-shell rubber premix, 20 parts of cyclic polyolefin, 60 parts of spherical silica, 0.1 parts of 2-methylimidazole, and 0.1 parts of zinc octanoate.

[0050] Example 2

[0051] The present embodiment is a curable resin composition, which includes, by weight: 40 parts of epoxy resin, 70 parts of cyanate resin, 20 parts of core-shell rubber premix, 20 parts of cyclic polyolefin, 60 parts of spherical silica, 0.1 parts of 2-methylimidazole, and 0.1 parts of zinc octoate.

[0052] Example 3

[0053] The present embodiment is a curable resin composition, which includes, by weight: 30 parts of epoxy resin, 60 parts of cyanate resin, 30 parts of core-shell rubber premix, 40 parts of cyclic polyolefin, 60 parts of spherical silica, 0.1 parts of 2-methylimidazole, and 0.1 parts of zinc octoate.

[0054] Example 4

[0055] The present embodiment is a curable resin composition, which includes, by weight: 30 parts of epoxy resin, 60 parts of cyanate resin, 40 parts of core-shell rubber premix, 30 parts of cyclic polyolefin, 60 parts of spherical silica, 0.1 parts of 2-methylimidazole, and 0.1 parts of zinc octanoate.

[0056] Comparative Example 1

[0057] This embodiment is a curable resin composition, which includes, by weight: 40 parts of epoxy resin, 70 parts of cyanate resin, 30 parts of core-shell rubber premix, 60 parts of spherical silica, 0.1 parts of 2-methylimidazole, and 0.1 parts of zinc octoate.

[0058] Comparative Example 2

[0059] The present embodiment is a curable resin composition, which includes, by weight: 40 parts of epoxy resin, 70 parts of cyanate resin, 20 parts of cyclic polyolefin, 20 parts of phenoloxy resin, 60 parts of spherical silica, 0.1 parts of 2-methylimidazole, and 0.1 parts of zinc octoate.

[0060] Comparative Example 3

[0061] This embodiment is a curable resin composition, which includes, by weight: 30 parts of epoxy resin, 60 parts of cyanate resin, 40 parts of phenolic resin, 60 parts of spherical silica, 0.1 parts of 2-methylimidazole, and 0.1 parts of zinc octoate.

[0062] Comparative Example 4

[0063] This embodiment is a curable resin composition, which includes, by weight: 62.5 parts of epoxy resin, 70 parts of cyanate resin, 7.5 parts of core-shell rubber, 20 parts of cyclic polyolefin, 60 parts of spherical silica, 0.1 parts of 2-methylimidazole, and 0.1 parts of zinc octoate.

[0064] The components and addition amounts of Examples 1-4 and Comparative Examples 1-4 are shown in Table 1 below.

[0065] Table 1

[0066] Components Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Epoxy resin 40 40 30 30 40 40 30 62.5 Cyanate ester resin 70 70 60 60 70 70 60 70 Core-shell rubber premix 30 20 30 40 30 0 0 0 Cyclic polyolefins 20 20 40 30 0 20 0 20 Phenoloxy resin 0 0 0 0 0 20 40 0 Spherical silica 60 60 60 60 60 60 60 60 2-Methylimidazole 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Zinc Octanoate 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Core-shell rubber 0 0 0 0 0 0 0 7.5

[0067] The raw material manufacturers and models of each component used in Examples 1-4 and Comparative Examples 1-4 are shown in Table 2 below.

[0068] Table 2

[0069] Components Brand Epoxy resin Nippon Kayaku, NC3000H Cyanate ester resin Lonza, phenolic cyanate resin Core-shell rubber premix Kaneka, MX217 Cyclic polyolefins Polyplastics, TOPAS6013 Phenoloxy resin Nippon Steel, YP-50 Core-shell rubber Made by Dow, PraraloidTMS-2670J Spherical silica Lianrui New Materials, D100=13um

[0070] The above-mentioned embodiments and comparative examples also disclose a semi-cured sheet, comprising glass fiber cloth as a reinforcing material and a curable resin composition coated on the glass fiber cloth by an impregnation method; wherein the glass fiber cloth is a fiber-spread cloth pre-treated with an epoxy silane coupling agent.

[0071] Specifically, the components of the resin compositions of the above-mentioned Examples 1-4 and Comparative Examples 1-4 were dissolved in xylene, stirred and mixed, and then diluted into a glue solution with a solid content of 55wt%; the E glass fiber cloth 1078 used as a reinforcing material was pretreated with an epoxy silane coupling agent, immersed in the above-mentioned glue solution, taken out after infiltration, placed in a 160°C blast drying oven, and baked for 3-6 minutes to obtain a semi-cured sheet.

[0072] The above embodiment and comparative example also disclose a laminate, which is prepared by the following method:

[0073] Take two of the above-mentioned semi-cured sheets, cut them into 300×300mm, and stack them into a composite sheet with a certain stacking structure. Then, place a low-profile electrolytic copper foil with a thickness of 12 microns on both sides of the composite sheet, place it in a vacuum hot press, and hot press it for 1.5 hours at a pressure of 1.5 MPa and a temperature of 220°C to obtain a copper-clad laminate.

[0074] The above-mentioned embodiments and comparative examples also disclose an insulating board, comprising at least one of the above-mentioned prepreg sheets.

[0075] The above embodiments and comparative examples also disclose an insulating film, including a carrier film and the above resin composition coated thereon.

[0076] The above-mentioned embodiment and comparative example also disclose a circuit substrate, including a prepreg sheet mentioned above, which is prepared by a conventional preparation method in the prior art, and will not be described in detail here.

[0077] The performance tests were conducted on the prepregs obtained in the above Examples 1-4 and Comparative Examples 1-4 and the copper-clad laminates pressed therefrom, respectively. The test results are shown in Table 3 below.

[0078] Table 3

[0079]

[0080] The properties of the copper-clad laminates prepared in the above examples and comparative examples were tested as follows:

[0081] (1) Glue overflow: measured according to IPC-TM650, 2.3.17.2 method;

[0082] (2) CVL adhesion: Sample width 10 mm, tested using a peel force tester;

[0083] (3) Powder loss rate: The prepreg sheet is 10 cm × 10 cm in size. Use a utility knife to score 20 times before calculating the weight loss.

[0084] (4) Tg: DMA, heating rate 10°C / min, frequency 10 Hz;

[0085] (5) Dk and Df: Dielectric properties at 10 GHz using the flat plate method in accordance with IPC-TM-650, 2.5.5.9;

[0086] (6) Peel strength: According to the "after thermal stress" experimental conditions in IPC-TM-650, method 2.4.8, the peel strength of the metal cover layer was tested;

[0087] (7) Internal substrate quality: The internal substrate quality was observed under a microscope. When there was no resin agglomeration within an area of ​​300 mm × 300 mm, it was indicated as 0. When there was resin agglomeration, it was indicated as ╳.

[0088] In summary, the present invention combines epoxy resin, cyanate ester and core-shell rubber premix and cyclic polyolefin, wherein the cyclic polyolefin is introduced to adjust the compatibility between the components and greatly improve the dielectric properties, thereby obtaining a resin composition with excellent low dielectric, heat resistance, non-flowability and low water absorption, which is used in the field of non-flowable semi-cured sheets with high heat resistance and low dielectric requirements.

[0089] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A high heat-resistant and low dielectric no-flow prepreg, characterized in that: include: Curable resin insulation layer and reinforcement material; In parts by weight, the curable resin insulation layer is a curable resin composition layer, and the curable resin composition includes the following components: (A) epoxy resin I: 10-50 parts; (B) cyanate resin: 20-80 parts; (C) core-shell rubber premix: 20-60 parts; (D) cyclic polyolefin: 5-40 parts; The core-shell rubber premix is ​​a mixed dispersion of epoxy resin II, organic solvent and core-shell rubber, wherein the content of the core-shell rubber is 10%-50% by mass percentage.

2. The high heat-resistant and low dielectric no-flow prepreg according to claim 1, characterized in that: The epoxy resin I and the epoxy resin II both contain at least two epoxy groups in one molecular structure.

3. The high heat-resistant and low dielectric no-flow prepreg according to claim 2, characterized in that: The epoxy resin I and epoxy resin II are the same or different, and are respectively selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, tetraphenylethane epoxy resin, triphenylmethane epoxy resin, biphenyl epoxy resin, naphthalene epoxy resin, dicyclopentadiene epoxy resin, isocyanate epoxy resin, aralkyl linear phenolic epoxy resin, bisphenol A novolac epoxy resin, polyphenylene ether modified epoxy resin, alicyclic epoxy resin, glycidyl amine epoxy resin, glycidyl ester epoxy resin, phosphorus-containing epoxy resin, nitrogen-containing epoxy resin, and multifunctional epoxy resin.

4. The high heat-resistant and low dielectric no-flow prepreg according to claim 1, characterized in that: The cyanate resin is selected from at least one of bisphenol A cyanate resin, bisphenol F cyanate resin, bisphenol E cyanate resin, bisphenol M cyanate resin, DCPD cyanate resin, naphthalene cyanate resin, phenolic cyanate resin and biphenyl cyanate resin.

5. The high heat-resistant and low dielectric no-flow prepreg according to claim 1, characterized in that: The shell part of the core-shell rubber is selected from at least one of methacrylates, acrylates and styrenes; the core part is selected from at least one of butadiene rubber, acrylate rubber, silicone rubber, NBR rubber and SBR rubber.

6. The high heat-resistant and low dielectric no-flow prepreg according to claim 1, characterized in that: The average particle size of the core-shell rubber is 0.1 micrometer to 3 micrometers.

7. The high heat-resistant and low dielectric no-flow prepreg according to claim 1, characterized in that: The curable resin insulating layer does not contain phenoloxy resin.

8. The high heat-resistant and low dielectric no-flow prepreg according to claim 1, characterized in that: The cyclic polyolefin is selected from unmodified cyclic polyolefin or modified cyclic polyolefin.

9. The high heat-resistant and low dielectric no-flow prepreg according to claim 1, characterized in that: The reinforcing material is glass fiber cloth, and the glass fiber cloth is surface treated with a silane coupling agent.

10. An application of a high heat-resistant and low dielectric no-flow prepreg, characterized in that: The application of the high heat-resistant and low dielectric no-flow prepreg described in any one of claims 1 to 9 in a rigid-flexible printed circuit board.

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