POLYPHENOL-MODIFIED HYDROCARBON COMPOSITION-BASED PREPREG AND COPPER CLAD LAMINATE PREPARED THEREFROM

Abstract

The present disclosure relates to a polyphenol-modified hydrocarbon composition-based prepreg and a copper clad laminate prepared therefrom. The present disclosure uses polyarylether or polyolefin resin modified with hydroxyl end, amino end or mercapto end as the matrix resin and epoxy resin as the main curing agent to construct a hydrocarbon composition with excellent dielectric properties.

Claims

1. A polyphenol-modified hydrocarbon composition-based prepreg, wherein being prepared by the following steps: S1, soaking a reinforced material with 0.1˜80 mg/mL polyphenol aqueous solution, air-drying in a non-inert atmosphere and under ultraviolet light for 5˜360 min such that a product is obtained by drying, namely, the reinforced material with polyphenol on a surface denoted as polyphenol @ reinforced material; S2, adding 0.1˜25 wt/v % filler to 0.1˜80 mg/mL polyphenol aqueous solution, stirring to dispense evenly in the non-inert atmosphere and under irradiating by ultraviolet light; and then performing filtering, washing, and drying after soaking for 5˜720 min, such that a product is obtained, namely, the filler with polyphenol on a surface is denoted as polyphenol @ filler; S3, preparing a uniform dispersion of a hydrocarbon composition with a solid content of 35˜75 wt/v %, and soaking the polyphenol @ reinforced material in the uniform dispersion, and baking and drying to obtain the prepreg, the polyphenol is a mixture of one or more of plant polyphenols with catechol or pyrogallol structure in a molecular formula, a pH value of the polyphenol aqueous solution is between 4.5 and 9.0, and the non-inert atmosphere is an atmosphere containing oxygen, where a content of oxygen in the non-inert atmosphere is ≥3 v/v %, a wavelength of the ultraviolet light is ≤340 nm, an intensity of the ultraviolet light is ≥1 mW/cm.sup.2, and a ambient temperature during ultraviolet light irradiation is ≤50° C., a distance between an ultraviolet light source and an irradiated object is ≤100 cm; the hydrocarbon composition comprises six types components such as end-group-modified hydrocarbon polymer, primary curing agent, secondary curing agent, curing accelerator, polyphenol @ filler and flame retardants.

2. The polyphenol-modified hydrocarbon composition-based prepreg according to claim 1, wherein: in step S1, the reinforced material is selected from a group consisting of 106, 1080, 2116 and 7628 electronic grade alkali-free glass fiber, and fluorine resin fiber woven cloth, the polyphenol in the polyphenol @ reinforced material accounts for 0.03-1.0 wt % of a mass of the reinforced material.

3. The polyphenol-modified hydrocarbon composition-based prepreg according to claim 1, wherein: in step S2, the filler comprises an organic filler, and the organic filler is a mixture of one or more selected from a group consisting of ultra-high molecular polyethylene fiber, Kevlar fiber, fluororesin, polyimide and derivatives thereof, or a mixture of some thereof; a content of the filler is 1-20 wt % of the hydrocarbon composition, and the polyphenol in the polyphenol @ filler accounts for 0.03-1.0 wt % of a mass of the filler.

4. The polyphenol-modified hydrocarbon composition-based prepreg according to claim 1, wherein: in step S3, the hydrocarbon polymer is a mixture of one or more selected from a group consisting of polyarylether, polyolefin and derivatives thereof, the end group is one or more selected from a group consisting of an amine group, a hydroxyl group and a sulfhydryl group, and the end-group-modified hydrocarbon polymer accounts for 4-25 wt % of the hydrocarbon composition.

5. The polyphenol-modified hydrocarbon composition-based prepreg according to claim 1, wherein: in step S3, the primary curing agent is epoxy resin, specifically a mixture of one or more selected from a group consisting of bisphenol-A epoxy resin, hydrogenated bisphenol-A epoxy resin, bisphenol-S epoxy resin, bisphenol-F epoxy resin, dicyclopentadiene epoxy resin, naphthalene ring structure epoxy resin, biphenyl epoxy resin, heterocyclic epoxy resin, novolac epoxy resin, silicone epoxy resin, multifunctional epoxy resin, aliphatic epoxy resin, cyanate ester modified epoxy resin and derivatives thereof, the primary curing agent accounts for 15˜68 wt % of the hydrocarbon composition; the secondary curing agent is a mixture of one or more selected from a group consisting of active polyester, glycol, polyol, diamine, polyamine, dithiol, polythiol, diphenol, polyphenol, phenolic resin, cyanate ester resin, acid anhydride, dicyandiamide, benzoxazine and derivatives thereof, the secondary curing agent accounts for 0.1-12 wt % of the hydrocarbon composition; the curing accelerator is a mixture of one or more selected from a group consisting of tertiary amine compounds, imidazole compounds, phosphine compounds, substituted urea compounds, phenol compounds and boron trifluoride amine complexes; the curing accelerator accounts for 0.02˜5.0 wt % of the primary curing agent; the flame retardants is mixture of one or more selected from a group consisting of aluminum magnesium flame retardant, boron zinc flame retardant, molybdenum tin flame retardant, bromine flame retardant, antimony trioxide, phosphorus flame retardant and nitrogen flame retardant and derivatives thereof, the flame retardant accounts for 1-50 wt % of the hydrocarbon composition.

6. The polyphenol-modified hydrocarbon composition-based prepreg according to claim 1, wherein: in step S3, a solvent of the uniform dispersion is a mixture of one or more selected from a group consisting of an organic solvent that can make the hydrocarbon composition evenly dispersed.

7. The polyphenol-modified hydrocarbon composition-based prepreg according to claim 1, wherein: in step S3, the baking and drying is divided into two stages: a baking and drying temperature in a first stage is 30˜110° C., and the baking drying temperature in a second stage is 110˜180° C.

8. A copper clad laminate prepared by using a polyphenol-modified hydrocarbon composition-based prepreg according to claim 1, wherein being prepared by the following steps: overlapping and laminating the prepreg and a copper foil coated in a surface of the prepreg to obtain the copper clad laminate, where a number of prepregs is 1, a number of copper foils is 1 or 2, a lamination temperature is 130˜280° C., and a lamination pressure is 80˜130 kg/cm.sup.2, a lamination duration is 5 min˜480 min.

Description

DESCRIPTION OF EMBODIMENTS

[0028] The following examples further describe in detail a hydrocarbon composition-based prepreg modified by polyphenol and a high-frequency copper clad laminate prepared by using the prepreg provided by the present disclosure. However, these examples are only provided for illustration, not for limiting the present disclosure.

Examples 1˜5

[0029] The 1080 glass fiber cloth may be soaked in a 40 mg/mL polyphenol aqueous solution for 30 minutes and simultaneously irradiated with ultraviolet light. The wavelength of the ultraviolet light is 26 0nm, the intensity of the ultraviolet light is 10 mW/cm.sup.2, the ambient temperature is 30° C., and the distance from the ultraviolet light source to the object to be irradiated is 30 cm, and then the 1080 glass fiber cloth with a surfaced modified with polyphenol may be taken out, which is recorded as “polyphenol @1080 glass fiber cloth”. The filler may be stirred and immersed in a 40 mg/mL polyphenol aqueous solution for 30 minutes and simultaneously irradiated with ultraviolet light. The wavelength of ultraviolet light was 260 nm, the intensity of ultraviolet light is 10 mW/cm.sup.2, and the ambient temperature is 30° C. The distance between the ultraviolet light source and the irradiated objects is 10 cm. After filtering, washing, and drying, a filler with polyphenol modified on the surface may be obtained, which is denoted as “polyphenol @ filler”. The end-hydroxyl—modified hydrocarbon polymer, the primary curing agent, the secondary curing agent, the curing accelerator, “polyphenol@filler” and flame retardant uniformly may be dispersed in toluene, and the solid content of the dispersion is controlled to 60 wt %, Then “polyphenol @ 1080 glass fiber cloth” may be soaked in the uniform dispersion, and the prepreg can be obtained after baking. The baking and drying temperature in the first stage may be 60˜100° C.; the baking and drying temperature in the second stage may be 100˜170° C. Eight prepregs may be taken and stacked together, 1 oz copper foils may be attached on both sides, and laminated under vacuum, pressure, and high temperature for several hours to obtain a copper clad laminate. The specific formula is shown in the table below.

TABLE-US-00001 Materials Exp. 1 Exp. 2 Exp. 3 Exp. 4 Exp. 5 Polyphenol Poly- Poly- Poly- Poly- Poly- tannins tannins tannic acid tannic acid tannins Inorganic SiO.sub.2 55 40 60 22 55 filler Al.sub.2O.sub.3 35 35 40 10 0 BN 0 5 0 20 0 Organic PTFE Pre-sintered 8 20 0 18 35 filler material(Shandong Dongyue) Krasol HLBH-9200 7 10 15 13 16 Hydrogenated hydroxyl end polyolefin (Clayville) End- Krasol (Clayville) modified Hydro- Krasol HLBH-9200 0 8 0 15 13 carbon Hydrogenated hydroxyl end polymer polyolefin (Clayville) Sabic SA-90 23 12 10 0 0 hydroxyl-terminated modified polyphenylene ether Primary Bisphenol-A epoxy resin 115 60 20 95 55 curing Brominated bisphenol-A 0 47 85 10 50 agent epoxy resin (Dow DER 530A80) Secondary Dicyandiamide 7 5 4 5 4 curing Novolac resin (Moitu) 3 5 6 6 6 agent Curing 2-phenylimidazole 0.10 0.10 0 0.10 0.05 accelerator 2-ethyl-4-methylimidazole 0.20 0.20 0.30 0.20 0.25 Flame Composition of 25 15 0 10 0 retardant decabromodiphenylethane and antimony oxide (3:1) Mg(OH).sub.2 (Albemarle, US) 10 0 0 0 20 Melamine pyrophosphate 0 20 0 25 10

Comparative Example 1

[0030] Comparative Example 1 adopted 1080 glass fiber cloth and filler that are not modified by polyphenol, and the other processes are the same as in Example 1.

Comparative Example 2

[0031] Comparative Example 2 adopted polyphenol-modified filler instead of polyphenol-modified 1080 glass fiber cloth, and other processes are the same as in Example 1.

[0032] Among them, the test performance of prepregs and copper clad laminates are as follows.

TABLE-US-00002 Cmp. Cmp. Product Parameter Exp. 1 Exp. 2 Exp. 3 Exp. 4 Exp. 5 Exp. 1 Exp. 2 Pre- Surface Flat Flat Flat Flat Flat Flat Flat preg Toughness Moderate Moderate Moderate Moderate Moderate Moderate Moderate Surface Moderate Moderate Moderate Moderate Moderate Moderate Moderate adhesion Copper Dielectric constant 4.20 3.99 4.44 3.95 3.81 4.18 4.20 clad Dielectric loss 0.010 0.009 0.0010 0.009 0.009 0.012 0.0013 laminate factor Tg (° C.) 145 144 147 144 146 147 144 Minimum >55 >55 >55 >55 >55 45 50 breakdown voltage (kV) Peel strength 1.90 1.81 1.85 1.84 1.74 1.83 1.82 (N/mm) Dip solder >10 min >10 min >10 min >10 min >10 min ~2 min ~4 min resistance (288° C.) Water 0.27 0.22 0.26 0.25 0.24 0.45 0.43 absorption (%) Combustibility V0 V0 V0 V0 V0 V0 V0 Drillability Good Good Good Good Good Fair Good Note: the above were average values; dielectric properties were measured by IPC TM-650 2.5.5.5 standard at 1 GHz frequency; breakdown voltage were measured by IPC TM-650 2.5.6 standard; peel strength were measured by IPC TM-650 2.4.8 standard.

[0033] As shown in Comparative Example 1, if the surface of the fiberglass cloth and the filler are not modified by polyphenol, the matrix resin cannot be directly bonded to the surface of the fiberglass cloth and the filler, and the adhesion among the three is not strong. The copper clad laminate has poor resistance to immersion soldering and drilling. If only polyphenol is applied to the surface of the filler alone, as shown in Comparative Example 2, the bonding force of the components in the copper clad laminate matrix is improved, and its solder dip resistance and drilling resistance are improved, but the degree is not obvious. Only the surfaces of the fiberglass cloth and the filler are modified with polyphenol, as shown in Examples 1 to 5, since polypolyphenols can participate in the crosslinking and curing reaction of end-group modified polyarylethers or polyolefins and epoxy resins, the matrix resin will directly bond to the surface of the fiberglass cloth and fillers, such that the bonding force among the components in the copper clad laminate matrix can further be maximized to promote and improve the solder resistance and drilling performance of the plates. At the same time, due to the improvement of the uniformity of the plates, the reduction of free volume and defects in the matrix resin, the water absorption and dielectric loss of the copper clad laminate also have a certain degree of decline.

[0034] The preparation conditions in the present disclosure is mild, the production cost is low, and it is easy for production in batch and large-scale, with a good industrial production basis and broad application prospects.