RESIN COMPOSITION, INSULATING RESIN FILM AND USE THEREOF

Abstract

Resin composition, insulating resin film and use thereof. The resin composition comprises the following components in parts by mass: 50-90 parts of a hydrogenated hydrocarbon resin and 10-50 parts of a benzocyclobutene resin; the benzocyclobutene resin comprises at least one structural unit A and at least one structural unit B. The hydrogenated hydrocarbon resin and the benzocyclobutene resin with a specific structure are both total-hydrocarbon structures, having low dielectric constant Dk, dielectric loss tangent Df, and water absorption rate. The benzocyclobutene resin can be thermally cured to obtain the high cross-linking density, high glass transition temperature, and excellent heat resistance. The resin composition and the insulating resin film prepared therewith have ultra-low dielectric constant and loss tangent, excellent dielectric properties, heat resistance, damp heat resistance, adhesion strength, and excellent mechanical properties such as flexibility, satisfying the performance requirements of electronic components being high frequency, high speed, and high integration.

Claims

1. A resin composition, comprising the following components in parts by mass: 50-90 parts of a hydrogenated hydrocarbon resin and 10-50 parts of a benzocyclobutene resin; the benzocyclobutene resin comprises at least one structural unit A and at least one structural unit B; the structural unit A has a structure as shown in formula I: ##STR00016## R.sub.1 is vinylidene and/or ethylidene; the structural unit B has a structure as shown in formula II: ##STR00017## R.sub.2 is vinyl, ethyl and/or phenyl.

2. The resin composition according to claim 1, wherein the hydrogenated hydrocarbon resin comprises a fully hydrogenated hydrocarbon resin and/or a partially hydrogenated hydrocarbon resin.

3. The resin composition according to claim 1, wherein the hydrogenated hydrocarbon resin comprises any one or a combination of at least two of a hydrogenated styrene-butadiene copolymer, a maleic anhydride grafted hydrogenated styrene-butadiene copolymer, and hydrogenated polybutadiene.

4. The resin composition according to claim 1, wherein the hydrogenated hydrocarbon resin has a number average molecular mass of 3000-200000.

5. The resin composition according to claim 1, wherein the structural unit A of the benzocyclobutene resin has a molar percentage of more than or equal to 5%.

6. The resin composition according to claim 1, wherein the structural unit B of the benzocyclobutene resin has a molar percentage of 15-90%.

7. The resin composition according to claim 1, wherein the benzocyclobutene resin further comprises structural unit C, and the structural unit C has a structure as shown in formula IIIA and/or a structure as shown in formula IIIB: ##STR00018##

8. The resin composition according to claim 7, wherein the structural unit C of the benzocyclobutene resin has a molar percentage of less than or equal to 40%.

9. The resin composition according to claim 1, wherein the benzocyclobutene resin has a number average molecular mass of 1000-20000.

10. The resin composition according to claim 1, wherein the resin composition further comprises an initiator.

11. The resin composition according to claim 1, wherein the resin composition further comprises a filler.

12. The resin composition according to claim 1, wherein the resin composition further comprises a flame retardant.

13. An insulating resin film, wherein a material of the insulating resin film comprises the resin composition according to claim 1.

14. A resin-coated copper foil, wherein the resin-coated copper foil comprises a copper foil layer and a resin layer, and a material of the resin layer comprises the resin composition according to claim 1.

15. A prepreg, wherein the prepreg comprises a reinforcing material and the resin composition according to claim 1 adhered on the reinforcing material.

16. The prepreg according to claim 15, wherein the resin composition is adhered on the reinforcing material by impregnation and drying.

17. A metal foil clad laminate, wherein the metal foil clad laminate comprises the insulating resin film according to claim 13.

18. A metal foil clad laminate, wherein the metal foil clad laminate comprises the resin-coated copper foil according to claim 14.

19. A metal foil clad laminate, wherein the metal foil clad laminate comprises the prepreg according to claim 15.

20. A printed circuit board, wherein the printed circuit board comprises the insulating resin film according to claim 13.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0086] FIG. 1 shows an infrared spectrum of the benzocyclobutene resin CH-BCB2 provided in Preparation Example 1; and

[0087] FIG. 2 shows a GPC spectrum of the benzocyclobutene resin CH-BCB2 provided in Preparation Example 1.

DETAILED DESCRIPTION

[0088] The technical solutions of the present application are further described below through embodiments. It should be apparent to those skilled in the art that the embodiments are merely used for a better understanding of the present application and should not be regarded as a specific limitation on the present application.

[0089] In an embodiment, the benzocyclobutene resin is obtained by subjecting a hydrocarbon resin and 4-halogen benzocyclobutene

##STR00009##

to coupling reaction; the hydrocarbon resin comprises polybutadiene or a styrene-butadiene copolymer, which comprises a structural unit

##STR00010##

formed by butadiene 1,2-polymerization; Hal is a halogen, which may be, for example, Cl, Br or I.

[0090] In an embodiment, the Hal is Br, which means that a raw material is 4-bromobenzocyclobutene

##STR00011##

[0091] In an embodiment, the coupling reaction is carried out in the presence of a palladium catalysis system.

[0092] In an embodiment, the palladium catalysis system comprises a palladium catalyst and an organophosphine ligand.

[0093] In an embodiment, the palladium catalyst is palladium acetate and the organophosphine ligand is tris(o-methylphenyl)phosphine.

[0094] In an embodiment, the coupling reaction is carried out in the presence of an acid binding agent.

[0095] In an embodiment, the acid binding agent comprises an organic base, more preferably triethylamine.

[0096] In an embodiment, the coupling reaction is carried out in an inert protective atmosphere, and the inert protective atmosphere comprises any one of a nitrogen atmosphere, an argon atmosphere, and a helium atmosphere.

[0097] In an embodiment, the coupling reaction has a temperature of 60-100? C., which may be, for example, 65? C., 70? ? C., 75? C., 80? C., 85? C., 90? ? C. or 95? C.

[0098] In an embodiment, the coupling reaction is carried out for a period of 5-36 h, which may be, for example, 6 h, 8 h, 10 h, 12 h, 14 h, 16 h, 18 h, 20 h, 24 h, 28 h, 32 h or 34 h.

[0099] In an embodiment, the preparation of the benzocyclobutene resin further comprises an optional step of hydrogenation reaction, which may be carried out before and/or after the coupling reaction, and the hydrogenation reaction may be full hydrogenation (which means that all of the C?C on the main and branched chains of the benzocyclobutene resin is hydrogenated, preferably, after the coupling reaction) or partial hydrogenation (which may be carried out before or after the coupling reaction). The hydrogenation reaction fully or partially hydrogenates the C?C double bonds of the hydrocarbon resin (for example, polybutadiene and/or a styrene-butadiene copolymer) to form saturated carbon chains (which means that R.sub.1 is ethylidene and/or R.sub.2 is ethyl); accordingly, the dielectric properties of the benzocyclobutene resin can be further improved.

[0100] The preparation method of the benzocyclobutene resin will be described hereinafter with reference to specific preparation examples: in the preparation examples, the specific information of the hydrocarbon resin involved is shown below:

[0101] B1000, polybutadiene, the structural unit formed by butadiene 1,2-polymerization

##STR00012##

similarly hereinafter) has a molar percentage of 85%, and the structural unit formed by 1,4-polymerization

##STR00013##

similarly hereinafter) has a molar percentage of 15%, Nippon Soda Co., Ltd.;

[0102] B2000, polybutadiene, the structural unit formed by 1,2-polymerization has a molar percentage of 88%, and the structural unit formed by 1,4-polymerization has a molar percentage of 12%, Nippon Soda Co., Ltd.;

[0103] B3000, polybutadiene, the structural unit formed by 1,2-polymerization has a molar percentage of 92%, and the structural unit formed by 1,4-polymerization has a molar percentage of 8%, Nippon Soda Co., Ltd.;

[0104] BI3060, partially hydrogenated polybutadiene resin, the structural unit formed by 1,2-polymerization has a molar percentage of 60%, the structural unit

##STR00014##

has a molar percentage of 32%, and the structural unit formed by 1,4-polymerization has a molar percentage of 8%, Nippon Soda Co., Ltd.;

[0105] Ricon 154, polybutadiene, the structural unit formed by 1,2-polymerization has a molar percentage of 90%, and the structural unit formed by 1,4-polymerization has a molar percentage of 10%, Sartomer Americas;

[0106] Ricon 184, butadiene-styrene copolymer, the structural unit formed by 1,2-polymerization has a molar percentage of 30%, the structural unit formed by 1,4-polymerization has a molar percentage of 48%, and the styrene structural unit

##STR00015##

has a molar percentage of 22%, Sartomer Americas:

[0107] Ricon 100, butadiene-styrene copolymer, the structural unit formed by 1,2-polymerization has a molar percentage of 70%, the structural unit formed by 1,4-polymerization has a molar percentage of 8%, and the styrene structural unit has a molar percentage of 22%, Sartomer Americas.

Preparation Example 1

[0108] A benzocyclobutene resin CH-BCB2 is provided, the preparation method of which is as follows:

[0109] as shown in Table 1, 169.44 g of 4-bromobenzocyclobutene (4-bromo-BCB), 100 g of poly butadiene B2000, 16.35 g of tris(o-methylphenyl)phosphine, 7.48 g of palladium acetate, 500 g of triethylamine and 1000 g of acetonitrile were added to a flask and reacted with stirring in an argon atmosphere at 85? C. for 24 h: the system was cooled and rotary-evaporated to dry the solvent; the residue was quickly passed through a column with neutral alumina, and rotary-evaporated to dry the solvent to obtain a viscous liquid; the viscous liquid was dissolved with toluene, then added with methanol in 4 times the amount of toluene, shaken thoroughly, and then allowed to stand, and the toluene layer was separated out: the residue was rotary-evaporated and concentrated and dried under vacuum to obtain a colorless viscous liquid, that is, benzocyclobutene resin CH-BCB2.

[0110] A Fourier transform infrared spectrometer (FTIR, IS10 FT-IR, Thermo Fisher) is used to characterize the structure of the benzocyclobutene resin CH-BCB2, and the infrared spectrum obtained is shown in FIG. 1. As can be seen from FIG. 1, the characteristic absorption peak at 1473 cm-1 which is assigned to the four-membered ring of benzocyclobutene indicates the CH-BCB2 resin contains the benzocyclobutene structure; the TLC column chromatography shows that the raw material disappears, indicating that the benzocyclobutene structure is completely grafted onto the polybutadiene.

[0111] With reference to GB/T 21863-2008, the molecular mass of the benzocyclobutene resin CH-BCB2 is determined by gel permeation chromatography (GPC) based on the polystyrene calibrant, and the GPC spectrum obtained is shown in FIG. 2. In FIG. 2, the marked 3241 is the viscosity average molecular mass of the benzocyclobutene resin CH-BCB2, and its number average molecular mass (Mn) is 2416.

Preparation Examples 2-7

[0112] A benzocyclobutene resin CH-BCB2 is provided, the preparation method of which differs from Preparation Example 1 in the species and amounts of the raw materials used, as shown in Table 1 specifically: the process parameters not shown in Table 1 are the same as those in Preparation Example 1. In Table 1, the structural unit A (%), structural unit B (%), and structural unit C (%) represent their respective molar percentages in the benzocyclobutene resin: the structural unit A (%) and structural unit B (%) are calculated from the addition amount of 4-bromo-BCB and the molar percentage of the structural unit formed by 1,2-polymerization in the resin raw material (the thin-layer chromatography was is employed in the preparation for monitoring to ensure that 4-bromo-BCB is completely reacted, and therefore, 4-bromo-BCB is completely converted into structural unit A, and the difference between the molar percentages of structural unit formed by 1,2-polymerization in the resin raw material and structural unit A is the amount of structural unit B (in a case where the resin raw material is polybutadiene); if the resin raw material is a butadiene-styrene copolymer, the molar percentage of structural unit B is calculated by the difference between the molar percentages of structural unit formed by 1,2-polymerization in the resin raw material and structural unit A plus the molar percentage of styrene structural unit: the structural unit C is derived from the hydrocarbon resin (polybutadiene or a butadiene-styrene copolymer), which is obtained from the raw material manufacturer.

TABLE-US-00001 TABLE 1 CH- CH- CH- CH- CH- CH- CH- BCB1 BCB2 BCB3 BCB4 BCB5 BCB6 BCB7 Resin species B1000 B2000 B3000 BI3060 Ricon 154 Ricon 184 Ricon 100 Resin mass/g 100 100 100 100 100 100 100 4-Bromo- 101.67 169.44 271.11 33.89 16.94 60.61 60.61 BCB/g Tris(o- 9.81 16.35 26.15 3.27 1.63 5.85 5.85 methylphenyl) phosphine/g Palladium 4.49 7.48 11.97 1.50 0.75 2.68 2.68 acetate/g Triethylamine/g 300 500 800 100 60 200 200 Acetonitrile/g 1000 1000 2000 500 200 700 700 Structural 30.00% 50.00% 80.00% 10.00% 5.00% 20.00% 20.00% unit A Structural 55.00% 38.00% 12.00% 82.00% 85.00% 32.00% 72.00% unit B Structural 15.00% 12.00% 8.00% 8.00% 10.00% 48.00% 8.00% unit C Mn 1235 2416 3655 3197 5335 9356 5106

Comparative Preparation Example 1

[0113] The method in Example 1 of prior art CN107501459A was used to synthesize the benzocyclobutene resin CH-BCB-D1, which was copolymerized from 4-vinylbiphenyl and 4-5 vinylbenzocyclobutene.

[0114] In the following embodiments of the present application, the materials involved are shown as follows.

(1) Benzocyclobutene Resin

[0115] Benzocyclobutene resins CH-BCB1 to CH-BCB7 provided in Preparation Examples 1-7;

[0116] CH-BCB-D1 provided in Comparative Preparation Example 1.

(2) Hydrogenated Hydrocarbon Resin

[0117] Fully hydrogenated SEBS, KIC19-023, Mn: 40000, Shanghai Kraton;

[0118] Fully hydrogenated SEBS, XPH-201-H, Mn: 120000, Shanghai Kraton;

[0119] Fully hydrogenated SEBS, H1221, Mn: 90000, Asahi Kasei, Japan;

[0120] Fully hydrogenated SEBS, P2000, Mn: 50000, Asahi Kasei, Japan;

[0121] Fully hydrogenated polybutadiene, BI-3000, Mn: 3000, Nippon Soda;

[0122] Partially hydrogenated polybutadiene, BI-3060, Mn: 3000, Nippon Soda.

(3) Initiator

[0123] Tert-butyl isopropyl phenyl peroxy, BIPB, Hunan Farida.

(4) Filler

[0124] Silica, HM102YJ, Jiangsu Finetal.

(5) Flame Retardant

[0125] SYTELX 8010, Albemarle, USA.

Example 1

[0126] A resin composition comprises the following components in parts by mass: 30 parts of benzocyclobutene resin CH-BCB1, 70 parts of SEBS (XPH-201-H), 300 parts of silica, and 10 parts of flame retardant SYTELX 8010.

[0127] An insulating resin film and a copper clad laminate comprising the resin composition are provided, the preparation method of which are as follows: [0128] (1) various components of the resin composition were mixed with toluene according to the formulation amounts to prepare a resin adhesive liquid with a solid content of 65%; [0129] (2) the resin adhesive liquid obtained in step (1) was coated on one side of a release film (PET film) and placed into an oven and baked at 130? ? C. for 4 min to remove the solvent, so as to obtain the insulating resin film; and [0130] (3) ten of the insulating resin films obtained in step (2) are laminated, clad with HOZ HVLP2 copper foils on both sides, and subjected to thermal press curing at 210? ? C., 30 kg/cm.sup.2 for 120 min to obtain the copper clad laminate.

[0131] The performance of the copper clad laminate is tested as follows: [0132] (1) glass transition temperature Tg: a dynamic mechanical analyzer (DMA) Rheometric RSAIII is used for the test: [0133] (2) dielectric constant Dk and dielectric loss tangent Df: the split post dielectric resonator (SPDR) method and a dielectric analyzer HP Agilent E4991A are used for the test at a frequency of 10 GHz: [0134] (3) peel strength PS: the peel strength between copper foil and circuit carrier board is determined after thermal stress with reference to IPC-TM-650 2.4.8 C standard: [0135] (4) damp heat resistance PCT: PCT is carried out for 6 h; the copper foil of the laminate is etched and made into three 100 mm?100 mm samples: the samples are placed in a pressure cooker and treated at 105? C. and 103.4 KPa for 360 min, and then impregnated in a 288? C. tin furnace, and the time when delamination and blistering occur is determined. If the time is less than 300 s, the specific time value will be recorded; if the time reaches 5 min, the test will be stopped and >300 s will be recorded. The mark ? means that there is no delamination and blistering within 300 s, and the sample is qualified in damp heat resistance: x means that there is delamination and blistering within 300 s, and the sample is not qualified in damp heat resistance; [0136] (5) heat resistance T300: the heat resistance of material is determined with reference to IPC-TM-650 2.4.24.1 standard: [0137] (6) flame resistance: the flame resistance is determined with reference to UL 94 standard: [0138] (7) bending angle: the laminate obtained by pressing the above resin adhesive film is subjected to etching to remove its copper foil and is prepared into 80 mm?80 mm samples, the samples are bended to determine the bending angle where the fracture occurs: a larger angle indicates a better flexibility: [0139] (8) chemical resistance (solvent resistance): the laminate is immersed in toluene at 25? C. for one day, and then taken out and dried; then the laminate is observed to see whether blistering or delamination occurs. No appearance change of the laminate means the chemical resistance is good, marked as ?; blistering or delamination means the chemical resistance is bad, marked as x; [0140] the test results are shown in Table 2.

Examples 2-8, Comparative Examples 1-4

[0141] A resin composition and an insulating resin film and a copper clad laminate comprising the same are provided, which differ from Example 1 in the formulation of the resin composition, as shown in Table 2 and Table 3 specifically; the unit of amount of each component is part, and -- represents the absence of the component; the preparation method and performance testing method of the insulating resin film and the copper clad laminate are the same as those in Example 1.

TABLE-US-00002 TABLE 2 Example Example Example Example Example Example 1 2 3 4 5 6 Benzocyclobutene CH-BCB1 30 resin CH-BCB2 20 CH-BCB3 20 10 CH-BCB4 40 CH-BCB5 50 CH-BCB6 CH-BCB7 Comparative CH-BCB- benzocyclobutene D1 resin Benzocyclobutene 4-bromo- monomer BCB Hydrocarbon B2000 resin Hydrogenated KIC19-023 90 hydrocarbon XPH-201-H 70 resin H1221 80 80 P2000 BI-3000 60 50 BI-3020 Initiator BIPB Filler HM102YJ 300 200 200 50 100 Flame SYTELX 10 20 28 30 40 28 retardant 8010 Performance test results Tg ? C. 200 202 187 190 180 181 Dk 10 GHz 3.20 3.10 3.10 2.38 2.50 2.80 Df 10 GHz 0.00080 0.00070 0.00080 0.00060 0.00050 0.00055 PS N/mm 1.05 1.18 1.15 1.85 0.85 0.92 PCT 6 h ??? ??? ??? ??? ??? ??? T300 min >60 >60 >60 >60 >60 >60 Flame V-0 V-0 V-0 V-0 V-0 V-0 resistance Bending ? >150 >150 >150 >150 >150 140 angle Chemical ? ? ? ? ? ? resistance

TABLE-US-00003 TABLE 3 Comparative Comparative Comparative Comparative Example Example Example Example Example Example 7 8 1 2 3 4 Benzocyclobutene CH-BCB1 resin CH-BCB2 CH-BCB3 5 CH-BCB4 CH-BCB5 CH-BCB6 60 CH-BCB7 70 80 Comparative CH-BCB- 70 benzocyclobutene D1 resin Benzocyclobutene 4-Bromo- 12.58 monomer BCB Hydrocarbon B2000 7.42 resin Hydrogenated KIC19-023 95 hydrocarbon XPH-201-H resin H1221 80 P2000 30 20 30 BI-3000 BI-3020 40 Initiator BIPB 3 0.5 0.5 0 Filler HM102YJ 100 100 100 100 200 Flame SYTELX 28 28 28 28 28 20 retardant 8010 Performance test results Tg ? C. 260 250 160 255 220 160 Dk 10 GHz 2.80 2.50 2.38 2.80 2.60 3.20 Df 10 GHz 0.00080 0.00070 0.00060 0.00065 0.00090 0.00100 PS N/mm 0.89 0.85 1.85 0.7 0.65 1 PCT 6 h ??? ??? ??? ??? ??? ??? T300 min >60 >60 40 >60 >60 42 Flame V-0 V-0 V-0 V-0 V-0 V-0 resistance Bending ? 120 120 >150 70 90 >150 angle Chemical ? ? X ? ? X resistance

[0142] Combining the performance test data in Table 2 and Table 3, it can be seen that by employing the resin composition provided by the present application to prepare the insulating resin film and copper clad laminate, Dk of the copper clad laminate is 2.38-3.20 at 10 GHz, Df is 0.0005-0.0008, the glass transition temperature Tg is 180-200? C., the PCT 6 h test is passed, the heat resistance at 300? C. is more than 60 min, the peel strength is 0.85-1.85 N/mm, the bending angle is more than or equal to 120?, the flame resistance reaches V-0, and the 24 h solvent resistance test is passed; the materials provided by the present application have excellent dielectric properties, heat resistance, damp heat resistance, chemical resistance and mechanical properties, and the reliability is good.

[0143] The amount of benzocyclobutene resin in Comparative Example 1 is too low, resulting in the copper clad laminate having low glass transition temperature, insufficient heat resistance and poor solvent resistance: the amount of benzocyclobutene resin in Comparative Example 2 is too high, and the heat resistance and dielectric properties become better, but the key flexibility, i.e., bending angle, becomes very low, indicating that the flexibility is poor. The resin composition of Comparative Example 3 does not contain the benzocyclobutene resin with the limited structure of the present application, and does not contain the reactive C?C double bond, and thus has low Tg; besides, due to containing a high content of the benzene ring in its structure, the resin composition of Comparative Example 3 has poor dielectric properties and low bending angle, i.e., poor flexibility. For the resin composition of Comparative Example 4, polybutadiene B2000 and 4-bromobenzocyclobutene are physically mixed according to the ratio in Preparation Example 2 and then added with other components same as in Example 2: because the benzocyclobutene has not been grafted onto the butadiene-styrene resin, the 4-bromobenzocyclobutene basically volatilizes away during the pre-curing process, resulting in a significant deterioration in the dielectric properties as well as in heat and solvent resistance of the Comparative Example 4.

[0144] The applicant declares that the resin composition, the insulating resin film, and the use thereof of the present application are illustrated by the embodiments in the present application, but the present application is not limited to the above process steps, which means that the present application is not necessarily relied upon the above process steps to be implemented. It should be clear to those skilled in the art that any improvement of the present application, equivalent substitution of the raw materials selected for the present application, addition of auxiliary ingredients, selection of specific methods, etc., shall fall within the protection scope and disclosure scope of the present application.