CIRCUIT MATERIAL AND CIRCUIT BOARD CONTAINING THE SAME

Abstract

The present application provides a circuit material and a circuit board containing the same. The circuit material comprises a conductive metal layer and a dielectric substrate layer, and an adhesive layer arranged therebetween, wherein the adhesive layer is made of a material which comprises an adhesive composition comprising a resin component and a non-resin component, wherein the resin component is composed of unsaturated polyphenylene ether resin, SBS resin and maleimide resin; and the non-resin component comprises an initiator; and the adhesive layer is obtained by applying the adhesive composition dissolved in a solvent onto the surface of the conductive metal layer or the dielectric substrate layer in the form of a solution, or by applying to a release material and removing the release material after partially curing or completely curing.

Claims

1. A circuit material, comprising a conductive metal layer and a dielectric substrate layer, and an adhesive layer arranged between the conductive metal layer and the dielectric substrate layer, wherein the adhesive layer is made of a material which comprises an adhesive composition; wherein the adhesive composition comprises a resin component and a non-resin component; wherein the resin component is composed of unsaturated polyphenylene ether resin, SBS resin and maleimide resin; and the non-resin component comprises an initiator; and the adhesive layer is obtained by applying the adhesive composition dissolved in a solvent onto the surface of the conductive metal layer or the dielectric substrate layer in the form of a solution, or by applying to a release material and removing the release material after partially curing or completely curing.

2. The circuit material of claim 1, wherein the resin component is composed of 40-80 wt. % of unsaturated polyphenylene ether resin, 10-50 wt. % of SBS resin and 3-40 wt. % of maleimide resin.

3. The circuit material of claim 1, wherein the unsaturated polyphenylene ether resin has the structural formula as shown in Formula (1) ##STR00007## wherein a and b are each independently an integer of 1-30; Z has the structure shown in Formula (2) or (3); O—Y has the structure shown in Formula (4); and O—X—O has the structure shown in Formula (5) ##STR00008## in Formula (3), A is any one selected from the group consisting of an arylene group, a carbonyl group and an alkylene group having 1-10 carbon atoms; m is an integer of 0-10; and R.sub.1-R.sub.3 are each independently a hydrogen atom or an alkyl group having 1-10 carbon atoms; in Formula (4), R.sub.4 and R.sub.6 are each independently any one selected from the group consisting of a hydrogen atom, a halogen atom, a phenyl group and an alkyl group having 1-8 carbon atoms; and R.sub.5 and R.sub.7 are each independently any one selected from the group consisting of a halogen atom, a phenyl group and an alkyl group having 1-8 carbon atoms; and in Formula (5), R.sub.8-R.sub.16 are each independently any one selected from the group consisting of a hydrogen atom, a halogen atom, a phenyl group and an alkyl group having 1-8 carbon atoms; B is a hydrocarbylene group having 20 carbon atoms or less, ##STR00009## n is 0 or 1; and R.sub.16 is a hydrogen atom or a hydrocarbon group having 1-10 carbon atoms.

4. The circuit material of claim 1, wherein the SBS resin has a number average molecular weight of 5,000-50,000.

5. The circuit material of claim 4, wherein the SBS resin has a number average molecular weight of 15,000-30,000.

6. The circuit material of claim 1, wherein the SBS resin has a side chain vinyl content of 60-99 mol. %.

7. The circuit material of claim 6, wherein the SBS resin has a side chain vinyl content of 75-93 mol. %.

8. The circuit material of claim 1, wherein the SBS resin has a styrene unit content of 35-55 mol. %.

9. The circuit material of claim 1, wherein the maleimide resin has the structural formula as shown in Formula (6) ##STR00010## wherein M is an m-valent aliphatic group or an aromatic group; Xa and Xb are each independently any one selected from the group consisting of a hydrogen atom, a halogen atom and an aliphatic group; and m is an integer ≥2.

10. The circuit material of claim 1, wherein M is any one selected from the group consisting of ##STR00011## ##STR00012## wherein a is a positive integer of 1-20; R.sub.17-R.sub.21 is a phenyl group or an alkyl group having 1-4 carbon atoms; n is an integer ≥0; and * represents the attachment position of the group.

11. The circuit material of claim 1, wherein the initiator is in an amount of 0.1-7% by weight of the resin component.

12. The circuit material of claim 11, wherein the initiator is a first initiator, a second initiator, or a combination of the first initiator and the second initiator; the first initiator has a 1 min half-life temperature of 50-160° C., and the second initiator has a 1 min half-life temperature of 160-300° C.

13. The circuit material of claim 12, wherein the first initiator is any one or a combination of at least two selected from the group consisting of tert-butyl peroxyacetate, 2,2-bis(tert-butylperoxy)octane, tert-butyl peroxyisopropyl carbonate, 1,1-bis(tert-butylperoxy)cyclohexanone, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexanone, tert-butyl peroxycaprylate, tert-butyl peroxyisobutyrate, disuccinate peroxide, di-m-toluoyl peroxide, xyloyl peroxide, diacetyl peroxide, cumyl peroxycaprylate, didecanoyl peroxide, dioctanoyl peroxide, didodecanoyl peroxide, bis(3,5,5-trimethylacetyl peroxide), tert-butyl peroxypivalate, tert-hexyl peroxytrimethyl acetate, tert-butyl peroxyneohexanoate, tert-hexyl peroxyneohexanoate, bis(3-methyl-3-methoxybutyl peroxyhydrocarbonate), tert-hexyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, cumyl peroxyneohexanoate, bismethoxyisopropyl peroxyhydrocarbonate, ditetradecyl peroxyhydrocarbonate, diallyl peroxyhydrocarbonate, cumyl peroxyneodecanoate, di-n-propyl peroxyhydrocarbonate, bis(2-hydroxyethylhexyl peroxyhydrocarbonate), bis(2-ethylhexyl peroxyhydrocarbonate), di-n-butyl peroxyhydrocarbonate, diisobutyl peroxyhydrocarbonate, diisobutylene peroxide, diisopropyl peroxyhydrocarbonate and acetylcyclohexylsulfonyl peroxide; and wherein the second initiator is any one or a combination of at least two selected from the group consisting of tert-butyl hydroperoxide, tetramethylbutane peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)-hexyne, di-tert-butyl peroxide, a,a-bis(tert-butylperoxy-m-cumyl), 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, tert-butylcumyl peroxide, tert-butylperoxyallyl hydrocarbonate, dicumyl peroxide (DCP), tert-butyl peroxybenzoate, di-tert-butyl peroxyisophthalate, n-butyl-4,4-bis(tert-butylperoxy)valerate, tert-butyl-peroxy(3,5,5-trimethyl acetate), tert-butyl peroxylaurate, 2,5-dimethyl-2,5-bis(dibenzoylperoxy)hexane and 2,2-bis(tert-butylperoxy)butane.

14. The circuit material of claim 1, wherein the non-resin component further comprises a flame retardant; wherein the flame retardant is in an amount of 10-40% by weight of the resin component.

15. The circuit material of claim 1, wherein the non-resin component further comprises a silane coupling agent; wherein the silane coupling agent is in an amount of 0.1-5% by weight of the resin component.

16. The circuit material of claim 1, wherein the non-resin component further comprises a crosslinking agent which is any one or a combination of at least two selected from the group consisting of triallyl isocyanurate, polytriallyl isocyanurate, triallyl cyanurate, trimethacrylic acid, diallyl phthalate and multifunctional acrylate; wherein the crosslinking agent is in an amount of 3-40% by weight of the resin component.

17. The circuit material of claim 1, wherein the non-resin component further comprises a filler, the filler is in an amount of 20-90% of the total weight of the adhesive composition.

18. The circuit material of claim 1, wherein the circuit material obtained by curing the dielectric circuit substrate layer and the adhesive layer has dielectric constant at 1-10 GHz of below 3.8, and dielectric loss factor of below 0.007; optionally, the adhesive layer has a grammage of 2-40 g/m.sup.2.

19. A circuit board comprising the circuit material of claim 1.

20. A multilayer circuit board comprising the circuit material of claim 1.

Description

DETAILED DESCRIPTION

[0068] The technical solutions of the present application will be further illustrated by specific embodiments below. Those skilled in the art should understand that the described embodiments are only to help understand the present application and should not be regarded as specific limitations to the present application.

[0069] The sources of raw materials used in the examples of the present application are listed as follows:

[0070] Unsaturated polyphenylene ether resin:

[0071] Polyphenylene ether resin MMA-PPE (SA9000, SABIC);

[0072] Polyphenylene ether resin St-PPE-2 (manufactured by Mitsubishi Chemical Corporation);

[0073] Polyphenylene ether resin St-PPE-1 (manufactured by Mitsubishi Chemical Corporation).

[0074] SBS resin:

[0075] D1118: Kraton Polymers;

[0076] A1901: Kraton Polymers;

[0077] D6670: Kraton Polymers.

[0078] Butadiene styrene resin:

[0079] TR2000: JSR Co. of Japan.

[0080] Maleimide resin:

[0081] bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI-5100, manufactured by Daiwa Chemical Industry Co., Ltd.);

[0082] 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane (BMI-4000, manufactured by Daiwa Chemical Industry Co., Ltd.);

[0083] bis(4-maleimidophenyl)methane (BMI-1000, manufactured by Daiwa Chemical Industry Co., Ltd.);

[0084] N-phenylmaleimide (Imilex-P, manufactured by Nippon Shokubai Co., Ltd.).

[0085] Initiator:

[0086] BPO: Dahe Oil & Fat Co., Ltd.;

[0087] DCP: Shanghai Fangruida Chemical.

EXAMPLES 1-5 AND COMPARATIVE EXAMPLES 1-8

[0088] Examples 1-5 and Comparative Examples 1-8 each provided a circuit material, and the preparation method is as follows.

[0089] (1) Prepreg

[0090] S7136 prepreg, a thermosetting hydrocarbon-based substrate material, made by Shengyi Technology, Guangdong, China;

[0091] or Synamic6 prepreg, a thermosetting hydrocarbon-based substrate material, made by Shengyi Technology, Guangdong, China.

[0092] (2) Preparation of Adhesive Layer:

[0093] Unsaturated polyphenylene ether resin, SBS resin, maleimide resin, initiator, silane coupling agent and flame retardant were dissolved in xylene and mixed at room temperature to obtain a glue. The glue was coated onto a copper foil by using a coating machine, and then baked in an oven at 155° C. for 5 minutes to obtain an adhesive layer (having a thickness of 30 μm).

[0094] (3) Preparation of Circuit Material:

[0095] Several sheets of the above-mentioned prepregs and the copper foil with an adhesive layer were stacked neatly (the adhesive layer was between the prepreg and the copper foil), laminated and cured in a press at 210° C. to obtain a circuit material.

Comparative Example 9

[0096] It discloses providing a circuit material, and it differs from Example 1 in replacing the raw material SBS resin of the adhesive layer with styrene butadiene resin.

[0097] The types and amounts of the raw materials of the adhesive layers in Examples 1-5 and Comparative Examples 1-9 above are shown in Tables 1 and 2 below.

[0098] The dielectric constant, dielectric loss factor, peel strength and float soldering resistance of the circuit materials provided in Examples 1-5 and Comparative Examples 1-9 above were tested by the following methods.

[0099] (1) Dielectric constant (Dk) and dielectric loss factor (Df): tested in accordance with SPDR method;

[0100] (2) Peel strength: tested according to IPC-TM-650, 2.4.8 method;

[0101] (3) Float soldering resistance: tested in accordance with IPC650-2.4.13.1 method.

[0102] The results of the above test are shown in Tables 1 and 2.

TABLE-US-00001 TABLE 1 Com. Com. Items Example 1 Example 2 Example 3 Example 4 Example 5 Example 1 Example 2 Raw SBS Type D1118 A1901 D6670 D1118 D1118 D1118 A1901 materials resin Amount/g 50 10 30 17 10 50 10 of the Maleimide Type BMI- 5100 BMI- 4000 Imilex-P BMI- 1000 BMI- 5100 BMI- 5100 BMI- 4000 adhesive Amount/g 10 10 20 3 40 30  3 layer PPO Type SA9000 St-PPE-2 St-PPE-1 SA9000 SA9000 SA9000 St-PPE-2 Resin Amount/g 40 80 50 80 50 20 87 Initiator Type BPO DCP DCP BPO BPO BPO DCP Amount/g 0.1 7 6 0.1 0.1 0.1  7 Flame Type — — — Decabromo- — — — retardant diphenylethane Amount/g — — — 20 — — — Silane Type — — — — Vinyl — — coupling trimethoxy- agent silane Amount/g — — — — 5 — — Prepreg / Type S7136 S7136 Synamic6 S7136 S7136 S7136 S7136 / Amount/g 4 sheets 4 sheets 4 sheets 4 sheets 4 sheets 4 sheets 4 sheets Permforance Dk (10 GHz) 3.36 3.68 3.54 3.58 3.67 3.38 — Df (10 GHz) 0.0029 0.0038 0.0036 0.0036 0.0034 0.0027 — Peel strength (N/mm) 1.09 1.37 1.23 1.30 1.30 0.71 — Float soldering Higher than Higher than Higher than Higher than Higher than Higher than — resistance 288° C., No 5 min 5 min 5 min 5 min 5 min 5 min layering, no foaming

TABLE-US-00002 TABLE 2 Com. Com. Com. Com. Com. Com. Com. Items Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Raw SBS Type D1118 D1118 A1901 D1118 D1118 A1901 TR2000 materials resin Amount/g 19 10 3 55 50 10 50 of the Maleimide Type BMI- 1000 BMI- 5100 BMI- 4000 BMI- 5100 BMI- 5100 BMI- 4000 BMI- 5100 adhesive Amount/g 1 50 17  5 10 10 10 layer PPO Type SA9000 SA9000 St-PPE-2 SA9000 SA9000 St-PPE-2 SA9000 Resin Amount/g 80 40 80 40 40 80 40 Initiator Type BPO BPO DCP BPO BPO DCP BPO Amount/g 0.1 0.1 7   0.1 0.05 15   0.1 Flame Type Decabromo- — — — — — — retardant diphenylethane Amount/g 20 — — — — — — Silane Type — Trimethoxy- — — — — — coupling silane vinyl agent silane coupling agent Amount/g — 5 — — — — — Prepreg / Type S7136 Synamic6 S7136 S7136 S7136 S7136 S7136 / Amount/g 4 sheets 4 sheets 4 sheets 4 sheets 4 sheets 4 sheets 4 sheets Performance Dk (10 GHz) 3.57 3.68 3.73 — 3.36    3.72 — Df (10 GHz) 0.0036 0.0033 0.0053 — 0.0029     0.0047 — Peel strength (N/mm) 0.75 1.29 1.40 — 1.09    1.41 — Float soldering Less than Less than Higher than — Less than Less than — resistance 288° C., No 5 min 10 s 5 min 10 s 10 s layering, no foaming

[0103] It can be seen from the test results in Tables 1 and 2 that the circuit materials provided by the examples of the present application have the peel strength reaching 1.09-1.37 N/mm, the dielectric constant (10 GHz) of 3.36 to 3.68, and the dielectric loss factor (10 GHz) of 0.0029-0.0038, and have good dielectric properties and peel strength, so as to meet the performance requirements of high-frequency boards.

[0104] The content of the unsaturated PPO resin used in Comparative Example 1 was less than 40 wt. %. As compared with Example 1, the peel strength of the obtained circuit material was reduced to only 0.71 N/mm.

[0105] The content of the unsaturated PPO resin used in Comparative Example 2 was greater than 80 wt. %. As compared with Example 2, the glue solution has poor film-forming properties, and no qualified film could be prepared.

[0106] In Comparative Example 3, the content of maleimide used was less than 3 wt. %. As compared with Example 4, the peel strength of the obtained circuit material was reduced to only 0.75 N/mm.

[0107] In Comparative Example 4, the content of maleimide used was greater than 40 wt. %. As compared with Example 5, the float soldering of the obtained circuit material was less than 10 s, and the heat resistance was reduced.

[0108] In Comparative Example 5, the content of SBS resin used was less than 10 wt. %. As compared with Example 2, the dielectric loss factor of the obtained circuit material was as high as 0.0053, and the dielectric properties became worse.

[0109] The content of SBS resin used in Comparative Example 6 was greater than 50 wt. %. As compared with Example 1, the viscosity of the glue solution was too high to prepare a film.

[0110] The initiator content used in Comparative Example 7 was less than 0.1 wt. %. As compared with Example 1, the float soldering of the obtained circuit material was less than 10 seconds, and the heat resistance was reduced.

[0111] The initiator content used in Comparative Example 8 was greater than 7 wt. %. As compared with Example 2, the float soldering of the obtained circuit material was less than 10 s, and the heat resistance was reduced.

[0112] In Comparative Example 9, the styrene-butadiene resin was used instead of SBS resin. As compared with Example 1, the glue solution had poor film-forming properties, and no qualified film could be prepared.

[0113] The applicant declares that the above descriptions are only specific implementations of the present application, but the protection scope of the present application is not limited thereto. Those skilled in the art should understand that any changes or replacements that can be easily conceived by those skilled in the art within the technical scope of the present application fall within the protection scope and disclosure of the present application.