Resin composition, and prepreg and circuit material using the same

Abstract

The present application provides a resin component, and a prepreg and a circuit material using the same. The resin component comprises unsaturated polyphenylene ether resin, polyolefin resin, terpene resin and an initiator. When the total weight of the unsaturated polyphenylene ether resin, polyolefin resin and terpene resin is defined as 100 parts by weight, the terpene resin is in an amount of 3-40 parts by weight. The polyolefin resin is one or a combination of at least two selected from the group consisting of unsaturated polybutadiene resin, SBS resin and styrene butadiene resin. The present application discloses that the resulting resin composition has good film-forming properties, adhesion and dielectric properties through the coordination of unsaturated polyphenylene ether resin, unsaturated polyphenylene ether resin, polyolefin resin and terpene resin, and the circuit boards using the same have higher interlayer peel strength and lower dielectric loss.

Claims

1. A resin composition, comprising unsaturated polyphenylene ether resin, polyolefin resin, terpene resin and an initiator, wherein when the total weight of the unsaturated polyphenylene ether resin, polyolefin resin and terpene resin is defined as 100 parts by weight, the terpene resin is in an amount of 3-40 parts by weight; and the polyolefin resin is one or a combination of at least two selected from the group consisting of unsaturated polybutadiene resin, SBS resin and styrene butadiene resin; wherein when the total weight of the unsaturated polyphenylene ether resin, polyolefin resin and terpene resin is defined as 100 parts by weight, the resin composition comprises 40-80 parts by weight of unsaturated polyphenylene ether resin, 10-50 parts by weight of polyolefin resin, 3-40 parts by weight of terpene resin and 0.1-7 parts by weight of an initiator.

2. The resin composition according to claim 1, wherein the unsaturated polyphenylene ether resin has the structural formula as shown in Formula (1): ##STR00004## 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) ##STR00005## 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.15 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, ##STR00006## n is 0 or 1; and R.sub.16 is a hydrogen atom or a hydrocarbon group having 1-10 carbon atoms.

3. The resin composition according to claim 1, wherein the polyolefin resin is unsaturated polybutadiene resin.

4. The resin composition according to claim 3, wherein the unsaturated polybutadiene resin has a number average molecular weight of 1,000-50,000.

5. The resin composition according to claim 3, wherein the unsaturated polybutadiene resin has a vinyl content of 60-99 mol. %.

6. The resin composition according to claim 5, wherein the unsaturated polybutadiene resin has a vinyl content of 75-93 mol. %.

7. The resin composition according to claim 3, wherein the unsaturated polybutadiene resin is unsaturated polybutadiene resin modified with polar groups; wherein the unsaturated polybutadiene resin modified with polar groups has a grafting rate of polar groups of 5-10%.

8. The resin composition according to claim 7, wherein the unsaturated polybutadiene resin modified with polar groups is one or a combination of at least two selected from the group consisting of epoxy modified unsaturated polybutadiene resin, maleic anhydride modified unsaturated polybutadiene resin, acrylic acid modified unsaturated polybutadiene resin, hydroxy-terminated unsaturated polybutadiene resin, carboxy-terminated unsaturated polybutadiene resin, and amine-modified unsaturated polybutadiene resin.

9. The resin composition according to claim 1, wherein the terpene resin has a number average molecular weight of 400-4,000.

10. The resin composition according to claim 1, wherein the terpene resin comprises at least one member selected from the group consisting of turpentine, α-pinene, β-pinene, limonene and β-phellandrene.

11. The resin composition according to claim 1, wherein the terpene resin is one or a combination of at least two selected from the group consisting of polyterpene resins, terpene-phenol resins, styrenated terpene resins, terpene-hydrocarbon resins and terpene-vinyl aromatic compound resins.

12. The resin composition according to claim 1, wherein the terpene resin comprises a polymer.

13. The resin composition according to claim 1, wherein the initiator is a first initiator, a second initiator, or a combination of the first initiator and the second initiator; wherein 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.

14. The resin composition according to claim 13, wherein the first initiator is 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 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.

15. The resin composition according to claim 1, wherein the resin composition further comprises a flame retardant; wherein the flame retardant is in an amount of 10-40 parts by weight, when the total weight of the unsaturated polyphenylene ether resin, polyolefin resin and terpene resin is defined as 100 parts by weight.

16. The resin composition according to claim 1, wherein the resin composition further comprises a silane coupling agent; wherein the silane coupling agent is in an amount of 0.1-5 parts by weight, when the total weight of the unsaturated polyphenylene ether resin, polyolefin resin and terpene resin is defined as 100 parts by weight.

17. The resin composition according to claim 1, wherein the resin composition further comprises a filler, wherein the filler is in an amount of 20-90% of the total weight of the resin composition.

18. A resin-coated copper foil, which is formed by coating the resin composition of claim 1 on a copper foil, baking and heating, and then semi-curing.

19. A laminate, comprising one or at least two stacked prepregs, wherein the prepreg comprising a reinforcing material, and the resin composition according to claim 1 which is attached to the reinforcing material after being impregnated and dried.

20. 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 obtained by applying the adhesive composition of claim 1 dissolved in a solvent to the surface of the conductive metal layer or the dielectric substrate layer in the form of a solution, or applying to a release material and removing the release material after partially curing or completely curing.

Description

DETAILED DESCRIPTION

(1) 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.

(2) The sources of raw materials used in the embodiments of the present application are listed as follows:

(3) Unsaturated Polyphenylene Ether Resin:

(4) Polyphenylene ether resin MMA-PPE (SA9000, SABIC);

(5) Polyphenylene ether resin St-PPE-2 (manufactured by Mitsubishi Chemical Corporation);

(6) Polyphenylene ether resin St-PPE-1 (manufactured by Mitsubishi Chemical Corporation).

(7) Unsaturated Polybutadiene Resin:

(8) B1000: Nippon Soda Corporation;

(9) B3000: Nippon Soda Corporation;

(10) R810: Japan JSR Corporation.

(11) Sbs Resin:

(12) D1118: Kraton Polymers;

(13) Terpene Resin:

(14) KT90, Guangdong KOMO Co., Ltd

(15) KT100, Guangdong KOMO Co., Ltd

(16) KT5090 Guangdong KOMO Co., Ltd

(17) Terpene Solvents:

(18) GP00007 (α-Pinene monomer), Fujian Green Pine Co., Ltd.

(19) Initiator:

(20) BPO: Dahe Oil & Fat Co., Ltd.;

(21) DCP: Shanghai Fangruida Chemical.

Examples 1-3 and Comparative Examples 1-6

(22) Examples 1-3 and Comparative Examples 1-6 each provided a circuit material, and the preparation method is as follows.

(23) Prepreg: Synamic6 prepreg, a thermosetting hydrocarbon-based substrate material, made by Shengyi Technology, Guangdong, China.

(24) Preparation of adhesive layer: Unsaturated polyphenylene ether resin, polyolefin resin, terpene resin, initiator, flame retardant and filler 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 a copper foil with an adhesive layer (the grammage of the adhesive layer was 20 g/m.sup.2).

(25) Preparation of Circuit Materials:

(26) 4 Synamic6 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.

Example 4

(27) This example provided a copper clad laminate, and the preparation method is as follows.

(28) Unsaturated polyphenylene ether resin, polyolefin resin, terpene resin, initiator, flame retardant and filler, etc. were dissolved in xylene in proportions, and mixed at room temperature to obtain a glue. The reinforcing material 2116 glass fiber was impregnated with the glue, dried and semi-cured to obtain a prepreg.

(29) The above-mentioned prepreg and a piece of copper foil were stacked neatly, laminated and cured in a press at 210° C. to obtain a copper-clad laminate.

Example 5

(30) This example provided a circuit material, and the preparation method is as follows.

(31) Prepreg: S7136 prepreg, a thermosetting hydrocarbon-based substrate material, made by Shengyi Technology, Guangdong, China.

(32) Preparation of adhesive layer: Unsaturated polyphenylene ether resin, polyolefin resin, terpene resin, initiator, flame retardant and filler 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 a copper foil with an adhesive layer (the grammage of the adhesive layer was 20 g/m.sup.2).

(33) Preparation of Circuit Materials:

(34) 4 S7136 prepregs and the copper foil with an adhesive layer were stacked neatly in order, laminated and cured in a press at 210° C. to obtain a circuit material.

Comparative Example 7

(35) A circuit material was provided. The difference from Example 1 is that the terpene resin, which is the raw material of the resin composition, was replaced with a terpene solvent.

(36) The types and amounts of the raw materials in Examples 1-5 and Comparative Examples 1-7 above are shown in Tables 1 and 2 below.

(37) The dielectric constant, dielectric loss factor, peel strength and float soldering resistance of the copper clad laminates and circuit materials provided in Examples 1-5 and Comparative Examples 1-7 above were tested by the following methods.

(38) (1) Dielectric constant (Dk) and dielectric loss factor (Df): tested in accordance with SPDR method in A state at 10 GHz;

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

(40) (3) Float soldering resistance: tested in accordance with IPC-TM-650 method.

(41) The results of the above test are shown in Tables 1 and 2.

(42) TABLE-US-00001 TABLE 1 Comp. Example Example Example Example Example Example Items 1 2 3 4 5 1 Resin Polyolefin Type B1000 B3000 R810 R810 D1118 B1000 composition resin Amount/g 50 10 10 32 50 50 terpene Type KT100 KT90 KT5090 KT5090 KT100 KT100 resin Amount/g 10 10 40 3 10 25 PPO resin Type SA9000 St-PPE-2 St-PPE-1 St-PPE-1 SA9000 SA9000 Amount/g 40 80 50 65 40 25 Initiator Type BPO DCP DCP DCP BPO BPO Amount/g 0.1 7 6 6 0.1 0.1 Performance Dk(10 GHz) 3.40 3.63 3.67 3.53 3.35 3.43 Df(10 GHz) 0.0030 0.0037 0.0033 0.0032 0.0029 0.0029 Peel strength (N/mm) 1.09 1.37 1.33 1.24 1.04 0.71 Float soldering Higher Higher Higher Higher Higher Higher resistance 288° C., No than than than than than than layering, no foaming 5 min 5 min 5 min 5 min 5 min 5 min

(43) TABLE-US-00002 TABLE 2 Comp. Comp. Comp. Comp. Comp. Comp. Example Example Example Example Example Example Items 2 3 4 5 6 7 Resin Polyolefin Type B3000 R810 R810 R810 B1000 B1000 composition resin Amount/g 10 32 10 5 57 50 terpene Type KT90 KT5090 KT5090 KT5090 KT100 GP00007 resin Amount/g 3 1 50 40 3 10 PPO resin Type St-PPE-2 St-PPE-1 St-PPE-1 St-PPE-1 SA9000 SA9000 Amount/g 87 67 40 55 40 40 Initiator Type DCP DCP DCP DCP BPO BPO Amount/g 7 6 6 6 0.1 0.1 Dk(10 GHz) — 3.53 — 3.69 3.37 3.39 Performance Df(10 GHz) — 0.0032 — 0.0039 0.0030 0.0028 Peel strength (N/mm) — 0.75 — 1.36 0.71 0.71 Float soldering — Higher — Higher Higher Less resistance 288° C., No than than than than layering, no foaming 5 min 5 min 5min 10 s

(44) It can be seen from the test results in Tables 1 and 2 that the copper clad laminates and circuit materials provided by the examples of the present application have the peel strength reaching 1.04-1.37 N/mm, the dielectric constant (10 GHz) of 3.35 to 3.67, and the dielectric loss factor (10 GHz) of 0.0029-0.0037, and have good dielectric properties, peel strength and float soldering resistance.

(45) 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 sheets was reduced to only 0.71 N/mm.

(46) 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 glue film could be prepared.

(47) In Comparative Example 3, the content of terpene resin used was less than 3 wt. %. As compared with Example 4, the peel strength of the obtained sheets was reduced to only 0.75 N/mm.

(48) In Comparative Example 4, the content of terpene resin used was greater than 40 wt. %. As compared with Example 3, the glue solution has poor film-forming properties, and no qualified glue film could be prepared.

(49) In Comparative Example 5, the content of polyolefin resin used was less than 10 wt. %. As compared with Example 3, the sheets had high dielectric loss, and the dielectric properties became worse.

(50) The content of polyolefin resin used in Comparative Example 6 was greater than 50 wt. %. As compared with Example 1, the peel strength of the obtained sheets was reduced to only 0.71 N/mm.

(51) As Compared with Example 1, the terpene solvent was used to replace the terpene resin in Comparative Example 7. The peel strength of the sheets was reduced to only 0.71 N/mm. The float soldering was less than 10 s, and the heat resistance was reduced.

(52) 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.