Degradable Resin Composition, and Prepreg, Laminate and Copper Clad Laminate Using Same, and Degrading method thereof

Abstract

Disclosed are a resin composition, and prepreg, laminate and copper clad laminate using the same, and degrading method thereof, the resin composition comprising: an epoxy resin, a degradable amine curing agent, a degradable mercaptan curing agent and an inorganic filler. A copper clad laminate manufactured by the resin composition comprises several pieces of stacked prepreg, and copper foil arranged at one side or two sides of stacked prepreg, each of the prepreg comprising a reinforced material and the resin composition adhered thereon after soaking and drying. The present invention mixes the degradable amine curing agent and the degradable mercaptan curing agent to obtain a curing system having an adjustable reaction rate, thus facilitating process control when manufacturing the copper clad laminate, and the manufactured copper clad laminate has high overall performance and is completely degradable, thus recycling and reusing each of the effective components.

Claims

1. A degradable resin composition, characterized in that the resin composition comprises an epoxy resin, a degradable amine curing agent, a degradable thiol curing agent, and an inorganic filler, wherein the degradable amine curing agent has the following structure: ##STR00025## the degradable thiol curing agent has the following structure: ##STR00026## wherein R.sub.1 and R.sub.2 are independently anyone selected from the group consisting of hydrogen atom, alkyl group, cycloalkyl group, heterocyclic group, heterocycloalkyl group, alkenyl group, cycloalkenyl group, aromatic group, heteroaromatic group, alkyl heteroalkyl group, alkynyl group, alkylene group, alkylene heteroalkylene, alkenylene group, alkylene heteroalkenylene, alkynylene group or alkylene heteroalkynylene; R.sub.3 and R.sub.4 are independently anyone selected from the group consisting of alkylene group, alkylene heteroalkylene, alkenylene group, alkenylene heteroalkenylene, alkylene heteroalkenylene, alkynylene group, cycloalkylene group, alkylene cycloalkylene, alkylene cycloalkylene alkylene, alkenylene cycloalkylene, alkenylene cycloalkylene alkenylene, alkylene cycloalkylene alkenylene, alkynylene cycloalkylene, alkynylene cycloalkylene alkynylene, heterocycloalkylene group, alkylene heterocycloalkylene, alkylene heterocycloalkyl alkylene, alkenylene heterocycloalkylene, alkenylene heterocycloalkyl alkenylene, alkylene heterocycloalkyl alkenylene, alkynylene heterocycloalkylene, alkynylene heterocycloalkyl alkynylene, cycloalkenylene, alkylene cycloalkenylene, alkylene cycloalkenylene alkylene, alkenylene cycloalkenylene, alkenylene cycloalkenylene alkenylene, alkylene cycloalkenylene alkenylene, alkynylene cycloalkenylene, alkynylene cycloalkenylene alkynylene, heterocycloalkenylene, alkylene heterocycloalkenylene, alkylene heterocycloalkenyl alkylene, alkenylene heterocycloalkenylene, alkenylene heterocycloalkenyl alkenylene, alkylene heterocycloalkenyl alkenylene, alkynylene heterocycloalkenylene, alkynylene heterocycloalkenyl alkynylene, arylene group, alkylene arylene group, alkylene arylene alkylene, alkenylene arylene group, alkenylene arylene alkenylene, alkylene arylene alkenylene, alkynylene arylene group, alkynylene arylene alkynylene, heteroarylene group, alkylene heteroarylene group, alkylene heteroarylene alkylene, alkenylene heteroarylene group, alkenylene heteroarylene alkenylene, alkylene heteroarylene alkenylene, alkynylene heteroarylene group, alkynylene heteroarylene alkynylene, 1,4-alkyl substituted piperazine, carbonyl group and thiocarbonyl group.

2. The resin composition according to claim 1, characterized in that the epoxy resin is anyone selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, isocyanate modified epoxy resin, o-cresol type epoxy resin, naphthalene type epoxy resin, alicyclic epoxy resin, resorcinol type epoxy resin, polyethylene glycol type epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, dicyclopentadiene type epoxy resin and phenolic type epoxy resin, or a mixture of at least two selected therefrom.

3. The resin composition according to claim 1, characterized in that the inorganic filler is anyone selected from the group consisting of silica, alumina, magnesium oxide, aluminum hydroxide, magnesium hydroxide, boehmite, aluminum nitride, boron nitride, silicon carbide, titanium dioxide, kaolin, calcium carbonate and talc powder, or a mixture of at least two selected therefrom.

4. The resin composition according to claim 1, characterized in that the epoxy groups in the epoxy resin and the active hydrogen in the degradable amine and thiol curing agents have a molar ratio of 0.8-1.2; the active hydrogen in the degradable amine curing agent and the active hydrogen in the degradable thiol curing agent have a molar ratio of 0.5-4.0.

5. The resin composition according to claim 1, characterized in that the inorganic filler is added in an amount of 0-30 parts by weight, based on 100 parts by weight of the resin composition comprising the inorganic filler.

6. (canceled)

7. A prepreg, characterized in that the prepreg comprises a reinforcing material and the resin composition according to claim 1 attached thereon after impregnation and drying.

8. A laminate characterized in comprising at least one prepreg claimed in claim 7.

9. A copper clad laminate, characterized in that the copper clad laminate comprises at least one laminated prepreg according to claim 7 and copper foil pressed onto one or both sides of the laminated prepreg.

10. A process for degrading the copper clad laminate claimed in claim 9, characterized in comprising the following steps: (1) etching copper foil from the copper foil laminate to obtain a copper recovery solution; (2) placing the core plate from which the copper foil is etched into an organic solvent, adjusting the pH to 4-6 with hydrochloric acid, holding at 100-140° C. for 2-4 h to completely degrade the resin to obtain a reinforcing material and a degradation solution, filtering and separating the degradation solution to obtain an inorganic filler and a resin solution; (3) adjusting the pH of the resin solution to 6-8 with sodium hydroxide or potassium hydroxide, precipitating the resin, filtering, drying to obtain a linear resin.

11. The resin composition according to claim 1, characterized in that, the degradable amine curing agent is ##STR00027## the degradable thiol curing agent is ##STR00028##

Description

EXAMPLE 1

[0033] Bisphenol A epoxy resin DER 530, having an epoxy equivalent of 430 g/mol, from DOW CHEMICAL.

[0034] Degradable amine curing agent

##STR00005##

prepared according to the process disclosed in CN103249712A.

[0035] Degradable thiol curing agent

##STR00006##

prepared according to the process disclosed in CN103249712A.

[0036] Silica powder, DS1032, from LIANYUNGANG DONGHAI SILICON MICROPOWDER CO., LTD

[0037] Butanone, Lanzhou Petrochemical Company

[0038] 125 parts of bisphenol A epoxy resin, 10 parts of degradable amine curing agent, 21 parts of degradable thiol curing agent, 60 parts of silica powder, and 133.3 parts of butanone were mixed to obtain a homogeneously dispersed glue solution. The gelation time (GT) of the glue solution was tested as 225s. A 2116 glass fiber cloth was impregnated into the composition for sizing, then baked in an oven at 155° C. for 3 min to prepare a prepreg.

[0039] Several prepregs were laminated, covered with electrolytic copper foils having a thickness of 35 μm onto each of the upper and bottom surfaces, hot-pressed in a vacuum press in accordance with an established procedure at 180° C. and 35 kgf/cm.sup.2 for 90 min to prepare a double-sided copper clad laminate having a thickness of 0.6 mm.

EXAMPLE 2

[0040] Bisphenol A epoxy resin DER 530, having an epoxy equivalent of 430 g/mol, from DOW CHEMICAL.

[0041] Degradable amine curing agent

##STR00007##

prepared according to the process disclosed in CN103249712A.

[0042] Degradable thiol curing agent

##STR00008##

prepared according to the process disclosed in CN103249712A.

[0043] Silica powder, DS1032, from LIANYUNGANG DONGHAI SILICON MICROPOWDER CO., LTD

[0044] Butanone, Lanzhou Petrochemical Company

[0045] 125 parts of bisphenol A epoxy resin, 4 parts of degradable amine curing agent, 33 parts of degradable thiol curing agent, 60 parts of silica powder, and 133.3 parts of butanone were mixed to obtain a homogeneously dispersed glue solution. The gelation time (GT) of the glue solution was tested as 105s. A 2116 glass fiber cloth was impregnated into the composition for sizing, then baked in an oven at 155° C. for 4 min to prepare a prepreg.

[0046] Several prepregs were laminated, covered with electrolytic copper foils having a thickness of 35 μm onto each of the upper and bottom surfaces, hot-pressed in a vacuum press in accordance with an established procedure at 180° C. and 35 kgf/cm.sup.2 for 90 min to prepare a double-sided copper clad laminate having a thickness of 0.6 mm.

EXAMPLE 3

[0047] Bisphenol A epoxy resin DER 530, having an epoxy equivalent of 430 g/mol, from DOW CHEMICAL.

[0048] Degradable amine curing agent

##STR00009##

prepared according to the process disclosed in CN103249712A.

[0049] Degradable thiol curing agent

##STR00010##

prepared according to the process disclosed in CN103249712A.

[0050] Silica powder, DS1032, from LIANYUNGANG DONGHAI SILICON MICROPOWDER CO., LTD

[0051] Butanone, Lanzhou Petrochemical Company

[0052] 125 parts of bisphenol A epoxy resin, 15.9 parts of degradable amine curing agent, 8.2 parts of degradable thiol curing agent, 60 parts of silica powder, and 133.3 parts of butanone were mixed to obtain a homogeneously dispersed glue solution. The gelation time (GT) of the glue solution was tested as 420s. A 2116 glass fiber cloth was impregnated into the composition for sizing, then baked in an oven at 155° C. for 5 min to prepare a prepreg.

[0053] Several prepregs were laminated, covered with electrolytic copper foils having a thickness of 35 μm onto each of the upper and bottom surfaces, hot-pressed in a vacuum press in accordance with an established procedure at 180° C. and 35 kgf/cm.sup.2 for 90 min to prepare a double-sided copper clad laminate having a thickness of 0.6 mm.

EXAMPLE 4

[0054] O-cresol novolac epoxy resin EPON164, having an epoxy equivalent of 225 g/mol, from MOMENTIVE.

[0055] Degradable amine curing agent

##STR00011##

prepared according to the process disclosed in CN103249712A.

[0056] Degradable thiol curing agent

##STR00012##

prepared according to the process disclosed in CN103249712A.

[0057] Silica powder, DS1032, from LIANYUNGANG DONGHAI SILICON MICROPOWDER CO., LTD

[0058] Butanone, Lanzhou Petrochemical Company

[0059] 100 parts of o-cresol novolac epoxy resin, 15.2 parts of degradable amine curing agent, 31.5 parts of degradable thiol curing agent, 60 parts of silica powder, and 133.3 parts of butanone were mixed to obtain a homogeneously dispersed glue solution. The gelation time (GT) of the glue solution was tested as 230s. A 2116 glass fiber cloth was impregnated into the composition for sizing, then baked in an oven at 155° C. for 8 min to prepare a prepreg.

[0060] Several prepregs were laminated, covered with electrolytic copper foils having a thickness of 35 μm onto each of the upper and bottom surfaces, hot-pressed in a vacuum press in accordance with an established procedure at 180° C. and 35 kgf/cm.sup.2 for 90 min to prepare a double-sided copper clad laminate having a thickness of 0.6 mm.

EXAMPLE 5

[0061] Bisphenol A epoxy resin DER 530, having an epoxy equivalent of 430 g/mol, from DOW CHEMICAL.

[0062] Degradable amine curing agent

##STR00013##

prepared according to the process disclosed in CN103249712A.

[0063] Degradable thiol curing agent

##STR00014##

prepared according to the process disclosed in CN103249712A.

[0064] Butanone, Lanzhou Petrochemical Company

[0065] 125 parts of bisphenol A epoxy resin, 10 parts of degradable amine curing agent, 21 parts of degradable thiol curing agent, and 72 parts of butanone were mixed to obtain a homogeneously dispersed glue solution. The gelation time (GT) of the glue solution was tested as 245s. A 2116 glass fiber cloth was impregnated into the composition for sizing, then baked in an oven at 155° C. for 5 min to prepare a prepreg.

[0066] Several prepregs were laminated, covered with electrolytic copper foils having a thickness of 35 μm onto each of the upper and bottom surfaces, hot-pressed in a vacuum press in accordance with an established procedure at 180° C. and 35 kgf/cm.sup.2 for 90 min to prepare a double-sided copper clad laminate having a thickness of 0.6 mm.

EXAMPLE 6

[0067] Bisphenol A epoxy resin DER 530, having an epoxy equivalent of 430 g/mol, from DOW CHEMICAL.

[0068] Degradable amine curing agent

##STR00015##

prepared according to the process disclosed in CN103249712A.

[0069] Degradable thiol curing agent

##STR00016##

prepared according to the process disclosed in CN103249712A.

[0070] Silica powder, DS1032, from LIANYUNGANG DONGHAI SILICON MICROPOWDER CO., LTD

[0071] Butanone, Lanzhou Petrochemical Company

[0072] 125 parts of bisphenol A epoxy resin, 12.4 parts of degradable amine curing agent, 26.1 parts of degradable thiol curing agent, 40 parts of silica powder, and 100 parts of butanone were mixed to obtain a homogeneously dispersed glue solution. The gelation time (GT) of the glue solution was tested as 220s. A 2116 glass fiber cloth was impregnated into the composition for sizing, then baked in an oven at 155° C. for 5 min to prepare a prepreg.

[0073] Several prepregs were laminated, covered with electrolytic copper foils having a thickness of 35 μm onto each of the upper and bottom surfaces, hot-pressed in a vacuum press in accordance with an established procedure at 180° C. and 35 kgf/cm.sup.2 for 90 min to prepare a double-sided copper clad laminate having a thickness of 0.6 mm.

EXAMPLE 7

[0074] Bisphenol A epoxy resin DER 530, having an epoxy equivalent of 430 g/mol, from DOW CHEMICAL.

[0075] Degradable amine curing agent

##STR00017##

prepared according to the process disclosed in CN103249712A.

[0076] Degradable thiol curing agent

##STR00018##

prepared according to the process disclosed in CN103249712A.

[0077] Silica powder, DS1032, from LIANYUNGANG DONGHAI SILICON MICROPOWDER CO., LTD

[0078] Butanone, Lanzhou Petrochemical Company

[0079] 125 parts of bisphenol A epoxy resin, 8.3 parts of degradable amine curing agent, 17.4 parts of degradable thiol curing agent, 55 parts of silica powder, and 100 parts of butanone were mixed to obtain a homogeneously dispersed glue solution. The gelation time (GT) of the glue solution was tested as 265s. A 2116 glass fiber cloth was impregnated into the composition for sizing, then baked in an oven at 155° C. for 5 min to prepare a prepreg.

[0080] Several prepregs were laminated, covered with electrolytic copper foils having a thickness of 35 μm onto each of the upper and bottom surfaces, hot-pressed in a vacuum press in accordance with an established procedure at 180° C. and 35 kgf/cm.sup.2 for 90 min to prepare a double-sided copper clad laminate having a thickness of 0.6 mm.

EXAMPLE 8

[0081] Bisphenol A epoxy resin DER 530, having an epoxy equivalent of 430 g/mol, from DOW CHEMICAL.

[0082] Degradable amine curing agent

##STR00019##

prepared according to the process disclosed in CN103249712A.

[0083] Degradable thiol curing agent

##STR00020##

prepared according to the process disclosed in CN103249712A.

[0084] Silica powder, DS1032, from LIANYUNGANG DONGHAI SILICON MICROPOWDER CO., LTD

[0085] Butanone, Lanzhou Petrochemical Company

[0086] 125 parts of bisphenol A epoxy resin, 20 parts of degradable amine curing agent, 21 parts of degradable thiol curing agent, 60 parts of silica powder, and 133.3 parts of butanone were mixed to obtain a homogeneously dispersed glue solution. The gelation time (GT) of the glue solution was tested as 330s. A 2116 glass fiber cloth was impregnated into the composition for sizing, then baked in an oven at 155° C. for 3 min to prepare a prepreg.

[0087] Several prepregs were laminated, covered with electrolytic copper foils having a thickness of 35 μm onto each of the upper and bottom surfaces, hot-pressed in a vacuum press in accordance with an established procedure at 180° C. and 35 kgf/cm.sup.2 for 90 min to prepare a double-sided copper clad laminate having a thickness of 0.6 mm.

EXAMPLE 9

[0088] Bisphenol A epoxy resin DER 530, having an epoxy equivalent of 430 g/mol, from DOW CHEMICAL.

[0089] Degradable amine curing agent

##STR00021##

prepared according to the process disclosed in CN103249712A.

[0090] Degradable thiol curing agent

##STR00022##

prepared according to the process disclosed in CN103249712A.

[0091] Silica powder, DS1032, from LIANYUNGANG DONGHAI SILICON MICROPOWDER CO., LTD

[0092] Butanone, Lanzhou Petrochemical Company

[0093] 125 parts of bisphenol A epoxy resin, 20 parts of degradable amine curing agent, 26 parts of degradable thiol curing agent, 60 parts of silica powder, and 133.3 parts of butanone were mixed to obtain a homogeneously dispersed glue solution. The gelation time (GT) of the glue solution was tested as 330s. A 2116 glass fiber cloth was impregnated into the composition for sizing, then baked in an oven at 155° C. for 3 min to prepare a prepreg.

[0094] Several prepregs were laminated, covered with electrolytic copper foils having a thickness of 35 μm onto each of the upper and bottom surfaces, hot-pressed in a vacuum press in accordance with an established procedure at 180° C. and 35 kgf/cm.sup.2 for 90 min to prepare a double-sided copper clad laminate having a thickness of 0.6 mm.

COMPARISON EXAMPLE 1

[0095] Bisphenol A epoxy resin DER 530, having an epoxy equivalent of 430 g/mol, from DOW CHEMICAL.

[0096] Degradable amine curing agent

##STR00023##

prepared according to the process disclosed in CN103249712A.

[0097] Silica powder, DS1032, from LIANYUNGANG DONGHAI SILICON MICROPOWDER CO., LTD

[0098] Butanone, Lanzhou Petrochemical Company

[0099] 100 parts of bisphenol A epoxy resin, 16 parts of degradable amine curing agent, 60 parts of silica powder, and 133.3 parts of butanone were mixed to obtain a homogeneously dispersed glue solution. The gelation time (GT) of the glue solution was tested as over 1000s. A 2116 glass fiber cloth was impregnated into the composition for sizing, then baked in an oven at 155° C. for 15 min to prepare a prepreg.

[0100] Several prepregs were laminated, covered with electrolytic copper foils having a thickness of 35 μm onto each of the upper and bottom surfaces, hot-pressed in a vacuum press in accordance with an established procedure at 180° C. and 35 kgf/cm.sup.2 for 90 min to prepare a double-sided copper clad laminate having a thickness of 0.6 mm.

COMPARISON EXAMPLE 2

[0101] Bisphenol A epoxy resin DER 530, having an epoxy equivalent of 430 g/mol, from DOW CHEMICAL.

[0102] Degradable thiol curing agent

##STR00024##

prepared according to the process disclosed in CN103249712A.

[0103] Silica powder, DS1032, from LIANYUNGANG DONGHAI SILICON MICROPOWDER CO., LTD

[0104] Butanone, Lanzhou Petrochemical Company

[0105] 100 parts of bisphenol A epoxy resin, 33.4 parts of degradable thiol curing agent, 60 parts of silica powder, and 133.3 parts of butanone were mixed to obtain a homogeneously dispersed glue solution. The gelation time (GT) of the glue solution was tested as 45s. A 2116 glass fiber cloth was impregnated into the composition for sizing, then baked in an oven at 155° C. for 2 min to prepare a prepreg.

[0106] Several prepregs were laminated, covered with electrolytic copper foils having a thickness of 35 μm onto each of the upper and bottom surfaces, hot-pressed in a vacuum press in accordance with an established procedure at 180° C. and 35 kgf/cm.sup.2 for 90 min to prepare a double-sided copper clad laminate having a thickness of 0.6 mm.

[0107] As for the degradation and recovery method of copper clad laminates, the following process was used in Examples 1-4 and Comparative Examples 1-2. Copper foils were etched from the copper foil laminate to obtain a recoverable copper recovery solution. The core plate from which the copper foils were etched was placed into an ethylene glycol solvent, to adjust the pH to 4-6 with hydrochloric acid, hold at 100° C. for 2 h, completely degrade the resin to obtain a glass fiber cloth and a degradation solution. The degradation solution was filtered to obtain a filler. Sodium hydroxide was added dropwise into the remaining degradation solution to adjust the pH thereof to 7, to precipitate the resin composition, filter, dry to obtain a linear resin, so as to achieve the recovery of all components in the copper clad laminates.

[0108] As for the copper clad laminates produced above, the glass transition temperature (Tg), peeling strength, interlayer adhesion and dip soldering resistance thereof were measured. The test results are shown in Table 1 and Table 2 below.

TABLE-US-00001 TABLE 1 Test Exam- Exam- Exam- Exam- Exam- Test items conditions ple 1 ple 2 ple 3 ple 4 ple 5 Tg(° C.) DSC 138 125 110 165 139 Peeling A 1.46 0.90 1.25 1.35 1.51 Strength (N/mm) Interlayer Axe blade 0.75 0.28 0.32 0.70 0.82 Adhesion method (N/mm) Dip 288° C. >300 25 65 >300 >300 soldering Limit resistance with (S) copper Degrad- Degrad- Degrad- Degrad- Degrad- Degrad- ability able able able able able

TABLE-US-00002 TABLE 2 Test Comp. Comp. Test items conditions Example 6 Example 7 Example 8 Example 9 Example 1 Example 2 Tg(° C.) DSC 136 132 140 142 95 118 Peeling A 1.32 1.47 1.40 1.41 0.75 0.45 Strength (N/mm) Interlayer Axe blade 0.73 0.81 0.71 0.70 0.12 0.1 Adhesion method (N/mm) Dip soldering 288° C. 240 260 >300 >300 10 5 resistance (S) Limit with copper Degradability Degradable Degradable Degradable Degradable Degradable Degradable

[0109] The methods for the performance tests above are as follows.

[0110] Tg: GBT 19466.2-2004;

[0111] Interlayer adhesion: peeling off with a knife 2 layers, about 20 mm, of adhesive sheets from the sample, clamping the sample on the test fixture, fixing the upper and lower ends, so as to make the sample maintain a vertical state, applying a tension force at a rate of 50 mm/min in the vertical direction, separating the same with axe blade for at least 50 mm, reading the data, to obtain the test results.

[0112] Dip soldering resistance: GB/T 4722-92;

[0113] Peeling strength: Tested by using IPC-TM-650 2.4.8 method;

[0114] Degradability: Methods described in Examples and Comparison Examples.

[0115] According to the examples and comparison examples, it can be seen that the use of a degradable amine as a curing agent for an epoxy resin alone is detrimental to the process control in the manufacturing process of copper-clad laminates, since it has a low reactivity and a long gelation time; the copper clad laminates have a poor performance. The use of degradable thiol alone as a curing agent for epoxy resin is not conducive to the process control in the manufacturing process of CCLs, due to its high reactivity and too short gelation time; the CCLs obtained have a poor performance. The equivalent ratio of epoxy group to active hydrogen also needs to be controlled within a reasonable range, otherwise it will lead to incomplete curing of CCLs or curing agent residual, thus affecting the performance of CCLs. By reasonably combining degradable amine and thiol curing agents, the reaction activity is moderate, and the process control is simple, so as to prepare CCLs having excellent comprehensive performance and to realize effective and green recovery.

[0116] The applicant claims that the present invention describes the detailed process of the present invention, but the present invention is not limited to the detailed process of the present invention. That is to say, it does not mean that the present invention shall be carried out with respect to the above-described detailed process of the present invention. Those skilled in the art shall know that any improvements to the present invention, equivalent replacement of the raw materials of the present invention, addition of auxiliary, selection of any specific ways all fall within the protection scope and disclosure scope of the present invention.