CN102390145B - Environment-friendly copper clad laminate and preparation method thereof - Google Patents

Abstract

The invention discloses an environment-friendly copper clad laminate and a preparation method thereof. A resin material in the laminate is an epoxy resin modified by a polyimide resin, and carbonate type aluminum magnesium hydrotalcite is added into a modified resin system. The preparation method for the environment-friendly copper clad laminate mainly comprises the following steps of: synthesizing the polyimide resin; and modifying the epoxy resin by using the polyimide resin, and preparing gelatinizing liquid by using the epoxy resin modified by the polyimide resin and the carbonate type aluminum magnesium hydrotalcite. The epoxy resin is modified by using the polyimide resin, so the crosslinking density of the environment-friendly copper clad laminate is much higher than that of the conventional epoxy resin; the environment-friendly copper clad laminate does not contain halogen or phosphorus, contains N, Al and Mg elements, and meets environmental protection requirements of European union restriction of hazardous substances (RoHS) and waste electrical and electronic equipment (WEEE) Directives; meanwhile, the heat resistance is also greatly improved, so that the environment-friendly copper clad laminate is more suitable for lead-free welding processes for printed circuit boards (PCB).

Description

The preparation method of environment-friendly type copper-clad laminate

Technical field

The invention belongs to copper-clad laminate (abbreviation copper-clad plate) technical field, be specifically related to material behavior and the manufacture craft of copper-clad plate.

Background technology

Copper-clad laminate used for printed circuit, all has fire-retardant characteristic, and traditional copper-clad plate is to adopt in halogen series bromine (Br) as fire retardant mostly.FR-1 in paper base plate, FR-2 series, CEM-1, CEM-3 series in FR-4, FR-5 series and composite base plate in glass fabricbase, these copper-clad plates are all adopt brominated epoxy resin or add other bromide fire retardant.In recent years, along with the promulgation of the RoHS of European Union, WEEE environmental protection instruction, halogens was put among electric equipment products banned substance because its burning produces nuisance dioxin afterwards.Therefore, non-halogen copper-clad plate fire retardant used turns to phosphorous flame-retardant aspect, current generally use be phosphorous epoxy resin.But P elements also can produce harm to environment after burning, as makes soil acidification etc.

In RoHS instruction, also specified must not contain lead element in electric equipment products, PCB welding material must be converted into lead-free solder by the original kupper solder that has so.The welding temperature of lead-free solder is higher 20～40 DEG C than the temperature that has kupper solder, and therefore, the heat resistance of copper-clad plate also must meet the requirement of this high-temperature soldering, has high heat decomposition temperature and heat-resisting quantity.Therefore, environmental protection PCB truly should be not halogen-containing, not phosphorous, not leaded, wants copper-clad plate non-halogen non-phosphate pb-free solder compatibility.

Summary of the invention

The object of the invention is to provide a kind of preparation method of environment-friendly type copper-clad laminate, not only has the environmental protection characteristic of non-halogen non-phosphate, also has the resistance to elevated temperatures being suitable for without lead welding.

A preparation method for environment-friendly type copper-clad laminate, comprises the following steps: the synthesis step of (1) polyimide resin; (2) make polyimide resin modified epoxy, and and the step of carbonate type magnalium hydrotalcite mixing manufacture gluing glue; (3) step to glass cloth gluing making prepreg; (4) by the step of prepreg and copper foil laminate, matching board and pressing; (5) tear the step of plate, sharp processing, inspection, packaging open.

The synthetic of described polyimide resin comprises: (1) metered DMF is warming up to 60～70 DEG C, under stirring, adds DDM, stirs 10～15min and is dissolved to bright completely; (2) when temperature rises to 80～90 DEG C, add BDM, stir and heat up, after 6～10min,, solution is bright when the temperature recovery to 85～90 DEG C; (3) be warming up to 125～130 DEG C, and control constant temperature, after this thermotonus 30～40min, vacuumize dehydration 3～5min; (4) approximately 60～70min of constant temperature, sampling, the GT:10 ± 1min/171 DEG C of control glue, the solids content 48～50% of glue; Wherein in above step, the mass ratio that feeds intake of DMF, DDM, BDM is 40～60%/9～12%/30～50%.

Describedly make gluing glue by polyimide resin and carbonate type magnalium hydrotalcite and comprise: (1), by the described polyimide resin of metering, adds the DMF of metering, is heated to 50～60 DEG C; (2) add Fj-43 type novolac epoxy resin, the E-20 type epoxy resin stirring and dissolving of pulverizing, after 40～50min, dissolve completely; (3) add again E-51 type epoxy resin, stir 30～40min, be cooled to room temperature; (4) add the carbonate type magnalium hydrotalcite of metering, dispersed with stirring, slaking 4～6h; Wherein in above step, the glue of polyimide resin, Fj-43 type novolac epoxy resin, E-20 type epoxy resin, E-51 type epoxy resin, DMF, the carbonate type magnalium hydrotalcite mass ratio that feeds intake is: 40～55%/1～3%/10～18%/1～3%/10～18%/15～20%.

Environment-friendly type copper-clad laminate provided by the invention, owing to having used polyimide resin modified epoxy, high more a lot, not halogen-containing, not phosphorous than conventional cross linking of epoxy resin density, contain N, Al, Mg element, reached the environmental requirement of the RoHS of European Union and WEEE instruction; Heat resistance is also able to very large improvement simultaneously, is more suitable for being applicable to the pb-free solder technique of PCB.

Brief description of the drawings

The production technological process that Fig. 1 provides for the embodiment of the present invention.

Detailed description of the invention

Keynote idea of the present invention is in copper-clad plate resin material used, to add N element environmental protection more, that simultaneously have anti-flaming function and Al element, and it is coordinated according to a certain percentage, utilizes its cooperative effect each other, reaches flame retardant effect.

Resin material in the copper-clad plate providing based on above-mentioned thought the present embodiment is selected polyimide resin, with modified epoxy, and then add carbonate type magnalium hydrotalcite, make to form N, AL, Mg(OH) ₂composite flame retardant system, heat resistance is also effectively ensured simultaneously.

Wherein, polyimide resin has outstanding heat resistance, and contains N element, and N content approximately 9.0%, has certain anti-flammability.In addition, described carbonate type magnalium hydrotalcite, is called for short LDHs, and chemical formula is: [Mg ₆al ₂(OH) ₁₆cO ₃] 4H ₂o, wherein contains the hydrate of Al, Mg, is called for short again magnalium hydrotalcite.Magnalium hydrotalcite has the feature of nontoxic, low cigarette, high performance-price ratio, can be used as the preferred inorganic combustion inhibitor of the present embodiment.

The manufacturing process of the copper-clad plate that the present embodiment provides is as follows:

One, material.

4,4 '-dimaleoyl imino diphenyl-methane (BDM), chemical formula is as follows:

Two amido diphenyl-methanes (DDM), chemical formula is as follows:

The E type epoxy resin of E-51 type;

The E type epoxy resin of E-20 type;

The orthoresol phenolic aldehyde epoxy of Fj-43 type;

Dimethyl formamide (DMF);

Carbonate type magnalium hydrotalcite: particle diameter 5 μ m;

7628 type glass fabrics;

Electrolytic copper foil.

Two, polyimide resin is synthetic.

Material therefor and measure as shown in the table:

Material	Mass ratio feeds intake
		BDM	895
DDM	198
		DMF	1093

(1) metered DMF is warming up to 70 DEG C, under stirring, adds DDM, stirs 10min and is dissolved to bright completely.

(2) when temperature rises to 80 DEG C, add BDM, stir and heat up, after 6min, when temperature recovery to 85 DEG C, solution is bright.

(3) be warming up to 125～130 DEG C, and control constant temperature, after this thermotonus 30min, vacuumize dehydration 5min.(this dehydration object, just in order to slough the moisture content of the absorption in material, does not have moisture content to produce in course of reaction)

(4) approximately 60～70min left and right of constant temperature, sampling, the GT:10 ± 1min/171 DEG C of control glue, the solids content of glue approximately 50%.

Three, the making of gluing glue.

Material	The glue mass ratio that feeds intake
		Polyimide resin	200
Fj-43	8
		E-20	50
E-51	8
		DMF	55
Hydrotalcite	71

(1) by the above-mentioned synthetic polyimides glue of metering, add the DMF of metering, be heated to 50～60 DEG C.

(2) add Fj-43, the E-20 stirring and dissolving of pulverizing, after about 40min, dissolve completely;

(3) add again E-51, stir 30min, be cooled to room temperature.

(4) add the hydrotalcite of metering, dispersed with stirring, slaking 4h.

Four, glass cloth gluing is made the process of prepreg: 7628 glass are distributed in to gluing on fall shaft hlue spreader, dry afterwards.Controlled condition comprises: gluing speed: 12m/min; Oven temperature: 200 DEG C; Prepreg GT controls: 80～100s/171 DEG C; Prepreg indicated weight: 3.6～3.8g/m2(specifically adjusts according to the thickness of making sheet material); RF:18～24% of prepreg.

Five, lamination, matching board, pressing process: by the prepreg of the superimposed corresponding number of technique thickness requirement, as 1.6mm needs 8,1.2mm needs 6, and 1.0mm needs 5; Be covered with electrolytic copper foil, in press, suppress.Controlled condition comprises: press temperature: 200 DEG C/2h; Pressure: vacuum press: 30kg/cm2.

Six, tear plate, sharp processing, inspection, packaging open.

The properties testing result of the copper foil covered plate that lower epi-position is made according to above embodiment:

In test data: T288, Tg, tri-indexs of Td are enough to reflect heat resistance that this sheet material is good and the adaptability of pb-free solder; Content of halogen also embodies the environmental protection characteristic of sheet material.

Claims (1)

1. a preparation method for environment-friendly type copper-clad laminate, comprises the following steps: the synthesis step of (1) polyimide resin; (2) make polyimide resin modified epoxy, and and the step of carbonate type magnalium hydrotalcite mixing manufacture gluing glue; (3) step to glass cloth gluing making prepreg; (4) by the step of prepreg and copper foil laminate, matching board and pressing; (5) tear the step of plate, sharp processing, inspection, packaging open; It is characterized in that:

The synthetic of described polyimide resin comprises: (1) metered DMF is warming up to 60～70 DEG C, under stirring, adds DDM, stirs 10～15min and is dissolved to bright completely; (2) when temperature rises to 80～90 DEG C, add BDM, stir and heat up, after 6～10min,, solution is bright when the temperature recovery to 85～90 DEG C; (3) be warming up to 125～130 DEG C, and control constant temperature, after this thermotonus 30～40min, vacuumize dehydration 3～5min; (4) approximately 60～70min of constant temperature, sampling, the GT:10 ± 1min/171 DEG C of control glue, the solids content 48～50% of glue; Wherein in above step, the mass ratio that feeds intake of DMF, DDM, BDM is 40～60%/9～12%/30～50%;

Describedly make gluing glue by polyimide resin and carbonate type magnalium hydrotalcite and comprise: (1), by the described polyimide resin of metering, adds the DMF of metering, is heated to 50～60 DEG C; (2) add Fj-43 type novolac epoxy resin, the E-20 type epoxy resin stirring and dissolving of pulverizing, after 40～50min, dissolve completely; (3) add again E-51 type epoxy resin, stir 30～40min, be cooled to room temperature; (4) add the carbonate type magnalium hydrotalcite of metering, dispersed with stirring, slaking 4～6h; Wherein in above step, the glue of polyimide resin, Fj-43 type novolac epoxy resin, E-20 type epoxy resin, E-51 type epoxy resin, DMF, the carbonate type magnalium hydrotalcite mass ratio that feeds intake is: 40～55%/1～3%/10～18%/1～3%/10～18%/15～20%.