WO2016019547A1

WO2016019547A1 - Thermosetting resin composition

Info

Publication number: WO2016019547A1
Application number: PCT/CN2014/083890
Authority: WO
Inventors: 柴颂刚; 郝良鹏
Original assignee: 广东生益科技股份有限公司
Priority date: 2014-08-07
Filing date: 2014-08-07
Publication date: 2016-02-11

Abstract

The present invention relates to a thermosetting resin composition, the composition comprising: 20-70 mass% of a thermosetting resin, 1-30 mass% of a curing agent, 0-10 mass% of an accelerator and 1-70 mass% of a high comparative tracking index (CTI) filler with an average particle size of 0.5 μm -15 μm; and the present invention further relates to a copper-clad plate made from the thermosetting resin composition. A composite material prepared from the thermosetting resin composition described in the present invention can have a high comparative tracking index, the highest CTI of the copper-clad plate prepared therefrom can reach not less than 600 V, and meanwhile, the alkali resistance of the plates is not influenced, which has an important economic significance.

Description

Thermosetting resin composition

The present invention relates to the field of copper clad laminates, and in particular to a resin composition, and more particularly to a thermosetting resin composition and a copper clad laminate produced therewith.

Background technique

As the electronic direction is light, thin, short and multi-functional, the printed circuit board, which is mainly supported by electronic components, is also moving toward thinness, miniaturization and high density. With the dense line, the line between the lines The insulation reliability can put forward higher requirements, especially under relatively harsh conditions.

When the surface of the insulating substrate of the board is contaminated by dust, moisture, condensation or moisture, and ionic contaminants, the leakage current of the surface is greatly increased due to the applied voltage, and the heat generated by the leakage current is greatly increased. Evaporation of wet contaminants causes the surface of the insulating substrate to be unstable, which is prone to sparks, which reduces the insulation and, in severe cases, breaks through short circuits or opens circuits.

Ordinary epoxy copper clad laminates have a relatively low tracking index and are generally difficult to reach.

240V, therefore, the improvement of the CTI (Comparative Tracking Index) has become the focus of research and development in the field of electronic technology.

CN101578010A discloses a high-comparison leakage tracking index lead-free compatible CEM-3 copper clad plate preparation method, which uses aluminum hydroxide filler to prepare high CTI CEM-3 plate. Although aluminum hydroxide has a high CTI, the aluminum hydroxide has poor chemical resistance, and when it is added too much, it will cause defects in chemical resistance in the processing of PCB.

CN102093670A discloses a method of preparing a high CTI copper clad laminate using barium sulfate. However, in this method, the barium sulfate ratio is large, and it is easy to settle in the laminate glue, which increases the difficulty in manufacturing the laminate. Therefore, how to produce a high-rise tracking index (CTI) while ensuring its excellent chemical resistance is an urgent problem to be solved.

Summary of the invention

An object of the present invention is to provide a resin composition, in particular, a thermosetting resin composition and a copper clad laminate produced using the composition.

To achieve the object of the present invention, the present invention adopts the following technical solutions:

In a first aspect, the present invention provides a thermosetting resin composition comprising the components and their weight percentages as follows: thermosetting resin 20-70% by mass, curing agent 1-30% by mass, accelerator 0-10% by mass High CTI filler 1-70% by mass; the high CTI filler comprises at least calcium fluoride.

As a preferred technical solution, the high CTI filler is subjected to surface treatment.

Preferably, the surface treatment is treated with a surfactant.

Preferably, the surfactant is any one or a mixture of at least two of cationic, anionic, amphoteric or neutral surfactants.

Preferably, the surfactant is a silane coupling agent, a titanate treating agent, an aluminate, a zirconate, stearic acid, oleic acid, lauric acid and metal salts thereof, a phenol resin, a silicone oil Or any one or a mixture of at least two polyethylene glycols.

As a preferred technical solution, the high CTI filler may be selected from the group consisting of aluminum hydroxide, barium sulfate, barium titanate, barium titanate, talc or titanium dioxide, or a mixture of at least two, in addition to calcium fluoride. .

Preferably, the calcium fluoride has an average particle diameter of 0.5 to 15 μm, preferably 1-10 μm, and further preferably 1-5 μη.

Preferably, the calcium fluoride content is from 1 to 70% by mass, preferably from 5 to 50% by mass, and more preferably from 10 to 40% by mass. As a preferred technical solution, the thermosetting resin is any one or a mixture of at least two of an epoxy resin, a cyanate ester, a bismaleimide, a polyimide, or a polybutadiene resin.

The present invention adds calcium fluoride to increase the relative tracking index (CTI) of the substrate, and is suitable for a halogen-based or halogen-free system, and has a remarkable effect.

Preferably, the thermosetting resin is any one or a mixture of at least two of a bisphenol A epoxy resin, an aliphatic epoxy resin or an alicyclic epoxy resin having a number average molecular weight of 500 to 4000.

As a preferred embodiment, the curing agent is an amine and/or an acid anhydride.

Preferably, the curing agent is any one or a mixture of at least two of dicyandiamide, diaminodiphenyl sulfone or diaminodiphenylmethane.

As a preferred technical solution, the resin composition of the present invention further includes a flame retardant.

Preferably, the flame retardant is a triazine compound and/or melamine and a salt thereof.

The present invention may also add a non-high CTI filler such as silica or the like.

In a second aspect, the present invention also provides a laminate produced using the thermosetting resin composition of the present invention, which comprises a prepreg.

Preferably, the prepreg comprises the thermosetting resin composition of the present invention to which the reinforcing material core is attached by dipping and drying.

As a preferred technical solution, the reinforcing material is any one of a natural fiber, an organic synthetic fiber, an organic fabric or an inorganic fiber or a mixture of at least two.

In a third aspect, the present invention further provides a method of increasing the tracking index (CTI) of a laminate compared to a thermosetting resin composition of the present invention.

Preferably, the thermosetting resin composition comprises a high CTI filler, and the high CTI filler comprises at least calcium fluoride.

The invention adopts direct addition of calcium fluoride to improve the compared tracking index (CTI) of the substrate, and the effect Obviously, the side effects are small. Fluoride of the same family of calcium, such as barium fluoride, magnesium fluoride, barium fluoride and barium fluoride, is not suitable for electronic products; fluoride of the same family of fluoride, such as calcium chloride, calcium bromide, iodine Calcium and calcium telluride are soluble in water, releasing ions, which affect the insulation of electronic materials, and are not suitable for use in electronic materials.

Compared with the prior art, the present invention has the following beneficial effects:

(1) The present invention adopts a filler directly added with a high tracking tracking index to improve the leakage tracking index of the copper clad laminate, and can make the CTI value reach 300 V or more, wherein when the calcium fluoride filler is used alone, The CTI value reaches the maximum value and achieves 600V or more.

(2) The invention separately adds the filler calcium fluoride with high leakage tracking index, solves the problem that the aluminum hydroxide filler has poor alkali resistance, and the barium sulfate is easy to settle, and the obtained copper clad plate has enhanced alkali resistance. 10% NaOH, at 80 ° C for two hours, no white spots appeared, and finally obtained a comprehensive performance of the copper clad laminate.

(3) When the calcium fluoride is mixed with other high CTI fillers in the present invention, the same CTI can be achieved, the amount of other high CTI fillers can be reduced, and some problems caused by the addition of other fillers can be improved, such as improving the resistance of the aluminum hydroxide filler. The problem of poor alkalinity and easy settlement of barium sulfate finally resulted in a copper clad laminate with excellent comprehensive properties. Concrete H ^

The technical solution of the present invention will be further described below by way of specific embodiments.

It should be understood by those skilled in the art that the present invention is not to be construed as limiting the invention.

The codes and their components used in the examples and comparative examples are as follows:

Thermosetting Resin A: Represents epoxy resin produced by Dow in the United States under the trade name DER530. The oxygen equivalent was 435 g/eq and the bromine content was 19 wt%.

Thermosetting Resin B: Represents a phenolic epoxy resin produced by American Lucerne Chemical Company (formerly American Bolton Chemical Company and Becklet, Germany) under the trade name EPR627-MEK80 with an epoxy equivalent of 160~250g/eq.

The curing agent is dicyandiamide, produced by Ningxia Darong.

The accelerator represents the 2MI produced by the Shikoku Chemicals Corporation of Japan.

Filler A represents calcium fluoride and has an average particle size of 3 μηι.

Filler Β represents the aluminum hydroxide of Sumitomo, Japan, under the trade name C-302A, with an average particle size of 2-3μη. Filler C represents the barium sulfate of Guizhou Red Star, and the trade name is ΒΜ/Ε.

Filler D represents the barium titanate of Shandong Guohua, the trade name is ΒΤ-300.

Filler Ε represents Shanghai Dianyang's barium titanate, trade name is barium titanate.

Example 1-8

The composition of the solid ingredients of Examples 1-8 is shown in Table 1, wherein Example 1 added 10 g of calcium fluoride, Example 2 added 50 g of calcium fluoride, 50 g of barium sulfate, and Example 3 added 100 g of Calcium fluoride and 50 g of barium sulfate, Example 4 added 150 g of calcium fluoride, Example 5 added 50 g of calcium fluoride and 50 g of barium titanate, and Example 6 added 50 g of calcium fluoride and 50 g of barium titanate, Example 7 added 50 g of calcium fluoride, and Example 8 added 100 g of calcium fluoride.

The thermosetting epoxy resin varnish used in the manufacture of a laminate was prepared by using methyl ethyl ketone, wherein the solid content was 65%.

The copper-clad substrates of Examples 1-8 were prepared in accordance with the following preparation procedures:

(1) Glue: Add the solvent to the ingredient container, add the solution of thermosetting resin, curing agent solution and accelerator separately when stirring; after stirring for 2 hours, add the filler, continue stirring for 4-8 hours, sample the test glue The gelation time (170 ° C constant temperature hot plate) is 200 to 300 seconds. (2) Impregnation: The layer of reinforcing material impregnated with the glue is passed through a vertical or horizontal impregnation machine. By controlling the conditions of the extrusion wheel speed, line speed, air temperature and furnace temperature, the example of the vertical impregnation machine is specifically : Squeeze wheel speed: -1.3~-2.5±0.1M/min; Main line speed: 4~18m/min; Air temperature: 120~170°C; Furnace temperature: 130~220°C, prepreg obtained by the above conditions .

(3) Pressing: After the cut prepreg is combined with the copper foil, it is placed in a vacuum hot press, and a copper clad plate is finally obtained according to a certain temperature, time and pressure. The specific examples are as follows:

Temperature program: 130 °C /30min+ 155 °C/30min+ 190 °C /90min+220 °C /60min; Pressure program:

25Kgf. cm" ² /30min+50Kgf. cm" ² /30min+90Kgf. cm" ² / 120min+3 OKgf. cm" ² /90min; Vacuum program: 30mmHg/130min+800mmHg/130min.

Through the above procedure, eight prepregs having a thickness of 0.2 mm were laminated between 35 μη thick copper foils, and a 1.6 mm thick laminate was obtained by hot pressing. After obtaining the copper clad laminate, the sheet properties were tested. Table 2 shows the performance comparison of the copper clad laminate.

Comparative example 1-3

Comparative Example 1-3 The composition of the solid component formulation is shown in Table 1. In Comparative Example 1, no filler was added, and in Comparative Example 2, 100 g of barium sulfate was added, and in Comparative Example 3, 100 g of aluminum hydroxide was added.

The thermosetting resin glue used in the manufacture of a laminate was prepared by using methyl ethyl ketone, wherein the solid content was 65%. The preparation methods of Comparative Examples 1-3 are as in Examples 1-8.

1

Filler B/g -- -- -- -- -- -- -- -- -- -- 100 Filler Cg -- 50 50 -- -- -- -- -- -- 100 -- Filler D/g -- -- -- -- 50 -- -- -- -- -- -- Filler E / g -- -- -- -- -- 50 -- -- -- -- -- The copper-clad substrates prepared in Examples 1-8 and Comparative Examples 1-3 were measured in comparison with the tracking index and alkali resistance, and the test results are shown in Table 2.

Table 2

It can be seen from Table 2 that the CTI values of the examples 1-8 are higher than those of the comparative example 1-2 for the CTI value of the copper-clad substrate, and the CTI values of the examples 5-7 are the same as those of the third embodiment, and the examples 3-4 The CTI values of 8 and 8 are higher than that of the embodiment 3, wherein the CTI value of the embodiment 4 is the highest, reaching 600 V or more; for the alkali resistance of the copper-clad substrate, the examples 1-8 are tested, and no white spots are generated. However, in Comparative Example 3, white spots appeared.

The following points can be seen from Examples 1-8 and Comparative Examples 1-3:

(1) In Examples 1, 4, 7 and 8, compared with Comparative Example 1, the CTI value was significantly higher, indicating that the CTI value of the copper-clad substrate was improved due to the addition of the calcium fluoride filler;

(2) In Example 2, compared with Comparative Example 2, although 100 g of the filler was also added, the CTI value of Example 2 was high, indicating that the calcium fluoride selected in the present invention was used in combination with barium sulfate alone. The copper-clad substrate prepared by the ruthenium filler has a higher CTI value;

(3) Compared with Comparative Example 3, the CTI value was significantly increased and the alkali resistance was enhanced, indicating that the selected calcium fluoride can increase the CTI value and alkali resistance accordingly;

(4) In Example 3, as compared with Example 4, 150 g of the filler was also added, but when the filler was all calcium fluoride, the CTI value was higher. In summary, the copper-clad substrate of the present invention can increase the CTI value after adding the calcium fluoride filler; when the filler is selected with calcium fluoride and other high CTI fillers, it can be improved compared with other high CTI fillers alone. The CTI value of the copper-clad substrate, and other problems caused by excessive use of other CTI fillers, has better comprehensive performance; the use of a higher content and a single component of calcium fluoride can make the copper-clad substrate The CTI value is obviously improved, reaching 600V or above, and the overall performance is optimal, and it has strong alkali resistance and is suitable for industrial mass production. The Applicant declares that the present invention illustrates the process of the present invention by the above-described embodiments, but the present invention is not limited to the above process steps, that is, it does not mean that the present invention must rely on the above process steps to be implemented. It will be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of the materials selected for the present invention, and the addition of the auxiliary ingredients, the selection of the specific means, etc., are all within the scope of the present invention.

Claims

WO 2016/019547 Claim PCT/CN2014/083890

A thermosetting resin composition characterized by comprising the following components in a weight percentage: thermosetting resin 20-70% by mass, curing agent 1-30% by mass, accelerator 0-10% by mass, and high CTI filler 1- 70% by mass; the high CTI filler contains at least calcium fluoride.

The thermosetting resin composition according to claim 1, wherein the high CTI filler is surface-treated.

The thermosetting resin composition according to claim 2, wherein the surface treatment is treated with a surfactant.

The thermosetting resin composition according to claim 3, wherein the surfactant is any one or a mixture of at least two of a cationic type, an anionic type, an amphoteric or a neutral surfactant.

The thermosetting resin composition according to claim 4, wherein the surfactant is a silane coupling agent, a titanate treating agent, an aluminate, a zirconate, stearic acid, or oleic acid. Any one or a mixture of at least two of lauric acid and a metal salt thereof, a phenol resin, a silicone oil or a polyethylene glycol.

The thermosetting resin composition according to claim 1, wherein the high CTI filler is selected from the group consisting of aluminum hydroxide, barium sulfate, barium titanate, barium titanate, and talc powder, in addition to calcium fluoride. Or any one or a mixture of at least two of titanium dioxide.

The thermosetting resin composition according to claim 1, wherein the calcium fluoride has an average particle diameter of from 0.5 to 15 μm, preferably from 1 to 10 μm, more preferably from 1 to 5 μm.

The thermosetting resin composition according to claim 1, wherein the calcium fluoride content is from 1 to 70% by mass, preferably from 5 to 50% by mass, and more preferably from 10 to 40% by mass.

The thermosetting resin composition according to claim 1, wherein the thermosetting resin is an epoxy resin, a cyanate ester, a bismaleimide, a polyimide or a polybutadiene resin. Any one Kind or a mixture of at least two.

The thermosetting resin composition according to claim 1, wherein the thermosetting resin is a bisphenol A epoxy resin having a number average molecular weight of 500 to 4000, an aliphatic epoxy resin or an alicyclic epoxy resin. Any one or a mixture of at least two.

The thermosetting resin composition according to claim 1, wherein the curing agent is an amine and/or an acid anhydride.

The thermosetting resin composition according to claim 1, wherein the curing agent is any one or a mixture of at least two of dicyandiamide, diaminodiphenyl sulfone or diaminodiphenylmethane.

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

The thermosetting resin composition according to claim 13, wherein the flame retardant is a triazine compound and/or melamine or a salt thereof.

A laminate produced by using the thermosetting resin composition according to any one of claims 1 to 14, characterized in that it comprises a prepreg.

The laminate according to claim 15, wherein the prepreg comprises a reinforcing material; and a thermosetting resin composition adhered thereto by dipping and drying.

The laminate according to claim 16, wherein the reinforcing material is any one or a mixture of at least two of natural fibers, organic synthetic fibers, organic fabrics or inorganic fibers.

A method for improving a tracking index of a leakage of a laminate, characterized in that the thermosetting resin composition according to any one of claims 1 to 14 is used.