KR102212721B1 - HALOGEN-FREE PHOSPHORUS-FREE NITROGEN-FREE FlAME RETATDANT RESIN COMPOSITION, PREPREG AND METAL FOIL-CLAD LAMINATES COMPRISING THE SAME - Google Patents

Abstract

The present invention provides a halogen-free, unmanned nitrogen-free flame-retardant resin composition, a prepreg including the same, and a metal clad laminate, wherein the resin composition comprises 100 parts of epoxy resin, 180-250 parts boehmite, 180-300 parts titanium A bag, and 50-170 parts of a curing agent, wherein the curing agent is a non-phenolic hydroxyl-based compound and/or a non-amine-based curing agent. In the present invention, the resin composition finally obtained by using a boehmite and a titanium bag in combination has an HB level of flame retardancy without being affected by reactivity; The resin composition provided by the present invention is halogen-free and nitrogen-free, and when the LED is packaged with an additive-type silica gel, silica gel "poisoning" can be prevented, and the heat resistance and yellowing resistance of the resin composition of the present invention are also LED substrate materials. Can meet the application needs of

Description

Halogen-free and nitrogen-free flame-retardant resin composition, prepreg and metal foil laminate comprising the same.

The present invention belongs to the LED copper clad laminate technology field, and relates to a halogen-free unmanned nitrogen-free flame-retardant resin composition, a prepreg including the same, and a metal clad laminate.

Traditional copper clad laminates for printed circuit boards can be divided into halogen-containing flame-retardant copper clad laminates, phosphorus-containing flame-retardant copper clad laminates, nitrogen-containing flame-retardant copper clad laminates, or composite flame-retardant copper clad laminates including two or three of them according to their flame retardant function. Waste electrical and electronic products containing halogens such as bromine and chlorine release hydrogen halides, which are carcinogens and poisonous substances such as dioxin and dibenzofuran during the combustion process. After officially implementing the environmental protection guidelines in Part 2 of the Treatment Guidelines (WEEE) and the ``Restriction on the Use of Hazardous Substances in Electrical and Electronic Products'' (RoHS), phosphorus-containing flame-retardant copper clad laminates, nitrogen-containing flame-retardant copper clad laminates, or phosphorus, nitrogen co-containing flame-retardant copper foils Laminates developed rapidly. Currently, all of the halogen-free flame-retardant copper clad laminates provided by a large number of companies use a phosphorus-containing flame retardant system or a nitrogen-containing flame retardant system.

Looking at the current direction of the mainstream technology of halogen-free flame-retardant copper clad laminates, it is easy to find that there are mainly a few things as follows: The first is a phosphorus-containing epoxy as the main resin, dicyandiamide (DICY), and a phenolic resin. Or an aromatic amine is used as a curing agent, and a certain amount of an inorganic flame retardant such as aluminum hydroxide, magnesium hydroxide, or the like is added; Second, a general epoxy (ie, a halogen-free epoxy) is used as the main resin, a phosphorus-containing phenol is used as a curing agent, and an appropriate amount of an organic filler or an inorganic filler is added; Third, general epoxy (i.e., halogen-free epoxy) is used as the main resin, DICY, phenolic resin or aromatic amine is used as a curing agent, and a certain amount of phosphorus-containing flame retardant such as phosphazene, phosphate ester, phosphate, etc. is added, It is to add a certain amount of organic fillers or inorganic fillers.

CN100523081C discloses that a phosphorus-containing epoxy resin is used as the main resin and an epoxy resin composition having excellent flame retardancy is obtained by compound curing using benzoxazine, styrene-maleic anhydride and other curing agents. CN103131131A suggested that the composite epoxy resin using benzoxazine, styrene-maleic anhydride, and an amine-based curing agent meets the requirements for use in the flame retardancy of the epoxy resin finally obtained by the nitrogen-containing flame retardant method.

Currently, in LED lighting, as it develops to have multifunctionality, miniaturization, and high yellowing resistance for the loading frame, high yellowing resistance, high heat resistance, and halogen-free unmanned and HB level flame-retardant for the PCB plate for packaging and loading the LED flat plate. Presenting a request. Therefore, a higher demand for halogen-free, unattended flame retardancy and high yellowing resistance for the substrate material was proposed.Compared to the conventional substrate material used in the conventional LED field, such a plate material has a higher glass transition temperature (Tg) And it must have yellowing resistance, and must be able to reach the requirements of halogen-free and HB level flame retardant. In order to improve the flame retardant properties of such a halogen-free unmanned substrate material, a method of adding a flame retardant containing nitrogen, sulfur, etc. is generally used to the system.For example, CN100383172C contains amide and hydroxyl functional groups. Using a flame retardant, first, a halogen-free, unmanned polycyclic compound with high nitrogen content is obtained by reacting with an epoxy resin to obtain a flame-retardant composition, and it is blended with an epoxy resin and inorganic filler to realize a halogen-free and unmanned flame retardant function. The epoxy resin semi-cured material and a composition prepared from the semi-cured material were disclosed.

However, organic substances containing elements such as phosphorus, sulfur, and nitrogen cause the accelerator to lose its effectiveness when the LED is packaged with an additive silica gel (a silica gel "poisoning" phenomenon) and affect the curing of the gel.

Accordingly, there is a need to develop a new resin composition capable of satisfying that the LED substrate material is halogen-free and nitrogen-free, the flame retardant performance can reach the HB level, and meet the heat resistance and yellowing resistance requirements of the substrate material.

An object of the present invention is to provide a halogen-free and nitrogen-free flame-retardant resin composition, a prepreg including the same, and a metal foil laminate. The resin composition provided by the present invention is halogen-free and nitrogen-free, and when packaging the LED with an additive silica gel, silica gel "poisoning" can be prevented, and the flame retardant performance can reach the HB level, and the LED substrate material It satisfies the requirements of the flame retardant performance of, and also satisfies the requirements of the LED substrate material with its heat resistance and yellowing resistance.

The present invention adopts the following technical solutions to achieve the above object:

A first aspect, the present invention provides a halogen-free, unmanned nitrogen-free flame-retardant resin composition, the resin composition comprises the following composition based on parts by weight:

100 parts of epoxy resin;

180-250 parts of Bohemite;

180-300 parts of a titanium bag;

50-170 parts hardener;

Among them, the curing agent is a non-phenolic hydroxyl group (Non-phenolic hydroxyl)-based compound and/or a non-amine-based curing agent.

In the present invention, the resin composition finally obtained by using a combination of boehmite and titanium bag can be secured so that the reactivity is not affected and at the same time has HB-level flame retardancy, and the heat resistance and yellowing resistance of the composition system satisfy the application requirements.

Preferably, the epoxy resin includes a bifunctional epoxy resin and/or a polyfunctional epoxy resin.

Preferably, the bifunctional epoxy resin includes any one or a combination of at least two of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, or a polymer of a bisphenol A type epoxy resin.

Preferably, the epoxy equivalent of the bifunctional epoxy resin is 140-900 g/eq, for example, 200 g/eq, 250 g/eq, 300 g/eq, 350 g/eq, 400 g/eq, 450 g /eq, 500 g/eq, 550 g/eq, 600 g/eq, 650 g/eq, 700 g/eq, 750 g/eq, 800 g/eq, 850 g/eq, and the like.

Preferably, the epoxy equivalent of the multifunctional epoxy resin is 140-900 g/eq, for example, 200 g/eq, 250 g/eq, 300 g/eq, 350 g/eq, 400 g/eq, 450 g /eq, 500 g/eq, 550 g/eq, 600 g/eq, 650 g/eq, 700 g/eq, 750 g/eq, 800 g/eq, 850 g/eq, etc.

Preferably, the polyfunctional epoxy resin is an epoxy resin containing at least 3 epoxy groups in a molecule and having an aromatic ring structure.

Preferably, the polyfunctional epoxy resin is a condensation product of tetraphenol ethane and epichlorohydrin, a novolak type epoxy resin, and a dicyclopentadiene type epoxy resin. epoxy resin) or a biphenyl type epoxy resin, or a combination of at least two.

Preferably, the novolak-type epoxy resin includes a novolac-type epoxy resin produced by reacting phenolic benzaldehyde and a phenolic resin produced by phenol with epichlorohydrin.

Preferably, the phenolic system includes one or a combination of at least two of phenol, ortho-cresol or bisphenol A.

Preferably, the novolak-type epoxy resin includes any one or a combination of at least two of a phenol-type novolac epoxy resin, an orthocresol-type novolac epoxy resin, or a bisphenol A-type novolac epoxy resin.

In the present invention, the boehmite is 180-250 parts, for example, 190 parts, 200 parts, 210 parts, 220 parts, 230 parts, 240 parts, and the like.

Preferably, the boehmite has a particle diameter of 0.5-10 μm, for example 1.0 μm, 2 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, 6 μm, 6.5 μm, 7 μm, 8 μm, 8.5 μm, 9 μm, 9.5 μm, etc.

In the present invention, the titanium bag is 180-300 parts, for example, 190 parts, 200 parts, 210 parts, 220 parts, 230 parts, 240 parts, 250 parts, 260 parts, 270 parts, 280 parts, 290 parts, etc. to be.

Preferably, the titanium bag is a rutile (Rutile) type titanium bag.

Preferably, the average particle diameter of the titanium bag is 0.30 μm or less (≤0.30 μm), for example, 0.25 μm, 0.20 μm, 0.15 μm, 0.10 μm, 0.05 μm, 0.01 μm, and the like.

Preferably, the whiteness of the titanium bag is 98% or more, for example, 98.2%, 98.5%, 99%, 99.1%, 99.2%, 99.5%, and the like.

In the present invention, the curing agent is 50-170 parts, for example, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts, 150 parts, 160 parts, etc. .

Preferably, the curing agent is an acid anhydride-based curing agent.

Preferably, the curing agent includes a copolymer of styrene and maleic anhydride and/or o-phthalic anhydride.

Preferably, the halogen-free nitrogen-free flame-retardant resin composition further includes 0.02-0.1 parts of a curing accelerator, for example, 0.03 parts, 0.05 parts, 0.06 parts, 0.08 parts, and 0.09 parts.

Preferably, the curing accelerator is an imidazole-based curing accelerator.

In a second aspect, the present invention provides a resin adhesive solution obtained by dissolving or dispersing a halogen-free unmanned nitrogen-free flame-retardant resin composition as described in the first aspect in a solvent.

Preferably, the solvent includes a ketone-based solvent and/or an ether-based solvent.

In a third aspect, the present invention provides a prepreg comprising a reinforcing material and the halogen-free unmanned nitrogen-free flame-retardant resin composition as described in the first aspect attached to the reinforcing material through impregnation drying.

Preferably, the reinforcing material is an electronic grade glass cloth.

Preferably, the reinforcing material is a glass fiber nonwoven fabric or a glass fiber woven fabric.

A fourth aspect, the present invention provides a metal foil laminate comprising at least one prepreg as described in the third aspect and a metal foil coated on one or both sides of the prepreg after being superposed.

Preferably, the metal foil is copper foil.

In a fifth aspect, the present invention provides a printed circuit board comprising one or at least two superposed prepregs as described in the third aspect or the metal foil laminate as described in the fourth aspect.

Compared with the existing technology, the present invention has the following advantageous effects:

(1) In the present invention, the resin composition finally obtained by using a boehmite and a titanium bag in combination does not affect the reactivity and has HB-level flame retardancy.

(2) The resin composition provided by the present invention has HB-level flame retardancy and is halogen-free and nitrogen-free, and when packaging the LED with an additive-type silica gel, silica gel "poisoning" can be prevented. The heat resistance and yellowing resistance of the resin composition can also satisfy the application requirements of the LED substrate material.

Hereinafter, the technical solutions of the present invention will be described in detail through specific implementation plans. Those skilled in the art can clearly see that the following examples are only intended to aid understanding of the present invention, and the present invention is not limited by the following examples.

Materials and mutual information mentioned in Examples and Comparative Examples are as follows:

(A) Epoxy resin:

에폭시 수지에서 생산);A-1: Bisphenol A type epoxy resin (NPEL-128E, epoxy equivalent is 187 g/eq, remaining

Produced from epoxy resin);

A-2: Bisphenol A type novolac epoxy resin (EPR627M80, epoxy equivalent is 210 g/eq, produced by Momentive Chemical Co., USA);

에폭시 수지에서 생산);A-3: Bisphenol F type epoxy resin (NPEL-170, epoxy equivalent is 170 g/eq, Nanya

Produced from epoxy resin);

(B) boehmite (APYRAL AOH 30, produced by Nabal tec AG, the particle diameter is D50=1.8 μm);

(C) Titanium bag

C-1: Titanium Bag (R-706, produced by Chemours Chemical Co., USA, particle diameter D50=0.23 μm, whiteness 98%);

회사에서 생산하고, 입경은 D50=0.19 μm이며, 백색도는 95%임);C-2: Titanium bag (CR828, Kemaiji, Australia

Produced by the company, the particle diameter is D50=0.19 μm, and the whiteness is 95%);

C-3: Titanium bag (R-960, produced by Chemours Chemical Co., USA, particle diameter D50=0.40 μm, whiteness 96%);

C-4: Titanium bag (T-RS-3-XF, produced by WuXi Noble Electronics Co., Ltd., the particle diameter is D50 = 20 μm, the whiteness is 93%);

(D) hardener

D-1: Styrene-maleic anhydride (SMA EF30, produced by Cray Valley, USA);

D-2: Styrene-maleic anhydride (SMA EF40, produced by Cray Valley, USA);

D-3: o-phthalic anhydride (produced by Shanghai Nuotai Chemical Co., Ltd.);

회사에서 생산);D-4: Methyl Tetrahydrophthalic Anhydride (Shengshida Guangdong)

Produced by the company);

회사에서 생산);D-5: Amine curing agent DICY (Ningha Darong

Produced by the company);

D-6: phenolic curing agent 759 (produced by ARAKAWA Chemical Industry Co., Ltd.);

(E) hardening accelerator (2-E4MI, produced by Shikoku Chemicals, Japan);

(E) Aluminum hydroxide (OL-104LEO, produced by Albemarle, USA).

Example 1-13

According to the composition shown in Tables 1 and 2, a halogen-free, unmanned nitrogen-free flame-retardant resin composition was prepared (all raw materials used in parts by weight), and a copper clad laminate sample was prepared according to the following manufacturing method:

Each composition according to the amount of the mixing method and propylene glycol monomethyl ether or butanone as a solvent are put in a container and stirred to be uniformly mixed, and the resin of the halogen-free, unmanned nitrogen-free flame retardant resin composition To obtain an adhesive solution.

2116 An electromagnetic-grade glass cloth is impregnated with an adhesive solution, fired with a prepreg through an oven, and then four prepregs are taken, coated with 35 μm thick electrolytic copper foil on both sides, vacuum-laminated in a hot press, and then vacuum-laminated at 190°C/ It cured at 90 min, and the copper clad laminated board sample was manufactured.

Comparative Example 1-9

According to the composition shown in Table 3, a halogen-free, nitrogen-free flame-retardant resin composition was prepared (all raw materials used in parts by weight), and a copper clad laminate sample was prepared according to the method of manufacturing the laminate described in Examples:

Table 1

Table 2

Table 3

Performance test:

The performance of the copper clad laminates provided in Examples 1-13 and Comparative Examples 1-9 was measured, and the test method is as follows:

(1) Glass transition temperature (Tg): Based on differential scanning calorimetry (DSC), it is measured by the DSC method specified in 2.25 of IPC-TM-650.

(2) Whiteness: After etching the substrate, test the whiteness in the A-stage, and then test the whiteness after treatment at 260°C and the whiteness after 24h irradiation with UV light.

(3) PCT: Measured according to the method specified in IPC-TM-650, and the test conditions are 105 KPa, 120 min, 288°C.

(4) Immersion solderability: Measure according to the method specified in IPC-TM-650.

(5) Combustibility: It is measured according to the vertical combustion method of UL 94 standard, and the pretreatment condition of the specimen is 168h treatment at 70℃ constant temperature.

For the test results of the copper clad laminates provided in Examples 1-13 and Comparative Examples 1-9, refer to Table 4-6:

Table 4

Table 5

Table 6

As can be seen from the examples and performance tests, the copper clad laminate made of the resin composition provided by the present invention has a flame retardant performance reaching HB level, and at the same time, has a relatively high whiteness, good yellowing resistance and heat resistance, and meets the application requirements of LED substrates. I can be satisfied.

Comparing Example 3 and Example 8-10, as can be seen, when a titanium bag having an average particle diameter of 0.30 μm or less (≤0.30 μm) and a whiteness of 98% or more (≥98%) is selected, the finally obtained copper clad laminate The whiteness and yellowing resistance of the may be better. As can be seen by comparing Example 1 and Comparative Example 1-2, the present invention allows the flame retardant level of the finally obtained copper clad laminate to reach the HB level by using a combination of boehmite and a titanium bag, and whiteness and yellowing resistance It makes it possible to satisfy the application requirements of this LED substrate, and even if any of them is insufficient, excellent performance cannot be reached. Comparing Examples 1, 3-5 and Comparative Examples 3-6, as you can see, the contents of boehmite and titanium bags must all be within the range of parts by weight provided in the present invention, and are less than or exceeding the corresponding weight range. None of the obtained copper clad laminates reach the technical effect of this application. As can be seen from comparing Example 3 and Comparative Example 7, the boehmite of the present invention should not be replaced with other fillers having a certain flame retardant effect. As can be seen from comparing Example 3 and Comparative Example 8-9, when the epoxy is cured using an acid anhydride curing agent, the finally obtained copper clad laminate has better heat resistance and weather resistance, and the yellowing resistance is better.

Accordingly, the resin composition of the present invention requires not only to blend an epoxy resin, boehmite, and titanium bag, but also satisfies the blending ratio of each composition, it is possible to manufacture a copper clad laminate having excellent performance.

The applicant of the present invention has described the halogen-free unmanned nitrogen-free flame-retardant resin composition of the present invention, the prepreg and the metal foil laminate comprising the same through the above examples, but the present invention is not limited to the above detailed method, that is, the present invention We declare that it does not imply that this can only be done by relying on the above detailed method. It should be understood by those skilled in the art that any improvement to the present invention, equivalent replacement for each raw material of the product of the present invention, addition of auxiliary components, selection of specific methods, etc. are all protection of the present invention. It belongs to the scope and the disclosed scope.

Claims (10)

Based on parts by weight,
100 parts of epoxy resin;
180-250 parts boehmite;
180-300 parts of a titanium bag; And
50-170 parts of an acid anhydride-based curing agent; halogen-free unmanned nitrogen-free flame-retardant resin composition comprising a. The method of claim 1,
The particle diameter of the boehmite is a halogen-free unmanned nitrogen-free flame retardant resin composition, characterized in that 0.5-10㎛. The method of claim 1,
The titanium bag is a halogen-free nitrogen-free flame-retardant resin composition, characterized in that the rutile type titanium white. The method of claim 1,
The average particle diameter of the titanium bag is less than 0.30㎛, halogen-free, nitrogen-free flame retardant resin composition, characterized in that. The method of claim 1,
The whiteness of the titanium bag is no less than 98%, halogen-free, nitrogen-free flame retardant resin composition, characterized in that. The method of claim 1,
The curing agent is a halogen-free nitrogen-free flame retardant resin composition, characterized in that it comprises a copolymer of styrene and maleic anhydride and/or o-phthalic anhydride. The method of claim 1,
The halogen-free unmanned nitrogen-free flame-retardant resin composition further comprises 0.02-0.1 parts of a curing accelerator. A prepreg comprising a reinforcing material and the halogen-free unmanned nitrogen-free flame retardant resin composition according to any one of claims 1 to 7 attached to the reinforcing material through impregnation drying. A metal foil laminate comprising at least one prepreg according to claim 8 and a metal foil coated on one or both sides of the prepreg after being superposed. A printed circuit board comprising the metal foil laminate according to claim 9.