CN100432170C - Resin composition and adhesive-backed ultrathin copper foil dielectric layer material containing same - Google Patents

Abstract

The present invention relates to a resin composition comprising 0.5 to 25 parts by weight of an adhesive high molecular compound; (b)10 to 45 parts by weight of a bromine-containing resin; (c) 10-60 parts by weight of an epoxy resin; and (d)5 to 35 parts by weight of a curing agent. The resin composition can be added with an organic solvent to prepare varnish, and the varnish is coated on an ultrathin copper foil to form a dielectric layer.

Description

Resin composition and adhesive-backed ultra-thin copper foil dielectric layer material containing the composition

technical field

The invention relates to a resin composition and an adhesive-backed ultra-thin copper foil dielectric layer material containing the resin composition.

Background technique

At present, electronic products are developing in the direction of thinness, lightness, high performance, and portability, so that downstream industries such as packaging and printed circuit boards (PCB) must meet the characteristics of high density and high reliability in terms of technology and materials.

Traditional PCB is composed of glass fiber cloth, resin and copper foil. Because the substrate contains glass fiber cloth, when the laser drilling machine is used to drill holes, the microhole formability will be poor, and the process is complicated and the cost is high. Therefore, the RCC process technology ("Resin Coated Copper", adhesive-backed copper foil), can save the procedure of impregnating glass fiber cloth with resin, not only simplify the process, but also reduce cost and weight. At present, it has been widely used in portable products such as notebook computers, mobile phones, and PDAs.

In addition, as a copper foil material for power and signal wires, it is an unavoidable trend to thin the thickness of the copper foil in order to achieve high-density thinning. Therefore, the thickness has been reduced from 18 μm or 35 μm to the current 3 to 6 μm, which is called It is ultra thin copper foil.

Generally, the ultra-thin adhesive-backed copper foil uses aluminum foil as a carrier, and then performs appropriate surface pretreatment and separation layer (or adhesive layer) treatment on the aluminum foil, and then electroplates a 3 to 6 μm thick copper foil layer. After roughening, heat-resistant and anti-oxidation layer treatment, and then coated with varnish to form a dielectric layer (dielectric layer), and finally the carrier aluminum foil is torn off. This ultra-thin self-adhesive copper foil is suitable for PCB and integrated circuit ("IC") substrates. However, the ultra-thin self-adhesive copper foil currently available on the market generally faces shortcomings such as too brittle dielectric layer, poor heat resistance, and poor contact effect with ultra-thin copper foil.

Copper foil substrates need to have high toughness and high temperature resistance. According to the existing technology, if the glass fiber cloth is removed to achieve the purpose of light and thin substrate, the substrate will be brittle; how to remove the glass fiber cloth while maintaining the function of the substrate , has become a problem that the industry seeks to solve.

The inventors of this case have found through extensive research that a resin composition with certain specific components can be prepared into a varnish by adding an organic solvent, and coated on a copper foil (conductive layer), a dielectric layer can be formed to replace the glass fiber tape ( prepreg), one can save glass fiber cloth, and two can withstand high temperature, and has strong toughness, which is suitable for various circuit designs. The printed circuit board using this ultra-thin self-adhesive copper foil substrate technology is more than half thinner than the traditional printed circuit board in thickness, and due to the simplification of the process and materials, it can greatly reduce the cost.

Contents of the invention

The object of the present invention is to provide a resin composition.

Another object of the present invention is to provide a self-adhesive ultra-thin copper foil dielectric layer material containing the resin composition.

Implementation

The present invention provides a resin composition comprising: (a) 0.5 to 25 parts by weight of an adhesive polymer compound ("binder polymer"); (b) 10 to 45 parts by weight of a bromine-containing resin; (c) 10 to 60 parts by weight of epoxy resin; and (d) 5 to 35 parts by weight of hardener.

The adhesive polymer compound used in the resin composition of the present invention preferably has a content of 5 to 15 parts by weight and an average molecular weight of 5,000 to 100,000.

The adhesive macromolecular compound used in the resin composition of the present invention is not particularly limited, and the adhesive macromolecular compound that can be used in the present invention can be for example, but not limited to mixed polybutadiene rubber ("mixed polybutadiene rubber"), polyester Resin ("polyester"), acrylic resin ("acrylic resin") and polyurethane resin ("polyurethane"), and mixtures of these polymer compounds, etc.

The bromine-containing resin that can be used in the resin composition of the present invention has a bromine-containing ratio of 5 to 25% by weight based on the total weight of the resin composition.

The bromine-containing resin used in the resin composition of the present invention is not particularly limited, and the bromine-containing resin that can be used in the present invention can be, but not limited to, bromine-containing epoxy resin, bromine-containing polyester resin and halon ("Halons") ) and mixtures thereof, etc.

The preferred content of the epoxy resin used in the resin composition of the present invention is 15 to 30 parts by weight.

The epoxy resin used in the resin composition of the present invention contains at least one kind having a high glass-transition temperature ("glass-transition temperature", Tg), wherein the high glass-transition temperature refers to above 100°C.

The epoxy resin used in the resin composition of the present invention is an epoxy resin containing two or more functional groups, such as, but not limited to, bisphenol ("bisphenol") epoxy resin, bisphenol A ring Oxygen resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, novolac type novolac epoxy resin, novolac type alkyl novolac epoxy resin, modified (Modified) novolac epoxy resin, dicyclopentadiene ( "dicyclopentadiene") epoxy resins or mixtures thereof.

The preferred content of the hardener used in the resin composition of the present invention is 17 to 25 parts by weight.

Hardeners used in the resin composition of the present invention are well known to those skilled in the art, non-limiting examples of which include: amine-containing compounds, guanidine ("guanidine") hardeners, and imidazole ("imidazole") hardeners agent.

The resin composition of the present invention may optionally include additives known to those skilled in the art, such additives may be defoaming agents (Defoaming Agent), leveling agents (LevellingAgent), adhesion promoters (Adhesive Promoter), Silane coupling agent (Silane CouplingAgent) or its mixture, etc.

The present invention further provides an adhesive-backed ultra-thin copper foil dielectric layer material, which comprises the above-mentioned resin composition and an organic solvent.

Adhesive ultra-thin copper foil dielectric layer material of the present invention, when the content of the adhesive polymer compound is less than 0.5 parts by weight, it cannot achieve a good contact effect with the ultra-thin copper foil, but if the content exceeds 25 parts by weight, Then the chemical resistance is not good; when the content of brominated resin is lower than 10 parts by weight, the flame resistance will be reduced; when the content of epoxy resin is lower than 10 parts by weight, the heat resistance will be greatly reduced, but if When it exceeds 60 parts by weight, the dielectric layer becomes brittle and difficult to rework; and when the content of the hardener is less than 5 parts by weight, the heat resistance decreases, but if the content exceeds 35 parts by weight, the chemical resistance will fall.

The organic solvent suitable for the dielectric layer material of the present invention is not particularly limited, as long as it can dissolve the above-mentioned resin composition. Examples include, but are not limited to, methanol, acetone, methyl ethyl ketone or toluene or their mixtures.

Example

The following examples will further illustrate the present invention, and are not intended to limit the scope of the present invention. Any modification and change achieved by those skilled in the art without violating the spirit of the present invention all belong to the scope of the present invention .

Example 1

15 parts by weight of carboxy-terminated butadiene propylene (Carboxyl Terminated ButadieneAcrylonitrile, CTBN) (1072CG, Nandi rubber) is component a, 25 parts by weight of brominated epoxy resin (epoxy equivalent=499, softening point temperature is 75 ℃ , bromine content is 21wt.%, YDB-500, Toto chemical Industry, Co., Ltd.) is component b, 10 parts by weight of bisphenol-A epoxy resin (epoxy equivalent=2000 and softening point is 124 ℃, Epicion7051 , Dai-Nippon Ink Chemistry, Co., Ltd.) and 15 parts by weight of cresol-novolac type ("cresol-novolac type") epoxy resin (epoxy equivalent=215 and softening point is 78 ℃, Epicion N-673 , Dai-Nippon Ink Chemistry, Co., Ltd.) is component c, the above resin is dissolved in methyl ethyl ketone (solvent), and 30 parts by weight of amine compounds (diamine diphenyl "Diamine Diphenyl Sulfone", DDS) and 2 Parts by weight (2-ethyl-4-methylimidazole, 2-E4MZ) is component d, 2 parts by weight of leveling agent and 4 parts by weight of adhesion promoter, and the varnish can be obtained.

Comparative example 1

15 parts by weight of CTBN (1072CG, Nandi rubber) is component a, 10 parts by weight of bisphenol A type epoxy resin (epoxy equivalent=2000 and softening point is 124 ℃, Epicion 7051, Dai-Nippon Ink Chemistry, Co. , Ltd.) and 15 parts by weight of cresol-novolac type epoxy novolac resin (epoxy equivalent = 215 and softening point is 78 ° C, Epicion N-673, Dai-Nippon InkChemistry, Co., Ltd.) as component c Dissolve the above resin in methyl ethyl ketone, add 30 parts by weight of amine compound (DDS) and 2 parts by weight of 2-E4MZ as component d, 2 parts by weight of leveling agent and 4 parts by weight of adhesion promoter, you can get varnish.

Example 2

10 parts by weight of CTBN (1072CG, Nandi Rubber) is component a, 35 parts by weight of bromine-containing epoxy resin (epoxy equivalent=499, softening point temperature is 75 ° C, bromine content is 21% by weight, YDB-500, Toto Chemical Industry, Co., Ltd.) as component b, 15 parts by weight of bisphenol A type epoxy resin (epoxy equivalent=2000 and softening point is 124°C, Epicion 7051, Dai-Nippon Ink Chemistry, Co., Ltd .) and 20 parts by weight of cresol-novolak type epoxy resin (epoxy equivalent = 215 and softening point is 78 ℃, Epicion N-673, Dai-Nippon InkChemistry, Co., Ltd.) as component c, the above resin Dissolve in methyl ethyl ketone, add 15 parts by weight of amine compound (DDS) and 2 parts by weight of 2-E4MZ as component d, 2 parts by weight of leveling agent and 4 parts by weight of adhesion promoter to obtain varnish.

Comparative example 2

35 parts by weight of bromine-containing epoxy resin (epoxy equivalent=499, softening point temperature is 75 ℃, bromine content is 21% by weight, YDB-500, Toto Chemical Industry, Co., Ltd.) is component b, 15 Parts by weight of bisphenol A type epoxy resin (epoxy equivalent=2000, softening point is 124 ℃, Epicion 7051, Dai-Nippon Ink Chemistry, Co., Ltd.) and 20 parts by weight of cresol-novolac type epoxy resin ( Epoxy equivalent = 215 and softening point is 78 ℃, Epicion N-673, Dai-Nippon Ink Chemistry, Co., Ltd.) is component c, the above resin is dissolved in methyl ethyl ketone, and 15 parts by weight of amine compounds (DDS ) and 2 parts by weight of 2-E4MZ are component d, 2 parts by weight of a leveling agent and 4 parts by weight of an adhesion promoter to obtain a varnish.

Comparative example 2-1

30 parts by weight of CTBN (1072CG, Nandi rubber) is component a, 35 parts by weight of bromine-containing epoxy resin (epoxy equivalent=499, softening point temperature is 75 ° C, bromine content is 21% by weight, YDB-500, Toto Chemical Industry, Co., Ltd.) as component b, 15 parts by weight of bisphenol A type epoxy resin (epoxy equivalent=2000 and softening point is 124°C, Epicion 7051, Dai-Nippon Ink Chemistry, Co., Ltd .) and 20 parts by weight of cresol-novolak type epoxy resin (epoxy equivalent = 215 and softening point is 78 ℃, Epicion N-673, Dai-Nippon InkChemistry, Co., Ltd.) as component c, the above resin Dissolve in methyl ethyl ketone, add 15 parts by weight of amine compound (DDS) and 2 parts by weight of 2-E4MZ as component d, 2 parts by weight of leveling agent and 4 parts by weight of adhesion promoter to obtain varnish.

Example 3

15 parts by weight of CTBN (1072CG, Nandi rubber) is component a, 40 parts by weight of bromine-containing epoxy resin (epoxy equivalent=499, softening point temperature is 75 ° C, bromine content is 21% by weight, YDB-500, Toto chemical Industry, Co., Ltd.) is component b, 20 parts by weight of bisphenol A type epoxy resin (epoxy equivalent = 2000 and softening point is 124 ° C, Epicion 7051, Dai-Nippon Ink Chemistry, Co., Ltd .) and 25 parts by weight of cresol-novolac type epoxy resin (epoxy equivalent = 215 and softening point is 78 ℃, Epicion N-673, Dai-Nippon InkChemistry, Co., Ltd.) as component c, the above resin Dissolve in methyl ethyl ketone, add 20 parts by weight of amine compound (DDS) and 2 parts by weight of 2-E4MZ as component d, 2 parts by weight of leveling agent and 4 parts by weight of adhesion promoter to obtain adhesive varnish.

Comparative example 3

15 parts by weight of CTBN (1072CG, Nandi rubber) is component a, 40 parts by weight of bromine-containing epoxy resin (epoxy equivalent=499, softening point temperature is 75 ° C, bromine content is 21% by weight, YDB-500, Toto Chemical Industry, Co., Ltd.) is component b, 25 parts by weight of cresol-novolak type epoxy resin (epoxy equivalent=215 and softening point is 78 ℃, Epicion N-673, Dai-Nippon Ink Chemistry, Co ., Ltd.) is component c, dissolve the above resin in methyl ethyl ketone, add 20 parts by weight of amine compound (DDS) and 2 parts by weight of 2-E4MZ as component d, 2 parts by weight of leveling agent and 4 parts by weight of Adhesion promoter to obtain adhesive varnish.

Comparative example 3-1

15 parts by weight of CTBN (1072CG, Nandi rubber) is component a, 40 parts by weight of bromine-containing epoxy resin (epoxy equivalent=499, softening point temperature is 75 ° C, bromine content is 21% by weight, YDB-500, Toto Chemical Industry, Co., Ltd.) is component b, 20 parts by weight of bisphenol A type epoxy resin (epoxy equivalent = 2000 and softening point is 124 ° C, Epicion 7051, Dai-Nippon Ink Chemistry, Co., Ltd .) and 25 parts by weight of cresol-novolac type epoxy resin (epoxy equivalent = 215 and softening point is 78 ℃, Epicion N-673, Dai-Nippon InkChemistry, Co., Ltd.) as component c, the above resin Dissolve in methyl ethyl ketone, add 40 parts by weight of amine compound (DDS) and 2 parts by weight of 2-E4MZ as component d, 2 parts by weight of leveling agent and 4 parts by weight of adhesion promoter to obtain adhesive varnish.

The varnish prepared in the above examples and comparative examples is coated on the rough surface of the anti-oxidation layer of ultra-thin copper foil (3 μm or 6 μm in thickness), and dried at a temperature of 80 to 100° C. for 10 minutes, so that the thickness of the glue solution is 60 to 80μm, made into ultra-thin copper foil with adhesive backing, according to ASTM specifications, tested for flame resistance, chemical resistance and peel strength. The obtained results are shown in Table 1.

Table 1

in conclusion:

1. Comparing the test results of Example 1 and Comparative Example 1, it can be seen that the addition of bromine-containing epoxy resin can increase the flame resistance of the adhesive-backed ultra-thin copper foil.

2. Comparing the test results of Example 2 and Comparative Example 2, it can be seen that adding the adhesive polymer compound can increase the peel strength of the adhesive-backed ultra-thin copper foil after lamination, which has a better adhesion effect.

3. Comparing the test results of Example 2 and Comparative Example 2-1, it can be seen that adding an excessive amount of adhesive polymer compound can increase the peel strength, but the chemical resistance will decrease, and it will cause too fast glue flow and poor hole filling. good question.

4. Comparing the test results of Example 3 and Comparative Example 3, it can be seen that if no epoxy resin with a softening point temperature higher than the lamination temperature is added, the glue-backed ultra-thin copper foil will flow too fast during the lamination process , is not conducive to hole filling.

5. Comparing the test results of Example 3 and Comparative Example 3-1, it can be known that adding too much curing agent will reduce the chemical resistance.

Claims (15)

1. resin combination, it comprises:

(a) the adhesion macromolecular compound of 0.5 to 25 weight part;

(b) the brominated resin of 10 to 45 weight parts;

(c) 25 to 60 parts by weight of epoxy resin; And

(d) 5 to 35 weight part stiffening agents.

2. composition as claimed in claim 1, the high molecular content of wherein should adhering is between 5 to 15 weight parts.

3. composition as claimed in claim 1, the high molecular molecular-weight average of wherein should adhering is between 5,000 to 100,000.

4. composition as claimed in claim 1, wherein this adhesion polymer is selected from and mixes polybutadiene rubber, vibrin, acrylic resin and polyamine base benzoic acid resin and composition thereof.

5. composition as claimed in claim 1, wherein the brominated ratio of this brominated resin in this resin combination gross weight, is 5 to 20 weight %.

6. composition as claimed in claim 1, wherein this brominated resin is to be selected from brominated Resins, epoxy, brominated vibrin and to breathe out dragon and composition thereof.

7. composition as claimed in claim 1, wherein the content of this Resins, epoxy is between 25 to 30 weight parts.

8. composition as claimed in claim 1, wherein this Resins, epoxy comprises at least a glass transition temp at the resin more than 100 ℃.

9. composition as claimed in claim 1, wherein this Resins, epoxy is for containing two or a plurality of functional groups' Resins, epoxy.

10. composition as claimed in claim 9, wherein this contain two or a plurality of functional groups' Resins, epoxy be selected from bisphenol epoxy, bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol aldehyde type novolac epoxy, phenol aldehyde type alkyl phenolic Resins, epoxy, modified phenolic Resins, epoxy and dicyclopentadiene Resins, epoxy and composition thereof.

11. composition as claimed in claim 1, wherein the content of this stiffening agent is between 17 to 25 weight parts.

12. composition as claimed in claim 1, wherein this stiffening agent is selected from amine-containing compound, guanidine class stiffening agent and imidazole hardeners and composition thereof.

13. composition as claimed in claim 1, it further comprises the additive that is selected from defoamer, flow agent, adhesion promotor and silane coupling agent and composition thereof.

14. a gum extra thin copper foil dielectric layer material is characterized in that comprising as each resin combination and organic solvent in the claim 1 to 13.

15. as the dielectric layer material of claim 14, wherein this organic solvent is methyl alcohol, acetone, methylethylketone or toluene or its mixture.