TWI626284B - Resin composition, film and circuit board using the same - Google Patents

Abstract

A resin composition comprising a modified polyether polymer compound, an epoxy resin, and a solvent, wherein the chemical structure of the modified polyether polymer compound is Wherein the Ar' group is at least one selected from the group consisting of a diphenyl sulfonium group, a diphenyl ether group, and a 3,5,3',5'-tetramethyldiphenylpropane group, the resin composition The molar ratio of the epoxy resin to the modified polyether polymer compound is 0.1 to 1. Further, the present invention provides a film to which the resin composition is applied, a circuit board produced by applying the resin composition.

Description

Resin composition and film and circuit board using the same

The present invention relates to a resin composition, a film to which the resin composition is applied, and a circuit board.

In the era of big data, the information processing of electronic products continues to develop in the direction of high-frequency signal transmission and high-speed digitalization. To ensure that the electronic product has good signal transmission quality under the condition of high-frequency signal transmission, it is required that the transmission line in the conductive copper foil of the flexible circuit board is in an impedance matching state with the electronic components connected thereto, thereby avoiding signal reflection, Scattering, attenuation, and delay. The dielectric constant and dielectric loss factor of the material of the adhesive layer in contact with the conductive line in the flexible circuit board are an important factor affecting the impedance matching of the high frequency transmission. The polyimide film layer used in the flexible printed circuit board in the prior art is generally prepared by using a diamine compound and a dianhydride compound, and the dielectric constant of the film layer is often caused by containing a polar functional group therein. Above 3.0, the flexible circuit board cannot achieve high-frequency signal transmission impedance matching, which affects the high-frequency signal transmission and high-speed digitalization.

In view of the above, it is necessary to provide a resin composition having a low dielectric constant and good heat resistance.

In addition, it is also necessary to provide a film to which the resin composition is applied.

Further, it is also necessary to provide a circuit board produced by applying the resin composition.

A resin composition comprising a modified polyether polymer compound, an epoxy resin, and a solvent, wherein the chemical structure of the modified polyether polymer compound is Wherein the Ar' group is selected from the group consisting of diphenyl sulfonium groups (chemical formula: ), diphenyl ether group (chemical structure is: And 3,5,3',5'-tetramethyldiphenylpropane group (chemical formula: At least one of the resin composition, the content of the modified polyether polymer compound is 100 parts by weight, and the molar ratio of the epoxy resin to the modified polyether polymer compound is 0.1~ 1.

Wherein the epoxy resin is selected from the group consisting of chemical structures and At least one of the resins.

Wherein, the resin composition further comprises a pore material, and the content of the pore material in the resin composition is 0.1 to 10 parts by weight.

Wherein, the viscosity of the resin composition is from 40000 cps to 60000 cps.

Wherein the solvent is N,N-dimethylacetamide.

A film using the resin composition, comprising a release film and a glue layer bonded to at least one surface of the release film, the glue layer being pre-baked by the resin composition and then heated and cured The modified polyether polymer compound in the resin composition forms a chemical cross-linking structure by reacting with an epoxy resin.

A circuit board produced by using the resin composition, comprising a circuit substrate and a glue layer bonded to at least one surface of the circuit substrate, wherein the glue layer is prepared by pre-baking the resin composition and then heating and solidifying. The modified polyether polymer compound in the resin composition forms a chemical cross-linking structure by reacting with an epoxy resin.

In the resin composition of the present invention, since the modified polyether polymer compound is contained in the adhesive layer obtained by the resin composition, the modified polyether polymer compound has an acrylate group bonded to the branch The acrylate group reacts with the epoxy resin during the subsequent curing process, so that the cured adhesive layer does not have a secondary alcohol polar group, and the dielectric constant of the adhesive layer is lowered. And in the process of heating the resin composition to form a glue layer, the modified polyether polymer compound is bonded together with the epoxy resin by the acrylate group thereon to form a chemical bond. The networked circuit structure can further increase the crosslink density of the resin composition so that the chemically crosslinked network structure in the adhesive layer does not fail in the subsequent soldering process of the conventional circuit board, and the The heat resistance of the adhesive layer of the circuit board produced by the resin composition. In addition, since the modified polyether polymer compound has an indirect 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide group, the obtained rubber layer is excellent. Flame retardant.

The resin composition of the preferred embodiment of the present invention is mainly used in a substrate, a glue layer or a cover film of a circuit board (for example, a rigid-flex board). The resin composition contains a modified polyether polymer compound, an epoxy resin, and a solvent. In the resin composition, the content of the modified polyether polymer compound is 100 parts by weight, and the molar ratio of the epoxy resin to the modified polyether polymer compound is 0.1 to 1. The viscosity of the resin composition is from 40,000 cps to 60000 cps.

The chemical structural formula of the modified polyether polymer compound is Wherein the Ar' group may be selected from, but not limited to, a diphenylhydrazine group (chemical formula: ), diphenyl ether group (chemical structure is: And 3,5,3',5'-tetramethyldiphenylpropane group (chemical formula: At least one of them. In the present embodiment, the degree of polymerization n of the modified polyether polymer compound is from 1 to 50.

In the present embodiment, the modified polyether polymer compound is prepared by the following steps: 1), 2), 3),

The epoxy resin may be selected from, but not limited to, a chemical structure and At least one of the epoxy resins.

In the present embodiment, the solvent is N,N-dimethylacetamide (DMAc). In other embodiments, the solvent may be other organic solvents commonly used in the art for dissolving ether polymer compounds and epoxy resins.

In the embodiment, the resin composition may further include a hole material. In this embodiment, the pore material may be selected from the molecular sieve of the model MCM-41 produced by Tianjin Nanhua Catalyst Co., Ltd. In the resin composition, the content of the pore material is 0.1 to 10 parts by weight.

The resin composition may be prepared by adding the modified polyether polymer compound, an epoxy resin and a solvent to a reaction bottle according to a predetermined ratio, and mixing and stirring to make the modified polyether polymer compound and ring. The resin composition is obtained by thoroughly mixing and dissolving an oxygen resin and a solvent.

A film obtained from the above resin composition, the film comprising a release film and a glue layer bonded to at least one surface of the release film. The adhesive layer is obtained by coating the resin composition on at least one surface of the release film, pre-baking, and then heating and solidifying. In the embodiment, the resin composition coated on the release film is baked at a temperature of 140 degrees Celsius for 30 minutes, and then cured at 180 degrees Celsius, 200 degrees Celsius, and 220 degrees Celsius for 2 hours. The film is obtained.

A circuit board made of the above resin composition, comprising at least one circuit substrate and a glue layer bonded to at least one surface of the circuit substrate. The adhesive layer is obtained by coating the resin composition on at least one surface of the circuit board, pre-baking, and then heating and solidifying. In the embodiment, the resin composition coated on the circuit substrate is baked at a temperature of 140 degrees Celsius for 30 minutes, and then cured at 180 degrees Celsius, 200 degrees Celsius, and 220 degrees Celsius for 2 hours. The film.

Since the modified polyether polymer compound is contained in the adhesive layer prepared by the resin composition, the modified polyether polymer compound has an acrylate group bonded to the branch, and the acrylate group Reacting with the epoxy resin during the subsequent curing process, so that the cured adhesive layer does not have a secondary alcohol polar group, and the dielectric constant of the adhesive layer is lowered. And in the process of heating the resin composition to form a glue layer, the modified polyether polymer compound is bonded together with the epoxy resin by the acrylate group thereon to form a chemical bond. The networked circuit structure can further increase the crosslink density of the resin composition so that the chemically crosslinked network structure in the adhesive layer does not fail in the subsequent soldering process of the conventional circuit board, and the The circuit board made of the resin composition The heat resistance of the adhesive layer. In addition, since the modified polyether polymer compound has an indirect 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide group, the obtained rubber layer is excellent. Flame retardant. Since the resin composition contains the pore material, the gel layer formed by curing has holes in the layer to facilitate air ingress, thereby further reducing the dielectric constant of the rubber layer.

The invention will now be specifically described by way of examples and comparative examples.

Example 1

60 g of 4,4'-difluorobenzophenone, 71.2 g of 4,4'-dihydroxydiphenyl hydrazine, 77.4 g of K ₂ CO ₃ , 30 mL of xylene and 393.6 g of N were sequentially added to the first reaction flask. , N-dimethylacetamide is stirred and dissolved, and then heated in a nitrogen atmosphere at 130 ° C for 12 hours to prepare a chemical formula of The first product.

50 g of the first product, 23.6 g of DOPO, 102.7 g of phenol and 0.9 g of sulfuric acid were sequentially added to the second reaction flask and stirred and dissolved, and then heated at a temperature of 140 ° C for 12 hours in a nitrogen atmosphere to prepare a chemical structural formula. The second product.

10 g of the second product, 3.5 g of 2-methacrylic anhydride, 0.1 g of sodium acetate and 100 mL of N,N-dimethylacetamide were sequentially added to the third reaction flask and stirred to dissolve, and then in a nitrogen atmosphere. The chemical structure was prepared by heating at a temperature of 80 ° C for 12 hours. Modified polyether polymer compound (I).

In the fourth reaction flask, 100 g of the modified polyether polymer compound (I) is sequentially added, and the chemical structure formula of the molar ratio of the modified polyether polymer compound (I) is 1. The epoxy resin and 100 g of N,N-dimethylacetamide were dissolved and dissolved to complete the resin composition. The resin composition had a viscosity of 53,000 cps.

Example 2

The 71.2 g of diphenyl hydrazine in Example 1 was replaced with 57.7 g of 4,4'-dihydroxydiphenyl ether and the other chemical conditions were unchanged. Modified polyether polymer compound (II).

100 g of the modified polyether polymer compound (II) is sequentially added to the reaction flask, and the chemical structure formula of the molar ratio of the modified polyether polymer compound (II) is 1. The epoxy resin and 100 g of N,N-dimethylacetamide were dissolved and dissolved to complete the resin composition. The resin composition had a viscosity of 52,000 cps.

Example 3

The 71.2 g of diphenyl hydrazine in Example 1 was replaced with 80.7 g of 3,5,3',5'-tetramethyl-4,4'-dihydroxydiphenylpropane and the chemical structure was prepared under other conditions. Formula Modified polyether polymer compound (III).

100 g of the modified polyether polymer compound (III) is sequentially added to the reaction flask, and the chemical structural formula of the molar ratio of the modified polyether polymer compound (III) is 1. The epoxy resin and 100 g of N,N-dimethylacetamide were dissolved and dissolved to complete the resin composition. The resin composition had a viscosity of 58,000 cps.

Example 4

100 g of the modified polyether polymer compound (I) of Example 1 and a molar ratio of 1 to the modified polyether polymer compound (I) were sequentially added to the reaction flask. The epoxy resin and 100 g of N,N-dimethylacetamide were dissolved and dissolved to complete the resin composition. The resin composition had a viscosity of 58,000 cps.

Comparative example 1

70 g of 4,4'-diaminodiphenyl ether, 30 g of 4,4'-oxydiphthalic anhydride and 100 g of N,N-dimethylacetamide were sequentially added to the reaction flask, and stirred and dissolved. The resin composition is configured to be completed. The resin composition had a viscosity of 40000 cps.

Comparative example 2

70 g of 4,4'-diaminodiphenyl ether, 30 g of 4,4'-oxydiphthalic anhydride modified with 2-methacrylic anhydride and 100 g of N,N-di were sequentially added to the reaction flask. Methylacetamide was dissolved and dissolved to complete the resin composition. The resin composition had a viscosity of 20,561 cps.

Comparative example 3

70 g of 4,4'-diaminodiphenyl ether, 30 g of 4,4'-oxydiphthalic anhydride, and 0.5 g of Tianjin Nanhua Catalyst Co., Ltd. model MCM-41 were sequentially added to the reaction flask. The molecular sieve and 100 g of N,N-dimethylacetamide were mixed and mixed to complete the resin composition. The resin composition had a viscosity of 25,656 cps.

The seven resin compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were respectively applied to one surface of seven copper foils to form seven kinds of circuit boards, and the surface of the copper foil was prepared in Examples 1 to 4. The four resin compositions were prebaked at 140 ° C for 30 minutes, and then cured at 180 ° C, 200 ° C and 220 ° C for 2 hours to form 4 kinds of adhesive layers, respectively. The copper foil surface was prepared in Comparative Examples 1 to 3. The three resin compositions were prebaked at 140 degrees Celsius for 30 minutes and then cured at 350 degrees Celsius for 1 hour to form three adhesive layers.

The dielectric constant D _k and the dielectric loss D _f of the four adhesive layers formed in the above Examples 1 to 4 and the three adhesive layers formed in Comparative Examples 1 to 3 were tested. The above seven kinds of boards were subjected to copper peel strength test and solder heat resistance test. Refer to the performance test data in Table 1 for the test results. Among them, if the soldering heat resistance test condition is greater than or equal to 320 ° C, 10 sec, the rubber layer does not cause foaming, peeling, etc., the soldering heat resistance test result is "pass", indicating that the circuit board meets the heat resistance requirements.

Table 1 shows the measured values of the relevant materials in the above-mentioned various circuit boards.

As can be seen from Table 1, the four adhesive layers formed by the resin compositions of Examples 1 to 4 of the present invention have lower dielectric layers than the three adhesive layers formed separately from the resin compositions of Comparative Examples 1-3. Electric constant D _k . Further, the four types of adhesive layers formed by the resin compositions of Examples 1 to 4 of the present invention have good heat resistance.

Since the modified polyether polymer compound is contained in the adhesive layer prepared by the resin composition, the modified polyether polymer compound has an acrylate group bonded to the branch, and the acrylate group Reacting with the epoxy resin during the subsequent curing process, so that the cured adhesive layer does not have a secondary alcohol polar group, and the dielectric constant of the adhesive layer is lowered. And in the process of heating the resin composition to form a glue layer, the modified polyether polymer compound is bonded together with the epoxy resin by the acrylate group thereon to form a chemical bond. The networked circuit structure can further increase the crosslink density of the resin composition so that the chemically crosslinked network structure in the adhesive layer does not fail in the subsequent soldering process of the conventional circuit board, and the The heat resistance of the adhesive layer of the circuit board produced by the resin composition. In addition, due to the indirect 9,10-dihydro-9-oxa in the modified polyether polymer compound -10-phosphaphenanthrene-10-oxide group, so that the obtained rubber layer has excellent flame retardancy. Since the resin composition contains the pore material, the gel layer formed by curing has holes in the layer to facilitate air ingress, thereby further reducing the dielectric constant of the rubber layer.

In addition, various other changes and modifications may be made in accordance with the technical concept of the present invention, and all such changes and modifications are intended to fall within the scope of the invention.

Claims (7)

A resin composition, wherein the resin composition contains a modified polyether polymer compound, an epoxy resin, and a solvent, and the chemical structure formula of the modified polyether polymer compound is Wherein the Ar' group is selected from the group consisting of diphenyl sulfonium groups (chemical formula: ), diphenyl ether group (chemical structure is: And 3,5,3',5'-tetramethyldiphenylpropane group (chemical formula: At least one of the resin composition, the content of the modified polyether polymer compound is 100 parts by weight, and the molar ratio of the epoxy resin to the modified polyether polymer compound is 0.1~ 1. The resin composition according to claim 1, wherein the epoxy resin is selected from the group consisting of chemical structures and At least one of the resins. The resin composition according to claim 1, wherein the resin composition further comprises a pore material, and the content of the pore material in the resin composition is 0.1 to 10 parts by weight. The resin composition according to claim 1, wherein the resin composition has a viscosity of from 40000 cps to 60000 cps. The resin composition according to claim 1, wherein the solvent is N,N-dimethylacetamide. A film comprising a release film and a glue layer bonded to at least one surface of the release film, the adhesive layer being modified by the resin composition according to any one of claims 1 to 5. After prebaking and then heating and solidifying, the modified polyether polymer compound in the resin composition forms a chemical crosslinked network structure by reacting with the epoxy resin. A circuit board comprising a circuit board and a glue layer bonded to at least one surface of the circuit board, wherein the glue layer is pretreated by the resin composition according to any one of claims 1 to 5. After the baking is further heated and solidified, the modified polyether polymer compound in the resin composition forms a chemical cross-linking structure by reacting with the epoxy resin.