TW202136411A - Fluorine-based resin modified composition, composite film, and copper-clad plate - Google Patents

Abstract

A fluorine-based resin modified composition includes a fluorine-based resin composition and a polyamic acid block copolymer composition. The fluorine-based resin composition includes a fluorine-based additive, a surfactant, and a solvent. The polyamide acid block copolymer composition includes a polyamic acid block copolymer. A weight ratio of the fluorine-based additive and the polyamic acid block copolymer is (85-95) / (5-15). In the fluorine-based resin composition, the weight percentage of the fluorine-based additive is 35% to 40%, and the weight percentage of the surfactant is 3% to 5%. The disclosure also relates to a composite film and a copper-clad plate. The fluorine-based resin modified composition provided by the present disclosure can perform UV laser drilling or cutting and reduce the technical limitations of the fluorine-based materials.

Description

Fluorine resin modified composition, composite film and copper clad laminate

The invention relates to a fluorine resin modified composition, a composite film and a copper clad laminate.

In recent years, communication software requires high-frequency and high-speed. Therefore, the insulator material in the flexible printed circuit board must also meet the requirements of the high-frequency flexible printed circuit board. The current common insulator material is polyimide, but the dielectric properties (Dk/ Df=3.3/0.01) is poor and cannot meet high frequency requirements. Fluorine-based materials have good dielectric properties (Dk/Df=2.5~2.0/0.003~0.001), and at the same time have low polarity, low moisture absorption, good mechanical and thermal properties, etc., suitable for high-frequency and high-speed communication. However, fluorine-based materials are synthesized and filmed by high-temperature melting method, and the process technology is limited. In addition, the structure of fluorine-based materials is mostly FC, -O- and -C- bonds, but does not include π bonds, and the energy absorption rate is low. , This will not be conducive to UV laser drilling and cutting, and cannot meet the demand for refined products in the future.

In view of this, the present invention provides a fluorine-based resin modified composition that can perform UV laser drilling or cutting and reduce the technological limitations of the fluorine-based material manufacturing process.

It is also necessary to provide a composite membrane formed by cyclization of the fluorine-based resin modified composition as described above.

It is also necessary to provide a copper clad laminate including the composite film described above.

A fluorine-based resin modification composition includes a fluorine-based resin composition and a polyamide acid block copolymer composition. The fluorine-based resin composition includes a fluorine-based additive, a surfactant, and a solvent. The polyamide The amino acid block copolymer composition includes a polyamide acid block copolymer. In terms of weight percentage, the fluorine-based additive/the polyamide acid block copolymer=85-95/5-15; In the fluorine-based resin composition, the weight percentage of the fluorine-based additives is 35%-40%, and the weight percentage of the interface active agent is 3%-5%.

Further, the viscosity of the fluorine-based resin modified composition is: 2000-3000 cps. Further, the fluorine-based additives are selected from at least one of polytetrafluoroethylene, polychlorotrifluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether, polyvinyl fluoride, polyvinylidene fluoride and fluoroplastic film In one, the fluorine-based additive is powder.

Further, the main chain of the polyamide block copolymer includes a plurality of repeating amide segments, and liquid crystal groups and flexible groups alternately arranged on the amide segments.

、

、

、

、

、

、

中的至少一種；所述橋鍵結構選自

、

、

、

、

、

、

、

、

中的至少一種。Further, the liquid crystal group includes a plurality of aromatic rings and a bridge structure connecting the plurality of aromatic rings, and the aromatic ring is selected from

,

,

,

,

,

,

At least one of; the bridge structure is selected from

,

,

,

,

,

,

,

,

At least one of them.

Further, the flexible group includes a long-chain saturated aliphatic hydrocarbon group, a long-chain unsaturated aliphatic hydrocarbon group or an ether group, and the long chain is a straight-chain hydrocarbon including four or more carbon atoms.

Further, the polyamide acid block copolymer is formed by the polymerization reaction of dianhydride monomer and diamine monomer in a second solvent; in the polyamide acid block copolymer composition, The weight percentage of the dianhydride monomer and the diamine monomer is 20%-25%; the dianhydride monomer and the diamine monomer respectively include a liquid crystal group and a flexible group.

A composite film is formed by heating the fluorine-based resin modification composition as described above; wherein, during the heating process, the polyamide acid block copolymer undergoes a cyclization reaction, and the fluorine-based resin The additive undergoes a sintering reaction; the composite film is formed by mixing the product formed by the cyclization reaction of the polyamide acid block copolymer and the product formed by sintering the fluorine-based additive.

A copper clad laminate includes at least one copper foil layer, and the copper clad laminate further includes a composite film as described above, and the composite film is formed on the copper foil layer.

The fluorine-based resin modified composition, composite film and copper clad laminate provided by the present invention have a polyamide acid block copolymer added to the fluorine-based resin composition, 1) the polyamide acid block copolymer has a benzene ring (π bond), which is good for absorbing UV light. Therefore, the fluorine-based resin modified composition and the composite film are suitable for UV laser drilling or cutting, which is conducive to fine processing; 2) the polyamide embedded The segment copolymer has a liquid crystal group and a flexible group, so that the hygroscopicity of the fluorine-based resin-modified composition can be reduced and the thermoplasticity of the fluorine-based resin-modified composition can be maintained. It can be processed by heat treatment. Coating and synthesizing the composite film can reduce the limitation of the process technology; 3) maintaining the dielectric properties of the fluorine-based resin modified composition.

In order to further illustrate the technical means and effects adopted by the present invention to achieve the intended purpose of the invention, the following detailed descriptions of the specific embodiments, structures, features and effects provided by the present invention will be given below in conjunction with attached drawings 1-5 and preferred embodiments. illustrate. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work shall fall within the protection scope of the present invention.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments, and are not intended to limit the present invention. The term "and/or" as used herein includes any and all combinations of one or more related listed items.

A preferred embodiment of the present invention provides a fluorine-based resin modified composition, the fluorine-based resin modified composition includes a fluorine-based resin composition and a polyamide acid block copolymer composition, the fluorine-based resin composition And the polyamide acid block copolymer composition is uniformly dispersed. Wherein, the viscosity of the fluorine-based resin modified composition is: 2000-3000 cps.

Wherein, the fluorine-based resin composition includes a fluorine-based additive, a surfactant, and a first solvent. In the fluorine-based resin composition, the weight percentage of the fluorine-based additives is 35%-40%, and the weight percentage of the interface active agent is 3%-5%.

Wherein, the polyamide acid block copolymer composition includes a polyamide acid block copolymer and a second solvent. In terms of weight percentage, the fluorine-based additives/the polyamide acid block copolymer=85-95/5-15. The polyamide acid block copolymer is produced by the polymerization reaction of dianhydride monomer and diamine monomer in a second solvent; in the polyamide acid block copolymer composition, the dianhydride The weight percentage of the monomer and the diamine monomer is 20%-25%. The dianhydride monomer and the diamine monomer respectively include a liquid crystal group and a flexible group.

Wherein, the fluorine-based additives are powders, and the fluorine-based additives are polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene-perfluoroalkyl vinyl Ether (perfluoroalkoxy polymer, PFA), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), ethylene tetrafluoroethylene (ETFE) and other common fluorine-based powders in the industry are at least A sort of. Preferably, the fluorine-based additive is PFA.

，所述聚三氟氯乙烯的結構式為：

，所述四氟乙烯-全氟烷基乙烯基醚的結構式為：

，所述聚氟乙烯的結構式為：

，所述聚偏二氟乙烯的結構式為：

，所述氟塑膜的結構式為：

。Specifically, the structural formula of the polytetrafluoroethylene is:

, The structural formula of the polychlorotrifluoroethylene is:

, The structural formula of the tetrafluoroethylene-perfluoroalkyl vinyl ether is:

, The structural formula of the polyvinyl fluoride is:

, The structural formula of the polyvinylidene fluoride is:

, The structural formula of the fluoroplastic film is:

.

The interface active agent is used to change the interface state of the solvent, so that the fluorine-based additive is better dissolved in the solvent.

Specifically, the interface active agent is D-500, D-562, D-576, D-578, D-581 from DOXA SPREDOX PLASTICS, Rhodoline 111 from Rhodoia, ZetaSperse 2500 and ZetaSperse 3400 from SKC, etc. At least one of the surfactants commonly used in the industry. Preferably, the surfactant is D-500.

Wherein, the chemical composition of the D-500 is: polyether polyamide with acidic functional groups. The D-500 has a special double anchor design, and can grind organic and inorganic pigments. When using the D-500 mixture to prepare color paste, there will be almost no problem of color separation. This proves that the D-500 has potential in epoxy and unsaturated polyester systems.

Wherein, the chemical composition of the D-562 is: polyether with acidic functional groups. The D-562 is suitable for dispersing calcium carbonate and aluminum hydroxide in unsaturated polyester and epoxy resin systems, and can effectively control the viscosity. The chemical composition of D-576 is: polyether polyamide. The D-576 is suitable for dispersing carbon black or organic toner in polyether polyol to make low-viscosity color paste and can exhibit excellent blackness to carbon black. The chemical composition of D-578 is: polyether polyamide. The D-578 is suitable for dispersing carbon black or organic toner in polyether polyol to make low-viscosity color paste and has good fluidity. The chemical composition of the D-581 is: polyester polyamide. The D-581 is suitable for thermoplastic plastic processing, and is widely used in polyvinyl chloride, polypropylene, polyethylene, etc., and exhibits excellent grinding and dispersing properties for organic pigments. The chemical composition of the Rhodoline 1111 is: sodium polycarboxylate. The polymer dispersant of polycarboxylate sodium salt has higher molecular weight, better water resistance and later dispersion stability. Mainly recommended for the dispersion of inorganic pigments. The ZetaSperse 2500 has excellent dispersion stability, long-term high temperature storage stability, good color development, and improves color and dispersion stability during the paint letting process. The ZetaSperse 3400 can improve the dispersion thixotropy of specific pigments, improve the color development and improve the color and dispersion stability during the paint let-down process.

Wherein, the first solvent is a bipolar aprotic solvent. Preferably, the bipolar aprotic solvent is selected from the group consisting of dimethylformamide (DMF), dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), dimethylsulfene (DMSO) At least one of them.

Wherein, the main chain of the polyamide acid block copolymer includes a plurality of repeating amide segments and liquid crystal groups and flexible groups alternately arranged on the amide segments.

、

、

、

、

、

、

中的至少一種；所述橋鍵結構選自

、

、

、

、

、

、

、

、

中的至少一種。The liquid crystal group includes a plurality of aromatic rings and a bridge structure bonding the plurality of aromatic rings, and the aromatic ring is selected from

,

,

,

,

,

,

At least one of; the bridge structure is selected from

,

,

,

,

,

,

,

,

At least one of them.

Wherein, the flexible group includes a long-chain saturated aliphatic hydrocarbon group, a long-chain unsaturated aliphatic hydrocarbon group or an ether group, and the long chain is a straight-chain hydrocarbon including four or more carbon atoms.

Wherein, the polyamide acid block copolymer is formed by copolymerization of dianhydride monomer and diamine monomer in the second solvent. In the polyamide acid block copolymer composition, the weight percentage of the dianhydride monomer and the diamine monomer is 20%-25%.

Wherein, the dianhydride monomer and the diamine monomer respectively include a liquid crystal group and a flexible group.

Specifically, the dianhydride monomer containing the liquid crystal group is selected from 3,3',4,4'-biphenyltetracarboxylic dianhydride, p-phenylbis(trimellitic acid ester) dianhydride and cyclic At least one of hexane-1,4-diylbis(methylene)bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid ethyl ester).

，所述對苯基二(偏苯三酸酯)二酸酐的結構式為

（p-Phenylene bis(trimellitate) dianhydride，TAHQ），所述環己烷-1,4-二基雙（亞甲基）雙（1,3-二氧代-1,3-二氫異苯並呋喃-5-羧酸乙酯）的結構式為：

。 具體地，含有所述液晶性基團的二胺單體選自對氨基苯甲酸對氨基苯酯、1,4-雙（4-氨基苯氧基）苯及對苯二甲酸二對氨基苯酯中的至少一種。 其中，所述對氨基苯甲酸對氨基苯酯的結構式為：

（4-Aminobenzoic acid 4-aminophenyl ester，APAB），所述1,4-雙（4-氨基苯氧基）苯的結構式為：

，所述對苯二甲酸二對氨基苯酯的結構式為：

。Wherein, the structural formula of the 3,3',4,4'-biphenyltetracarboxylic dianhydride is

, The structural formula of the p-phenylbis(trimellitic acid ester) dianhydride is

(P-Phenylene bis(trimellitate) dianhydride, TAHQ), the cyclohexane-1,4-diyl bis(methylene) bis(1,3-dioxo-1,3-dihydroisobenzo The structural formula of ethyl furan-5-carboxylate is:

. Specifically, the diamine monomer containing the liquid crystal group is selected from the group consisting of p-aminophenyl p-aminobenzoate, 1,4-bis(4-aminophenoxy)benzene and di-p-aminophenyl terephthalate At least one of them. Wherein, the structural formula of p-aminophenyl p-aminobenzoate is:

(4-Aminobenzoic acid 4-aminophenyl ester, APAB), the structural formula of the 1,4-bis(4-aminophenoxy)benzene is:

, The structural formula of the di-p-aminophenyl terephthalate is:

.

Specifically, the dianhydride monomer containing the flexible group is selected from 4,4'-oxydiphthalic anhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 3,3 At least one of',4,4'-benzophenone tetracarboxylic dianhydride, 3,3,4,4-diphenyl tetracarboxylic dianhydride, hexafluoro dianhydride and bisphenol A type diether dianhydride A sort of.

（4,4′-Oxydiphthalic anhydride，ODPA），所述2,3,3',4'-二苯醚四甲酸二酐的結構式為：

，所述3,3',4,4'-二苯甲酮四甲酸二酐的結構式：為

，所述3,3,4,4-二苯基碸四羧酸二酸酐的結構式為：

，所述六氟二酐的結構式為：

，所述雙酚A型二醚二酐的結構式為

（4,4'-(4,4'-isopropylidenediphenoxy)bis-(phthalic anhydride)，BPADA）。Wherein, the structural formula of the 4,4'-oxydiphthalic anhydride is:

(4,4'-Oxydiphthalic anhydride, ODPA), the structural formula of the 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride is:

, The structural formula of the 3,3',4,4'-benzophenone tetracarboxylic dianhydride:

, The structural formula of the 3,3,4,4-diphenyl tetracarboxylic dianhydride is:

, The structural formula of the hexafluorodianhydride is:

, The structural formula of the bisphenol A diether dianhydride is

(4,4'-(4,4'-isopropylidenediphenoxy)bis-(phthalic anhydride), BPADA).

Specifically, the diamine monomer containing the flexible group is selected from 4,4'-diaminodiphenyl ether, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2'-bis [4-(4-Aminophenoxyphenyl)]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoro At least one of propane, 1,3-bis(4'-aminophenoxy)benzene, and 1,3-bis(3-aminophenoxy)benzene.

，所述4,4'-二(4-氨基苯氧基)聯苯的結構式為：

（4,4'-Bis(4-aminophenoxy)biphenyl，BAPB），所述2,2'-雙[4-(4-氨基苯氧基苯基)]丙烷的結構式為：

（4,4'-(4,4'-Isopropylidenediphenyl-1,1'-diyldioxy)dianiline，BAPP），所述2,2-雙[4-(4-氨基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷的結構式為：

（2,2-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane，HFBAPP），所述1,3-雙(4'-氨基苯氧基)苯的結構式為：

，所述1,3-雙(3-氨基苯氧基)苯的結構式為：

（1,3-Bis(3-aminophenoxy)benzene，TPE-M）。Wherein, the structural formula of the 4,4'-diaminodiphenyl ether is:

, The structural formula of the 4,4'-bis(4-aminophenoxy)biphenyl is:

(4,4'-Bis(4-aminophenoxy)biphenyl, BAPB), the structural formula of the 2,2'-bis[4-(4-aminophenoxyphenyl)]propane is:

(4,4'-(4,4'-Isopropylidenediphenyl-1,1'-diyldioxy)dianiline, BAPP), the 2,2-bis[4-(4-aminophenoxy)phenyl]-1, The structural formula of 1,1,3,3,3-hexafluoropropane is:

(2,2-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, HFBAPP), the structural formula of the 1,3-bis(4'-aminophenoxy)benzene is:

, The structural formula of the 1,3-bis(3-aminophenoxy)benzene is:

(1,3-Bis(3-aminophenoxy)benzene, TPE-M).

Wherein, the second solvent is a bipolar aprotic solvent. Preferably, the bipolar aprotic solvent is selected from the group consisting of dimethylformamide (DMF), dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), dimethylsulfene (DMSO) At least one of them.

Please refer to FIG. 1. In the first embodiment, the present invention also provides a copper clad laminate 100, which is used to make a circuit board (not shown). The copper clad laminate 100 includes a first copper foil layer 10 and a first composite film 20 bonded to a surface of the first copper foil layer 10. The surface of the first copper foil layer 10 has relatively low roughness. Wherein, the surface roughness of the first copper foil layer 10 is between 0.12um and 2.1um. The first composite film 20 is formed by coating the fluorine-based resin modified composition on the surface of the first copper foil layer 10 and then heating it; wherein, during the heating process, the polyamide acid block copolymerization The fluorine-based additive undergoes a cyclization reaction, and the fluorine-based additive undergoes a sintering reaction; the first composite film 20 is formed by sintering the product formed by the cyclization reaction of the polyamide acid block copolymer and the fluorine-based additive The products are mixed to form.

Referring to FIG. 2, in the second embodiment, the present invention also provides a copper clad laminate 200. The structure of the copper clad laminate 200 is similar to that of the copper clad laminate 100. The only difference is that the copper clad laminate 200 also includes a The second copper foil layer 30 is formed on the first composite film 20.

3, in the third embodiment, the present invention also provides a copper clad laminate 300, the structure of the copper clad laminate 300 is similar to the copper clad laminate 200, the difference is only that the copper clad laminate 300 also includes a A first dielectric layer 40 and a second dielectric layer 50, and the first dielectric layer 40 and the second dielectric layer 50 are respectively located on opposite sides of the first composite film 20, the first A dielectric layer 40 is located on the first copper foil layer 10, and the second dielectric layer 50 is located on the second copper foil layer 30.

4, in the fourth embodiment, the present invention also provides a copper clad laminate 400, the structure of the copper clad laminate 400 and the copper clad laminate 200 are similar, the only difference is that the copper clad laminate 400 also includes a The second composite film 60 and a first dielectric layer 40, the first dielectric layer 40 is located between the first composite film 20 and the second composite film 60, and the second copper foil layer 30 is located The second composite film 60 is on.

Of course, the copper clad laminate in this case may also include more copper foil layers, composite films, and dielectric layers, as long as the composite film is coated and formed on the copper foil layer or the dielectric layer.

In the above-mentioned first to fourth embodiments, the first composite film 20 and/or the second composite film 60 can replace the adhesive layer and play the role of bonding the copper foil layer or the dielectric layer to obtain Copper clad laminate.

The present invention also provides a composite film, which is formed by heating the fluorine-based resin modification composition as described above; wherein, during the heating process, the polyamide acid block copolymer undergoes a cyclization reaction, The fluorine-based additive undergoes a sintering reaction; the composite film is formed by mixing the product formed by the cyclization reaction of the polyamide acid block copolymer and the product formed by the sintering of the fluorine-based additive. The thickness of the composite film is more than 25um.

。Among them, the dianhydride monomer and the diamine monomer undergo a polymerization reaction to form the polyamide acid block copolymer and the polyamide acid block copolymer in the fluorine-based resin modification composition is cyclized at high temperature to form the composite film The principle is:

.

The following specific examples further illustrate the polyamide acid block copolymer of the present invention.

Comparative example 1 Add NMP (55g) and surfactant (5g) into a 500ml reaction flask, stir at high speed until uniformly dispersed, then pour fluorine-based powder PTFE (40g) slowly, and stir at high speed until the whole amount is poured in at the same time. Continue to high speed After stirring for 24 hours, the PTFE fluorine-based resin composition is configured.

Comparative example 2 Add NMP (55g) and surfactant (5g) into a 500ml reaction flask, stir at high speed until evenly dispersed, then pour fluorine-based powder PFA (40g) slowly, and stir at high speed until the entire amount is poured in at the same time. Continue to high speed After stirring for 24 hours, the PFA fluororesin composition is configured.

Comparative example 3 Add NMP (233.91g) and TPE-M (0.05 mol, 14.61g) into a 500mL reaction flask. After stirring at high speed to dissolve, add TAHQ (0.05 mol, 22.93 g) and stir for 1 hour before adding APAB. (0.05 mol, 11.41 g), after stirring at high speed to dissolve, add BPADA (0.05 mol, 26.02 g) and stir for 48 hours to complete the configuration of the polyamide block copolymer.

Comparative example 4 Add the PTFE fluorine resin composition (Comparative Example 1, 123.9 g) into a 500 mL reaction flask, and stir at low speed. At the same time, slowly add the polyamide acid block copolymer (Comparative Example 3, 6.1 g), and continue stirring at low speed for 24 hours. , That is, the fluorine-based resin modified composition is configured.

Comparative example 5 PFA fluorine resin composition (Comparative Example 2, 123.9 g) was added into a 500 mL reaction flask, and stirred at low speed. At the same time, polyamide acid block copolymer (Comparative Example 3, 6.1 g) was slowly added, and stirring was continued at low speed for 24 hours , That is, the fluorine-based resin modified composition is configured.

Comparative example 6 Add the PTFE fluorine resin composition (Comparative Example 1, 119.9 g) into a 500 mL reaction flask, and stir at low speed. At the same time, slowly add the polyamide acid block copolymer (Comparative Example 3, 10.1 g), and continue stirring at low speed for 24 hours. , That is, the fluorine-based resin modified composition is configured.

Comparative example 7 Add the PFA fluorine resin composition (Comparative Example 2, 119.9 g) into a 500 mL reaction flask, and stir at low speed. At the same time, slowly add the polyamide acid block copolymer (Comparative Example 3, 10.1 g), and continue stirring at low speed for 24 hours. , That is, the fluorine-based resin modified composition is configured.

Comparative example 8 Add the PTFE fluorine resin composition (Comparative Example 1, 110.4 g) into a 500 mL reaction flask, and stir at low speed. At the same time, slowly add the polyamide acid block copolymer (Comparative Example 3, 19.6 g), and continue stirring at low speed for 24 hours. , That is, the fluorine-based resin modified composition is configured.

Comparative example 9 PFA fluorine resin composition (Comparative Example 2, 110.4 g) was added into a 500 mL reaction flask, and stirred at low speed. At the same time, polyamide acid block copolymer (Comparative Example 3, 19.6 g) was slowly added, and stirring was continued at low speed for 24 hours , That is, the fluorine-based resin modified composition is configured.

Comparative example 10 PFA fluorine resin composition (Comparative Example 2, 101.4 g) was added into a 500 mL reaction flask, and stirred at low speed. At the same time, polyamide acid block copolymer (Comparative Example 3, 28.6 g) was slowly added, and stirring was continued at low speed for 24 hours. , That is, the fluorine-based resin modified composition is configured.

Comparative example 11 PFA fluorine resin composition (Comparative Example 2, 92.9 g) was added into a 500 mL reaction flask, and stirred at low speed. At the same time, the polyamide acid block copolymer (Comparative Example 3, 37.1 g) was slowly added, and stirring was continued at low speed for 24 hours. , That is, the fluorine-based resin modified composition is configured.

Comparative example 12 PFA fluorine resin composition (Comparative Example 2, 84.8 g) was added into a 500 mL reaction flask, and stirred at low speed. At the same time, the polyamide acid block copolymer (Comparative Example 3, 45.2 g) was slowly added, and stirring was continued at low speed for 24 hours. , That is, the fluorine-based resin modified composition is configured.

Comparative example 13 Add the PFA fluorine resin composition (Comparative Example 2, 77.1 g) into a 500 mL reaction flask, and stir at low speed. At the same time, slowly add the polyamide acid block copolymer (Comparative Example 3, 52.9 g), and continue stirring at low speed for 24 hours. , That is, the fluorine-based resin modified composition is configured.

Example 1 Add the PFA fluorine resin composition (Comparative Example 2, 119.9 g) into a 500 mL reaction flask, and stir at low speed. At the same time, slowly add the polyamide acid block copolymer (Comparative Example 3, 10.1 g), and continue stirring at low speed for 24 hours. , That is, the fluorine-based resin modified composition is configured.

Example 2 PFA fluorine resin composition (Comparative Example 2, 110.4 g) was added into a 500 mL reaction flask, and stirred at low speed. At the same time, polyamide acid block copolymer (Comparative Example 3, 19.6 g) was slowly added, and stirring was continued at low speed for 24 hours , That is, the fluorine-based resin modified composition is configured.

Example 3 PFA fluorine resin composition (Comparative Example 2, 101.4 g) was added into a 500 mL reaction flask, and stirred at low speed. At the same time, polyamide acid block copolymer (Comparative Example 3, 28.6 g) was slowly added, and stirring was continued at low speed for 24 hours. , That is, the fluorine-based resin modified composition is configured.

The fluorine-based resin composition formed in Comparative Example 1-2, the polyamide acid block copolymer formed in Comparative Example 3, and the fluorine-based resin modified composition formed in Comparative Examples 4-13 were respectively coated on a copper foil layer. And high-temperature cyclization into a film to form a copper clad laminate. The fluorine-based resin composition formed in Comparative Example 1-2, the polyamide acid block copolymer formed in Comparative Example 3, and the fluorine-based resin modified composition formed in Comparative Examples 4-13 were subjected to viscosity tests respectively, and the high temperature The film formed by cyclization is tested for peel strength, 25um film formation (no holes), bleaching property, UV laser blind hole, dielectric constant, dielectric loss, and moisture absorption rate. The test results are shown in Table 1-3.

Please refer to Figure 5. The present invention also performs UV light absorbance test on the PTFE fluorine resin composition formed in Comparative Example 1 and the film formed by the fluorine resin composition formed in Example 1. The test results are shown in Figure 5. UV laser Drilling and cutting (300~400 nm UV absorption>90%). Table 1 Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2 Comparative example 3 Ingredients (% by weight) PTFE - - - 100 - - PFA 95 90 85 - 100 - Polyamic acid block copolymer 5 10 15 - - 100 Viscosity (cps) 2300 2553 2530 133 205 40,000~50,000 Peel strength (kgf/cm) 0.83 1.09 1.20 0.35 0.41 1.33 25um film formation (no holes) PASS PASS PASS NG NG PASS Floating tin test (288℃/10sec) PASS PASS PASS PASS PASS PASS UV laser blind hole PASS PASS PASS NG NG PASS Dk (10GHz) 2.3 2.5 2.6 2.1 2.1 3.0 Df (10GHz) 0.002 0.003 0.003 0.002 0.002 0.003 Moisture absorption rate (%) 0.02 0.03 0.03 0.01 0.02 0.3 Table 2 Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2 Comparative example 3 Ingredients (% by weight) PTFE - - - 100 - - PFA 95 90 85 - 100 - Polyamic acid block copolymer 5 10 15 - - 100 Viscosity (cps) 2300 2553 2530 133 205 40,000~50,000 Peel strength (kgf/cm) 0.83 1.09 1.20 0.35 0.41 1.33 25um film formation (no holes) PASS PASS PASS NG NG PASS Floating tin test (288℃/10sec) PASS PASS PASS PASS PASS PASS UV laser blind hole PASS PASS PASS NG NG PASS Dk (10GHz) 2.3 2.5 2.6 2.1 2.1 3.0 Df (10GHz) 0.002 0.003 0.003 0.002 0.002 0.003 Moisture absorption rate (%) 0.02 0.03 0.03 0.01 0.02 0.3 table 3 Comparative example 10 Comparative example 11 Comparative example 12 Comparative example 13 Ingredients (% by weight) PTFE - - - - PFA 85 80 75 70 Polyamic acid block copolymer 15 20 25 30 Viscosity (cps) 9830 2300 2750 2800 Peel strength (kgf/cm) 0.81 0.76 0.63 0.58 25um film formation (no holes) NG NG NG NG Floating tin test (288℃/10sec) PASS PASS PASS PASS UV laser blind hole PASS PASS PASS PASS Dk (10GHz) 2.8 2.8 2.9 2.9 Df (10GHz) 0.003 0.003 0.003 0.003 Moisture absorption rate (%) 0.09 0.13 0.18 0.22

Examples 1 to 3 and Comparative Examples 6 to 13 are PTFE and PFA fluorine resin compositions, mixed with thermoplastic polyimide block copolymers with low dielectric loss, and can be coated into single-sided copper clad laminates, composite films, and The double-sided copper clad laminate is formed by high temperature pressing, and UV laser cutting and drilling can be performed in the UV laser test. The UV absorbance test result shown in Figure 5 shows that the fluorine-based resin modified composition can successfully improve the fluorine It is a material processing problem; and the UV laser drilling test of Comparative Examples 1~2 (perfluorinated film) and Comparative Examples 4~5, there is a phenomenon that cannot be penetrated, and in the UV absorbance test results shown in Figure 5 The reason why the absorption of the wavelength 300~400nm is low is caused by the insufficient proportion of polyimide block copolymer.

Comparative Example 4, Comparative Example 6 and Comparative Example 8 are PTFE fluorine resin compositions, and their dispersion conditions are not good. It is necessary to reduce the viscosity and adjust the dispersion uniformity. Therefore, the viscosity is all> 500 cps, and the film thickness is all> 25 um during coating. Comparative Example 7, Comparative Example 9 and Comparative Example 10 are PFA resin compositions with relatively better dispersibility, and can be configured with a higher viscosity of 4000 to 10,000 cps, but during coating and film formation, phase separation occurs, and fine particles are formed. Hole. In Examples 1 to 3, the viscosity was adjusted to increase the uniformity of dispersion. After coating and forming the film, the film surface was intact (no holes were formed) and the viscosity was 2000-3000 cps (conducive to film thickness control), and after pressing into a double-sided copper clad laminate , The peeling strength is also relatively improved; Comparative Examples 11-13 are PFA dispersions, the viscosity of which is controlled at 2000-3000cps, when coating and film formation, severe separation (hole formation) will occur, and the water absorption will be greatly improved.

Examples 1~3 have good electrical properties (Dk/Df = 2.3~2.6/0.002~0.003), low moisture absorption (0.02~0.03%) and viscosity 2000~3000cps (conducive to film thickness control). After coating and film formation, The film surface is intact and has no holes, laminated into a double-sided board, no curling phenomenon, peeling strength> 0.8kgf/cm, and UV laser cutting and drilling can be performed; the present invention uses PFA dispersion and thermoplastic polyimide with low dielectric loss The block copolymers are matched to adjust the optimal ratio and viscosity to successfully improve the defects of the fluorine-based substrate that cannot be UV lasered, and have both electrical and thermoplastic properties.

The fluorine-based resin modified composition, composite film and copper clad laminate provided by the present invention have a polyamide acid block copolymer added to the fluorine-based resin composition, 1) the polyamide acid block copolymer has a benzene ring (π bond), can absorb UV light, therefore, the fluorine-based resin modified composition and the composite film can be drilled or cut by UV laser, which is conducive to fine processing; 2) the fluorine-based resin is modified The composition can be coated by heat treatment and synthesize the composite film, which can reduce the limitation of the process technology; 3) The polyamide acid block copolymer has liquid crystal groups and flexible groups, which can improve the The dielectric properties of the fluorine-based resin-modified composition, reduce the hygroscopicity of the fluorine-based resin-modified composition, and retain the thermoplasticity of the fluorine-based resin-modified composition; 4) modify the fluorine-based resin The viscosity of the composition is set in the range of 2000-3000 cps to facilitate the control of the coating thickness (≥25um) of the fluorine-based resin modified composition and obtain a flawless composite film.

The above are only the preferred embodiments of the present invention and do not limit the present invention in any form. Although the present invention has been disclosed as the preferred embodiments, it is not intended to limit the present invention. Anyone who is familiar with the profession Without departing from the scope of the technical solution of the present invention, when the technical content disclosed above can be used to make some changes or modification into equivalent implementations of equivalent changes, but all that does not deviate from the technical solution of the present invention, according to the technical essence of the present invention Any simple modifications, equivalent changes and modifications made to the above embodiments still fall within the scope of the technical solutions of the present invention.

100, 200, 300, 400: copper clad laminate 10: The first copper foil layer 20: The first composite membrane 30: The second copper foil layer 40: first dielectric layer 50: second dielectric layer 60: The second composite membrane

Fig. 1 is a schematic cross-sectional view of a copper clad laminate according to a first embodiment of the present invention.

Fig. 2 is a schematic cross-sectional view of a copper clad laminate according to a second embodiment of the present invention.

Fig. 3 is a schematic cross-sectional view of a copper clad laminate according to a third embodiment of the present invention.

Fig. 4 is a schematic cross-sectional view of a copper clad laminate of a fourth embodiment of the present invention.

Fig. 5 is a test result of the UV absorbance of the PTFE fluorine resin composition and the fluorine resin composition after film formation.

100: Copper Clad Laminate

10: The first copper foil layer

20: The first composite membrane

Claims (9)

A fluorine-based resin modification composition includes a fluorine-based resin composition and a polyamide acid block copolymer composition, wherein the fluorine-based resin composition includes a fluorine-based additive, a surfactant, and a solvent. The polyamide acid block copolymer composition includes a polyamide acid block copolymer. In terms of weight percentage, the fluorine-based additive/the polyamide acid block copolymer=85-95/5-15 In the fluorine-based resin composition, the weight percentage of the fluorine-based additives is 35% to 40%, and the weight percentage of the interface active agent is 3% to 5%. The fluorine-based resin modified composition according to claim 1, wherein the viscosity of the fluorine-based resin modified composition is 2000 to 3000 cps. The fluorine-based resin modification composition according to claim 1, wherein the fluorine-based additive is selected from the group consisting of polytetrafluoroethylene, polychlorotrifluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether, polyfluoroethylene At least one of ethylene, polyvinylidene fluoride, and fluoroplastic film, and the fluorine-based additive is powder. The fluorine-based resin modified composition according to claim 1, wherein the main chain of the polyamide acid block copolymer includes a plurality of repeating amide segments and alternately arranged in the amide segments On the liquid crystal group and flexible group. The fluorine-based resin-modified composition according to claim 4, wherein the liquid crystal group includes a plurality of aromatic rings and a bridge structure bonding the plurality of aromatic rings, and the aromatic ring is selected from

,

,

,

,

,

,

At least one of; the bridge structure is selected from

,

,

,

,

,

,

,

,

At least one of them. The fluorine-based resin modification composition according to claim 4, wherein the flexible group includes a long-chain saturated aliphatic hydrocarbon group, a long-chain unsaturated aliphatic hydrocarbon group or an ether group, and the long chain includes four or four Straight chain hydrocarbons of the above carbon atoms. The fluorine-based resin modification composition according to claim 4, wherein the polyamide acid block copolymer is produced by the polymerization reaction of a dianhydride monomer and a diamine monomer in a second solvent; In the polyamide acid block copolymer composition, the weight percentage of the dianhydride monomer and the diamine monomer is 20%-25%; the dianhydride monomer and the diamine monomer are respectively Including liquid crystal groups and flexible groups. A composite film, wherein the composite film is formed by heating the fluorine-based resin modified composition according to any one of claims 1 to 7; during the heating process, the polyamide acid block copolymer is formed In the cyclization reaction, the fluorine-based additive undergoes a sintering reaction; the composite film is formed by mixing the product formed by the cyclization reaction of the polyamide acid block copolymer and the product formed by the sintering of the fluorine-based additive. A copper clad laminate includes at least one copper foil layer, wherein the copper clad laminate further includes a composite film according to claim 8, and the composite film is formed on the copper foil layer.

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