TWI557180B - Composition for forming dissolvable polyimide, coverlayer, and manufacturing method thereof - Google Patents

Description

Composition for forming soluble polyimine, cover film and method for producing same

The present invention relates to a composition comprising a film of a film made from the composition and a method of manufacturing the same, and more particularly to a composition for forming a soluble polyimine, including A cover film of a polyimide film obtained by forming a composition of a soluble polyimide, and a method for producing the same.

As portable electronic products are gradually moving toward thin and light, the demand for flexible circuit boards has also increased significantly. The main upstream material of the flexible circuit board is a flexible copper foil substrate, which is usually made by covering a cover film on a copper foil, wherein the cover film comprises a polyimide film. Although the thickness of the polyimide film used in the industry is as thin as 5 μm, the process for forming a polyimide film having such a thickness is too complicated, resulting in a problem that production is difficult and the cost is increased. In addition, the polyimine film currently used in the industry also has the disadvantages of poor dielectric properties, high moisture absorption rate, high explosives in the reflow process, and high Young's modulus and strong anti-reflective force. therefore, How to effectively produce a polyimide film with low thinness, good dielectric properties, low moisture absorption rate and low Young's modulus is one of the urgent problems to be overcome.

The invention provides a composition for forming a soluble polyimine, which can prepare a polyimide film which is easy to be thin, has good dielectric properties, low moisture absorption rate, low Young's modulus and good chemical resistance. And the polyimine film is suitable for use in a cover film.

The composition for forming a soluble polyimine of the present invention comprises a long carbon chain aliphatic diamine monomer, a monomer containing a group selected from a hydroxyl group, a carboxyl group and a C=C group, and a tetracarboxylic dianhydride monomer. , bridging agent or initiator and solvent. The carbon number of the main chain of the long carbon chain aliphatic diamine monomer is 16 or more.

In one embodiment of the present invention, the carbon number of the main chain of the long carbon chain aliphatic diamine monomer is 36 or more.

In one embodiment of the present invention, the monomer having a group selected from the group consisting of a hydroxyl group, a carboxyl group, and a C=C includes a diamine monomer selected from a hydroxyl group, an acid anhydride monomer having a carboxyl group, and a diamine having a carboxyl group. At least one of a group consisting of a monomer and a diamine monomer containing C=C.

In one embodiment of the invention, the above-mentioned bridging agent includes a compound containing an epoxy group or an isocyanate group, and the initiator includes a peroxide.

In one embodiment of the invention, the solvent includes toluene, xylene, cyclohexane, cyclohexanone, N-methylpyrrolidone, dimethylacetamide, dimethylformamide or a mixture thereof.

In an embodiment of the invention, the above-described composition for forming a soluble polyimine further includes an additive including a flame retardant, a colorant, a filler, or a combination thereof.

The method for producing a cover film of the present invention comprises the following steps. First, the above-mentioned composition for forming a soluble polyimine is formed into a mixed solution containing polyienimine. Next, a mixed solution containing polyimine was applied onto the release layer. Subsequently, the coating of the mixed solution containing the polyimine is subjected to a heating process to form a polyimide film on the release layer. Thereafter, an adhesion layer was formed on the polyimide film.

In an embodiment of the invention, the method of forming the above polyimine-containing mixed solution comprises the following steps. First, a long carbon chain aliphatic diamine monomer, a monomer containing a group selected from a hydroxyl group, a carboxyl group, and a C=C group, and a tetracarboxylic dianhydride monomer are dissolved in a solvent, and reacted to form a polyfluorene. Amino acid solution. Next, the polyproline solution is subjected to a cyclization process to form a polyimine solution. Thereafter, a bridging agent or initiator is added to the polyimine solution.

In an embodiment of the invention, the process temperature of the heating process is between 100 ° C and 180 ° C, and the process temperature of the cyclization process is between 160 ° C and 200 ° C.

In an embodiment of the invention, the polyimine film has a thickness of between 1 μm and 20 μm.

In an embodiment of the invention, the release layer is flat or matte.

In an embodiment of the invention, the release layer is a single-sided release type, and the method for manufacturing the cover film further includes forming a protective layer on the adhesive layer, The protective layer includes a release material.

In an embodiment of the invention, the release layer is a double-sided release.

The cover film of the present invention comprises a release layer, a polyimide film, and an adhesive layer. The polyimide film is disposed on the release layer, and the polyimide film is formed from the above-described composition for forming a soluble polyimide. The layer is then placed on a polyimide film.

In an embodiment of the invention, the polyimine film has a thickness of between 1 μm and 20 μm.

In an embodiment of the invention, the release layer is flat or matte.

In an embodiment of the invention, the release layer is a single-sided release, and the cover film further includes a protective layer disposed on the adhesive layer, and the protective layer includes a release material.

In an embodiment of the invention, the release layer is a double-sided release.

Based on the above, the composition for forming a soluble polyimine according to the present invention comprises a long-chain aliphatic diamine monomer having a carbon number of 16 or more in the main chain, and a monomer selected from the group consisting of a hydroxyl group, a carboxyl group and C=C. The monomer of the group, the tetracarboxylic dianhydride monomer, the bridging agent or the initiator and the solvent, so that the polyimide film obtained by the same can have a low dielectric constant, a low dielectric loss, and a low moisture absorption rate. , low Young's modulus, good chemical resistance and heat resistance, and can achieve the requirements of thinning.

The above described features and advantages of the present invention will be more apparent from the following description.

100‧‧‧ release layer

102‧‧‧ Polyimine film

104‧‧‧Next layer

1000‧‧‧ Cover film

S10, S20, S30, S40‧‧‧ steps

1 is a flow chart showing the manufacture of a cover film in accordance with an embodiment of the present invention.

2 is a schematic view of a cover film in accordance with an embodiment of the present invention.

In the present specification, the range represented by "a value to another value" is a schematic representation that avoids enumerating all the values in the range in the specification. Therefore, the recitation of a particular range of values is intended to include any value in the range of values and the range of values defined by any value in the range of values, as in the specification. The scope is the same.

In order to prepare a polyimide film which is easy to be thin, has good dielectric properties, low moisture absorption rate, low Young's modulus and good chemical resistance and is suitable for use in a cover film, the present invention proposes to form a soluble poly The composition of the quinone imine can achieve the above advantages by the polyimide film obtained by the composition. Hereinafter, the specific embodiments are described as examples in which the present invention can be implemented.

An embodiment of the present invention provides a composition for forming a soluble polyimine comprising a long carbon chain aliphatic diamine monomer, a monomer containing a group selected from a hydroxyl group, a carboxyl group, and a C=C group, A carboxylic acid dianhydride monomer, a bridging agent or initiator, and a solvent. Hereinafter, the various components described above will be described in detail.

The carbon number of the main chain of the long carbon chain aliphatic diamine monomer is 16 or more, preferably 36 or more. When the carbon number of the main chain is less than 16, the aliphatic chain is too short, so that Polyimine obtained by the diamine monomer has poor solubility and relatively poor water absorption and electrical properties. Further, in one embodiment, the carbon number of the main chain of the long carbon chain aliphatic diamine monomer is 40 or less.

Specifically, the long carbon chain aliphatic diamine monomer includes, but is not limited to, 1,16-hexadecane diamine (1,16-Hexadecane diamine), 1,18-octadecanediamine (1,18). -Octadecane diamine). Further, as a long carbon chain aliphatic diamine monomer group may also be used commercially available products, e.g. Priamine ^TM 1074-Dimer diamine or Priamine ^TM 1075 (Croda Japan (Croda Japan) Ltd.) or Versamine 551 (BASF Corp.) .

It should be noted that in the present embodiment, the composition for forming a soluble polyimine is such that a long-chain aliphatic diamine monomer having a carbon number of 16 or more in the main chain is used to form a soluble solvent. The purpose of polyimine. In addition, the composition for forming a soluble polyimine is also passed through a long-chain aliphatic diamine monomer having a carbon number of 16 or more in the main chain, so that the polyimide film obtained therefrom can At the same time, it has low dielectric constant, low dielectric loss, low moisture absorption rate and low Young's modulus.

The monomer having a group selected from a hydroxyl group, a carboxyl group and a C=C includes a diamine monomer selected from a hydroxyl group, an acid anhydride monomer containing a carboxyl group, a diamine monomer having a carboxyl group, and a diamine monomer containing C=C. At least one of the groups consisting of bodies. In one embodiment, the monomer containing a group selected from a hydroxyl group, a carboxyl group, and C=C includes, for example, an acid anhydride monomer having a carboxyl group and a diamine monomer having a carboxyl group.

Specifically, the hydroxyl group-containing diamine monomer includes, but is not limited to, 3, 3'-di 3,3'-Dihydroxy-4,4'-diamino-biphenyl (HAB); carboxylate-containing anhydride monomers including but not limited to: trimellitic acid Anhydride (referred to as TMA); a carboxyl group-containing diamine monomer including but not limited to: 3,5-diaminobenzoic acid (DABZ), 6,6'-bisamino-3,3' - methylene bis (anthranilic acid, abbreviated as MBAA); diamine monomers containing C=C include but are not limited to: 2-vinyl-4,6-diamino-1,3,5 -Triazine (2-vinyl-4,6-diamino-1,3,5-triazine), 2,4-diamino-6-(isobutenyloxy)ethyl-1,3,5-triazine ( 2,4-diamino-6-(methacryloyloxy)ethyl-1,3,5-triazine). In one embodiment, the monomer containing a group selected from the group consisting of a hydroxyl group, a carboxyl group, and C=C includes, for example, trimellitic anhydride and 3,5-diaminobenzoic acid.

The tetracarboxylic dianhydride monomer can be any tetracarboxylic dianhydride compound known to those of ordinary skill in the art. Specifically, the tetracarboxylic dianhydride monomer includes, but is not limited to, 4,4'-oxyphthalic anhydride (Bis-(3-phthalyl anhydride)ether, ODPA), 3,3', 4, 4'-benzophenone tetracarboxylic dianhydride (3,3',4,4'-Benzophenonetetracarboxylic dianhydride, BTDA for short), pyromellitic Dianhydride (PMDA), bisphenol A diether II Anhydride (4,4'-(4,4'-isopropylidenediphenoxy)bis (phthalic anhydride), or BP3,4,4'-biphenyltetracarboxylic dianhydride (3,3',4, 4'-Biphenyltetracarboxylic dianhydride (BPDA). Further, in the present embodiment, the above-mentioned tetracarboxylic dianhydride monomer may be single Used alone or in combination.

The bridging agent includes a compound containing an epoxy group or an isocyanate group. Specifically, the bridging agent includes, but is not limited to, a phenol novolac type epoxy resin, a naphthalene type epoxy resin, or a bisphenol A type epoxy resin. . Further, as the bridging agent containing an epoxy group, a commercially available product such as CNE-200EL or PNE-177 (manufactured by CCP Changchun Co., Ltd.), EPOXY 4700 (manufactured by DIC Corporation) or ESCV-90CR (manufactured by Nippon Steel Chemical Co., Ltd.) can be used. And as a bridging agent containing an isocyanate group, a commercially available product such as Desmodur N 3600 or Desmodur VK10 (manufactured by Bayer Co., Ltd.) can be used. The starter includes a peroxide. Specifically, the initiators include, but are not limited to, benzoyl peroxide (BPO), tert-Butyl hydroperoxide (TBH) or dilauroyl peroxide.

It is worth mentioning that the bridging agent can crosslink with a hydroxyl group or a carboxyl group in a monomer having a hydroxyl group or a carboxyl group, and the initiator can assist the crosslinking reaction in the C=C in the monomer containing C=C. That is, if a composition containing a hydroxyl group or a carboxyl group is used as a composition for forming a soluble polyimine, a bridging agent is selected, and if a composition for forming a soluble polyimine is used, a C= is used. For the monomer of C, the initiator is selected. In this way, the composition for forming the soluble polyimine is permeated through a monomer comprising a group selected from a hydroxyl group, a carboxyl group and a C=C, and a bridging agent or a starter. The amine film can have good chemical resistance and heat resistance.

Solvents include, but are not limited to, toluene, xylene, cyclohexane, cyclohexanone, N-methylpyrrolidone, dimethylacetamide, dimethylformamide or mixtures thereof. In one embodiment, the solvent is, for example, a mixture of cyclohexanone and N-methylpyrrolidone.

Further, the composition for forming a soluble polyimine of the present invention may further comprise other diamine monomers such as 2,2'-bis[4-(4-aminophenoxyphenyl)]propane (2). , 2'-Bis[4-(4-aminophenoxy)phenyl]propane, abbreviated as BAPP), 4,4'-Methylene dianiline, α,α'-di(4- Aminophenyl)-1,4-diisopropylbenzene (α,α'-bis(4-aminophenyl)-1,4-diisopropylbenzene), 4,4'-diaminodiphenyl ether (4,4'- Oxydianiline), 3,3'-dimethyl-4,4'-diaminobiphenyl (3,3'-Dimethyl-4,4'-diaminobiphenyl) or 1,4-bis(4-aminophenoxy) Benzene (1,4-Bis(4-aminophenoxy)benzene).

Further, the composition for forming a soluble polyimine may further contain an additive as needed within a range that does not impair the effect of the composition for forming a soluble polyimine of the present invention. The additive includes a flame resistant agent, a colorant, a filler, or a combination thereof.

The flame retardant includes, but is not limited to, an organophosphorus compound, an organic nitrogen compound, or an inorganic aluminum hydroxide. In detail, the composition for forming a soluble polyimine is permeated by including a flame retardant, so that the polyimide film produced therefrom can have good flame resistance.

Colorants include, but are not limited to, pigments, dyes, carbon powder or titanium dioxide. In detail, the composition for forming a soluble polyimine is permeated by including a coloring agent, so that the color of the polyimide film produced therefrom can be adjusted.

Fillers include, but are not limited to, cerium oxide or calcium carbonate. In detail, the composition for forming a soluble polyimine comprises a filler, so that the polyimide film produced therefrom can have good hardness and wear resistance.

In addition, since the composition for forming a soluble polyimine of the present invention is capable of forming a soluble polyimine, it is applied to a polyimide film formed in a cover film, so that the cover film can be made thinner. Demand. Hereinafter, a detailed description will be given with reference to FIGS. 1 and 2 .

1 is a flow chart showing the manufacture of a cover film in accordance with an embodiment of the present invention. 2 is a schematic view of a cover film in accordance with an embodiment of the present invention. In Figure 2, the layers are not drawn to scale.

Referring to FIG. 1, step S10 is performed to form a polyimine-containing mixed solution of the composition for forming a soluble polyimine in any of the foregoing embodiments. In detail, the method of forming a mixed solution containing a polyimine comprises the following steps. First, a long carbon chain aliphatic diamine monomer, a monomer containing a group selected from a hydroxyl group, a carboxyl group, and a C=C group, and a tetracarboxylic dianhydride monomer are dissolved in a solvent, and reacted to form a polyfluorene. Amino acid solution. In one embodiment, in the foregoing step, the reaction time is, for example, between 1 hour and 6 hours; and the solid content of the polyaminic acid solution is, for example, between 10% and 50%, but the present invention Not limited to this.

Next, the polyproline solution is subjected to a cyclization process to form a polyimine solution. In the step, the process temperature of the cyclization process is, for example, between 160 ° C and 200 ° C; the process time is, for example, between 1 hour and 6 hours; and the solid content of the polyimine solution is, for example, Between 10% and 50%. In detail, in the ring In the process, poly-proline will undergo a ruthenium imidization reaction (ie, dehydration cyclization reaction) to form a polyimide soluble in a solvent, that is, a polyimine solution. More specifically, as described above, the composition for forming a soluble polyimine is a long-chain aliphatic diamine monomer having a carbon number of 16 or more in the main chain, thereby achieving solubility. The purpose of polyimine.

Thereafter, a bridging agent or a starter is added to the polyimine solution to form a mixed solution containing polyimine. In detail, as described above, according to the kind of the monomer containing a group selected from a hydroxyl group, a carboxyl group, and a C=C used in the composition for forming a soluble polyimine, in one embodiment, The polyimine-containing mixed solution may include a soluble polyimine, a solvent, and a bridging agent; and in another embodiment, the polyimine-containing mixed solution may include a soluble polyimine, a solvent, and a starter. .

Next, referring to FIG. 1 and FIG. 2 simultaneously, step S20 is performed to apply a polyimine-containing mixed solution to the release layer 100 to form a coating layer (not shown) on the release layer 100. In this step, the coating means includes, but is not limited to, blade coating, wire bar coating or screen printing. Further, the release layer 100 is realized, for example, as a release film capable of providing sufficient supporting force for the polyimide film formed in the subsequent step. In addition, the release layer 100 may be flat or matte to adjust the surface roughness and gloss of the polyimide film formed in the subsequent step. In addition, the release layer 100 is a double-sided release type.

Next, in step 30, a coating of the polyimine-containing mixed solution is subjected to a heating process to form a polyimide film 102 on the release layer 100. In an embodiment, in the step, the process temperature of the heating process is, for example, between 100 ° C and Between 180 ° C; the process time is, for example, between 1 hour and 6 hours; and the thickness of the polyimide film 102 is, for example, between 1 μm and 20 μm. In another embodiment, in the step, the process temperature of the heating process is, for example, between 100 ° C and 180 ° C; the process time is, for example, between 1 minute and 20 minutes; and the polyimide film The thickness of 102 is, for example, between 1 μm and 20 μm. In detail, in the heating process, the solvent in the mixed solution containing the polyimine is removed, and at the same time, the soluble polyimide and the bridging agent in the mixed solution containing the polyimide are cross-linked. Or the soluble polyimine in a mixed solution containing polyimine will be initiated by a starter to carry out a crosslinking reaction. More specifically, as described above, a long carbon chain aliphatic diamine monomer having a carbon number of 16 or more in the main chain is used as a composition for forming a soluble polyimine to form a polyimide film. 102 is capable of having both a low dielectric constant, a low dielectric loss, a low moisture absorption rate, and a low Young's modulus; and a composition selected from the group consisting of a hydroxyl group, a carboxyl group, and a C through a composition for forming a soluble polyimine. The monomer of the group of =C and the bridging agent or initiator make the polyimide film 102 capable of having good chemical resistance and heat resistance. However, the invention is not limited thereto. In other embodiments, only the solvent in the polyimine-containing mixed solution is removed during the heating process.

In addition, since the polyimide film 102 is formed by a heating process of a polyimine-containing mixed solution formed on the release layer 100 by a coating method, the polyimide film is formed. The thickness of 102 can be controlled between 1 μm and 20 μm, and the demand for thinning is effectively achieved. Further, when the thickness of the polyimide film 102 is thinner, the amount of the polyimine-containing mixed solution used for coating is increased. Less, the cost is reduced.

Thereafter, in step 40, an adhesive layer 104 is formed on the polyimide film 102, thereby completing the production of the cover film 1000. The method of forming the adhesive layer 104 on the polyimide film 102 includes applying an adhesive to the polyimide film 102 by a coating process, including but not limited to: doctor blade coating, Wire bar coating or screen printing, and adhesives include, but are not limited to, epoxy resin adhesives, acrylic resin adhesives or polyurethane resin adhesives. In addition, the thickness of the subsequent layer 104 is between 5 μm and 50 μm. Further, in the present embodiment, since the release layer 100 is double-sided release type, the cover film 1000 can be directly wound.

Further, by performing all of the above steps (S10 to S40), the cover film 1000 of one embodiment of the present invention can be obtained. Referring again to FIG. 2, the cover film 1000 includes a release layer 100, a polyimide film 102 disposed on the release layer 100, and an adhesive layer 104 disposed on the polyimide film 102. The materials, characteristics, formation methods, and effects of the release layer 100, the polyimide film 102, and the adhesive layer 104 have been described in detail above, and thus will not be described herein.

It should be noted that in the cover film 1000, the release layer 100 on which the polyimide film 102 and the adhesive layer 104 are disposed may be regarded as a support, thereby making the polyimide polyimide use the cover film 1000. The size of the film 102 and the adhesive layer 104 are not easily deformed, and have good dimensional stability. Further, as described above, since the Young's modulus of the polyimide film 102 is low, the use of the upper cover film 1000 can have good handleability. In one embodiment, the cover film 1000 can be attached to the copper foil by the adhesive layer 104 to form a soft copper foil substrate.

Further, when the cover film 1000 is applied to a flexible copper foil substrate, since the polyimide film 102 has a low dielectric constant, low dielectric loss, chemical resistance, and heat resistance, the flexible copper foil substrate can have a good Reliability and process yield. In detail, the polyimide film 102 has a low dielectric constant and a low dielectric loss, thereby reducing electrical interference between lines in a flexible circuit board made of a soft copper foil substrate, and helping to avoid parasitic occurrence. Capacitance and its derived power load, and avoiding signal delay or interference, resulting in increased power consumption. In addition, when the cover film 1000 is applied to a flexible copper foil substrate, since the polyimide film 102 has low hygroscopicity, the cover film 1000 can be prevented from undergoing another process before the reflow process as compared with the conventional cover film. The baking process still makes the explosion plate not occur in the reflow process, thereby achieving the advantages of reducing the process steps, reducing the manufacturing cost, and improving the process yield.

Further, in the embodiment of FIGS. 1 and 2, the release layer 100 in the cover film 1000 is a double-sided release type, but the present invention is not limited thereto. In other embodiments, the release layer 100 in the cover film 1000 can also be a single-sided release. At this time, the cover film 1000 further includes a protective layer (not shown) disposed on the adhesive layer 104 to protect the adhesive layer 104, and the protective layer includes a release material. In detail, the protective layer is, for example, a release film or a release paper.

The features of the present invention will be more specifically described below with reference to Examples 1 to 4 and Comparative Examples 1 and 2. Although the following Examples 1 to 4 are described, the materials used, the amounts and ratios thereof, the processing details, the processing flow, and the like can be appropriately changed without departing from the scope of the invention. Therefore, the invention should not be construed restrictively by the examples described below.

The information on the main materials and equipment used in the preparation of the polyimides and the cover films of Examples 1 to 4 and Comparative Examples 1 and 2 is as follows.

The long chain aliphatic diamine monomer: tradename Priamine ^TM 1074-Dimer diamine, manufactured by Croda Japan, in which the carbon number of the main chain is 36.

a monomer containing a group selected from a hydroxyl group, a carboxyl group, and a C=C: trimellitic anhydride (hereinafter abbreviated as TMA), purchased from Eastcom Corporation; 3,5-diaminobenzoic acid (hereinafter referred to as DABZ), purchased from Koi Company; 2-vinyl-4,6-diamino-1,3,5-triazine, purchased from Shikoku Chemicals Corporation.

Tetracarboxylic dianhydride monomer: 4,4'-oxydiphthalic anhydride (hereinafter referred to as ODPA), available from TCI Corporation.

Other diamine monomers: 2,2'-bis[4-(4-aminophenoxyphenyl)]propane (hereinafter referred to as BAPP) were purchased from Eastcom Corporation.

Bridging agent: The trade name is EPOXY 4700, manufactured by DIC Corporation.

Starting agent: Benzoyl peroxide (hereinafter referred to as BPO), manufactured by Xin Industrial.

Solvent: cyclohexanone, purchased from Shengyi Chemical Company; N-methylpyrrolidone (hereinafter referred to as NMP), purchased from Bolu.

Copper foil: purchased from Japan Electrolysis Corporation.

Polyimine film: trade name 30EN, purchased from DuPont.

Release film: trade name PET-50-SHP-A, purchased from Fujiko.

The following agent: epoxy resin adhesive, manufactured by Taihong Company.

Low force meter: manufactured by Mitutoyo America Corporation under the name Litematic LV-50A.

Experiment 1

Hereinafter, the properties of the polyimide film proposed in the above embodiment will be described in detail by Example 1 and Comparative Example 1.

Example 1

The ODPA 4mole of, 1.2mole of TMA, 3mole the ^{Priamine TM 1074-Dimer diamine, DABZ} 1.5mole and 0.5mole of BAPP dissolved in a mixture of cyclohexanone and NMP in. Next, the resulting mixed solution was subjected to a reaction for 2 hours to obtain a polyamine acid solution having a solid content of 40%. Next, the polyaminic acid solution was subjected to hydrazine imidation reaction at 180 ° C for 3 hours to obtain a polyienimine solution having a solid content of 44%. Next, 0.3 mole of EPOXY 4700 was added to the polyimine solution to form a mixed solution containing polyimine. Thereafter, the polyimine-containing mixed solution was applied onto a copper foil with a doctor blade, and then heated at 160 ° C for 2 hours to remove cyclohexanone and NMP, and to make polyimine and EPOXY 4700 A crosslinking reaction is carried out. Subsequently, the copper foil was removed by an etching process to obtain a polyimide film of Example 1, in which the thickness was measured with a low force meter and the thickness was 7 μm.

Example 2

The 4mole of ODPA, 1.2mole of ^{TMA, Priamine TM 1074-Dimer diamine} 3mole of 1.5mole of 2-vinyl-4,6-diamino-1,3,5-triazine ring and 0.5mole of BAPP was dissolved In a mixture of ketone, NMP and toluene. Next, the resulting mixed solution was subjected to a reaction for 2 hours to obtain a polyamine acid solution having a solid content of 40%. Next, the polyaminic acid solution was subjected to hydrazine imidation reaction at 170 ° C for 2 hours to obtain a polyimine solution having a solid content of 42%. Next, 0.3 mole of EPOXY 4700 and BPO added in an amount of 5 wt% based on the weight of the polyimine were added to the polyimine solution to form a mixed solution containing polyimine. Thereafter, the polyimine-containing mixed solution was applied onto a copper foil with a doctor blade, and then heated at 160 ° C for 2 hours to remove cyclohexanone, NMP, and toluene, and to make the polyimide. EPOXY 4700 performs a crosslinking reaction and cross-links the polyimine by starting with BPO. Subsequently, the copper foil was removed by an etching process to obtain a polyimide film of Example 2, in which the thickness was measured with a low force meter and the thickness was 7 μm.

Comparative example 1

Unlike Example 1, in Comparative Example 1, the polyimide film was not prepared by itself, but a commercially available product polyimide film 30EN (thickness: 7 μm) was directly used.

Thereafter, the polyimine films of Example 1, Example 2, and Comparative Example 1 were measured for Young's modulus, dielectric constant, dielectric loss, and moisture absorption rate, respectively. The description of each of the foregoing tests is as follows, and the results of the tests are shown in Table 1.

<Determination of Young's Modulus>

The Young's modulus of the polyimide film of Example 1, Example 2 and Comparative Example 1 was measured in accordance with the provisions of ASTM-D882-02. In Table 1, the lower the numerical value, the smaller the rigidity of the polyimide film.

<Measurement of dielectric constant and dielectric loss>

According to IPC-TM-650 2.5.5.5.1B, the network analyzer (model ZVB20, manufactured by ROHDE & SCHWARZ) was used to measure Example 1, Example 2 and compare respectively. The dielectric constant and dielectric loss of the polyimide film of Example 1, wherein the measurement frequency was 10 GHz. In Table 1, the lower the value, the better the dielectric properties of the polyimide film.

<Measurement of moisture absorption rate>

The moisture absorption rate of the polyimide film of Example 1, Example 2, and Comparative Example 1 was measured in accordance with the provisions of IPC-TM-650 2.6.2.1. In Table 1, the lower the value, the poly The lower the moisture absorption rate of the quinone imine film.

As is clear from Table 1, the long-chain aliphatic diamine monomer having a carbon number of 16 or more in the main chain of the present invention is contained in comparison with the polyimine film of Comparative Example 1 (i.e., a commercially available product). Polyamides of Examples 1 and 2 prepared by a monomer selected from the group consisting of a hydroxyl group, a carboxyl group and a C=C group, a tetracarboxylic dianhydride monomer, a bridging agent or a starter and a solvent. The amine film has both a low Young's modulus, a dielectric constant, a dielectric loss, and a moisture absorption rate.

Experiment 2

Hereinafter, the characteristics of the cover film proposed by the above embodiment will be described in detail by the third embodiment, the fourth embodiment, and the comparative example 2.

Example 3

The ODPA 4mole of, 1.2mole of TMA, 3mole the ^{Priamine TM 1074-Dimer diamine, DABZ} 1.5mole and 0.5mole of BAPP dissolved in a mixture of cyclohexanone and NMP in. Next, the resulting mixed solution was subjected to a reaction for 2 hours to obtain a polyamine acid solution having a solid content of 40%. Next, the polyaminic acid solution was subjected to hydrazine imidation reaction at 180 ° C for 3 hours to obtain a polyienimine solution having a solid content of 44%. Next, 0.3 mole of EPOXY 4700 was added to the polyimine solution to form a mixed solution containing polyimine. Thereafter, the polyimine-containing mixed solution was applied onto a release film PET-50-SHP-A with a doctor blade, and then heated at 160 ° C for 3 minutes to remove cyclohexanone and NMP. The polyimide film of Example 3 was obtained. Next, an epoxy resin adhesive was applied onto the polyimide film of Example 3 by a doctor blade, followed by baking at 160 ° C for 3 minutes to remove the solvent of the epoxy resin adhesive to obtain an example. 3 cover film.

Example 4

The 4mole of ODPA, 1.2mole of ^{TMA, Priamine TM 1074-Dimer diamine} 3mole of 1.5mole of 2-vinyl-4,6-diamino-1,3,5-triazine ring and 0.5mole of BAPP was dissolved In a mixture of ketone, NMP and toluene. Next, the resulting mixed solution was subjected to a reaction for 2 hours to obtain a polyamine acid solution having a solid content of 40%. Next, the polyaminic acid solution was subjected to hydrazine imidation reaction at 170 ° C for 2 hours to obtain a polyimine solution having a solid content of 42%. Next, 0.3 mole of EPOXY 4700 and BPO added in an amount of 5 wt% based on the weight of the polyimine were added to the polyimine solution to form a mixed solution containing polyimine. Thereafter, the polyimine-containing mixed solution was applied onto a release film PET-50-SHP-A with a doctor blade, followed by heating at 160 ° C for 3 minutes to remove cyclohexanone, NMP, and toluene. Further, the polyimide film of Example 4 was obtained. Next, an epoxy resin adhesive was applied onto the polyimide film of Example 4 by a doctor blade, followed by baking at 160 ° C for 3 minutes to remove the solvent of the epoxy resin adhesive to obtain an example. 4 cover film.

Comparative example 2

In Comparative Example 2, the cover film was applied by directly applying an epoxy resin adhesive to a commercially available product polyimide film 30EN (thickness: 7 μm), followed by baking at 160 ° C for 3 minutes. Obtained by removing the solvent of the epoxy resin.

Thereafter, the cover films of Example 3, Example 4, and Comparative Example 2 were subjected to a half-field heat resistance test and a back-force test. The description of each of the foregoing tests is as follows, and the results of the tests are shown in Table 2.

<Hakata Heat Resistance Test>

The solder resist test pieces of Example 3, Example 4, and Comparative Example 2 were prepared: the cover films of Example 3, Example 4, and Comparative Example 2 were respectively bonded to a copper foil at 190 ° C, and then at 160 ° C. The mixture was heated for 2 hours to cause the polyimine in the cover film of Example 3 to be cross-linked with EPOXY 4700 and cross-linked with an epoxy resin adhesive; the polyazide in the cover film of Example 4 was obtained. The amine is cross-linked with EPOXY 4700, cross-linked with an epoxy resin binder, and cross-linked by initiation of BPO; and the epoxy resin binder in the cover film of Comparative Example 2 is cross-linked. .

Then, according to the provisions of IPC-TM-650 No.2.4.13, respectively The solder resist test pieces of Example 3, Example 4 and Comparative Example 2 were subjected to a half-field heat resistance test. In Table 2, the higher the temperature value indicates the higher the temperature that the cover film can withstand without bursting.

<Anti-power test>

The back-force test pieces of Example 3, Example 4, and Comparative Example 2 were prepared. First, the cover films of Example 3, Example 4, and Comparative Example 2 were cut to have a width of 10 mm × 30 mm. Next, the cut cover films of Example 3, Example 4, and Comparative Example 2 were placed so that the backing layer was faced upward, and then heated at 160 ° C for 2 hours to make the polyimide in the cover film of Example 3. The imine is cross-linked with EPOXY 4700 and cross-linked with an epoxy resin adhesive; the polyimine in the cover film of Example 4 is cross-linked with EPOXY 4700, and is bonded to an epoxy resin adhesive. The reaction was carried out, and the crosslinking reaction was carried out by the initiation of BPO; and the epoxy resin adhesive in the cover film of Comparative Example 2 was subjected to a crosslinking reaction.

Next, using a reverse force tester (manufactured by SHIMADZU Co., Ltd., model: AUY220), the counter-force test pieces of Example 3, Example 4, and Comparative Example 2 were subjected to a reverse force test according to the following procedures. First, adjust the balance to zero. Next, one end of the back-force test piece of Example 3, Example 4 and Comparative Example 2 was respectively fixed at the holder above the test piece tray, and the other end was stuck on the holder at the center of the test piece tray, The counter-force test pieces of Example 3, Example 4, and Comparative Example 2 were bent into a U-shape. After that, slowly lower the deck at the center of the test strip tray until it comes into contact with the underlying gasket, at the same time, the balance reading is accompanied The deck is changed and the change is recorded. The maximum value of this change is the counter-power value. In Table 2, the lower the value, the lower the counterforce of the cover film.

As can be seen from Table 2, in the half-field heat resistance test, the cover films of Examples 3 and 4 of the present invention were able to be at a higher temperature (288 ° C) before being baked than in the cover film of Comparative Example 2. ) without exploding. Further, as is clear from Table 2, the cover films of Example 3 and Example 4 of the present invention have a lower counter-initiation force than the cover film of Comparative Example 2.

The present invention has been disclosed in the above embodiments, but it is not intended to limit the invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims.

S10, S20, S30, S40‧‧‧ steps

Claims (20)

A composition for forming a soluble polyimine, comprising: a long carbon chain aliphatic diamine monomer, wherein the long carbon chain aliphatic diamine monomer has a carbon number of 16 or more; a monomer selected from the group consisting of a hydroxyl group, a carboxyl group, and a C=C group, wherein the monomer having a group selected from the group consisting of a hydroxyl group, a carboxyl group, and a C=C includes a group selected from the group consisting of a hydroxyl group-containing diamine monomer and a carboxyl group. At least two of the group consisting of an acid anhydride monomer, a carboxyl group-containing diamine monomer, and a C=C containing diamine monomer; a tetracarboxylic dianhydride monomer; a bridging agent or a starter; and a solvent . The composition for forming a soluble polyimine according to the first aspect of the invention, wherein the long carbon chain aliphatic diamine monomer has a carbon number of 36 or more. The composition for forming a soluble polyimine as described in claim 1, wherein the carboxyl group-containing diamine monomer comprises 3,5-diaminobenzoic acid. The composition for forming a soluble polyimine as described in claim 1, wherein the bridging agent comprises a compound containing an epoxy group or an isocyanate group, and the initiator comprises a peroxide. The composition for forming a soluble polyimine according to claim 1, wherein the solvent comprises toluene, xylene, cyclohexane, cyclohexanone, N-methylpyrrolidone, and dimethyl Indoleamine, dimethylformamide or a mixture thereof. The composition for forming a soluble polyimine, as described in claim 1, further comprising an additive comprising a flame retardant, a colorant, a filler, or a combination thereof. A method for producing a cover film comprising: forming a composition containing a polyimine according to the composition for forming a soluble polyimine according to claim 1 of the patent application; forming the polyimide-containing mixed solution; a mixed solution is coated on the release layer; a heating process of the polyimine-containing mixed solution is performed to form a polyimide film on the release layer; and on the polyimide film An adhesive layer is formed. The method for producing a cover film according to claim 7, wherein the method for forming the polyimine-containing mixed solution comprises: the long carbon chain aliphatic diamine monomer, the containing a monomer derived from a hydroxyl group, a carboxyl group, and a C=C group, and the tetracarboxylic dianhydride monomer are dissolved in the solvent, and reacted to form a polyaminic acid solution; the polyamic acid solution is A cyclization process is performed to form a polyimine solution; and the bridging agent or the initiator is added to the polyimine solution. The method for manufacturing a cover film according to claim 8, wherein the process temperature of the heating process is between 100 ° C and 180 ° C, and the process temperature of the cyclization process is between 160 ° C and 200 ° C. between. The method for producing a cover film according to claim 7, wherein The polyimide film has a thickness of between 1 μm and 20 μm. The method for producing a cover film according to claim 7, wherein the release layer is flat or matte. The method for producing a cover film according to claim 7, wherein the release layer is a single-sided release. The method for producing a cover film according to claim 12, further comprising forming a protective layer on the adhesive layer, the protective layer comprising a release material. The method for producing a cover film according to claim 7, wherein the release layer is a double-sided release type. A cover film comprising: a release layer; a polyimide film disposed on the release layer, wherein the polyimide film is formed by forming a soluble polyfluorene as described in claim 1 The composition of the imine is formed; and the adhesive layer is disposed on the polyimide film. The cover film of claim 15, wherein the polyimide film has a thickness of between 1 μm and 20 μm. The cover film of claim 15, wherein the release layer is flat or matte. The cover film of claim 15, wherein the release layer is a single-sided release. The cover film as described in claim 18, further comprising a protective layer, Disposed on the adhesive layer, the protective layer comprises a release material. The cover film of claim 15, wherein the release layer is a double-sided release.