TWI902275B - Polyamic acid resin composition and application thereof - Google Patents

Abstract

A polyamic acid resin composition comprising: (a) polyamic acid resin; (b) an ester compound; (c) a free radical trap; (d) a slip agent; and (e) a solvent is provided. The resin coating formed by the composition is removable by an alkaline solution.

Description

Polyamide resin compositions and their applications

This invention relates to a polyamide resin composition that can serve as a high-temperature lamination support layer and has the function of isolating and protecting the underlying copper foil circuit substrate. After the high-temperature lamination process is completed, this resin composition can be removed with an alkaline aqueous solution.

In recent years, due to advancements in semiconductor and electronic components, electronic devices are developing towards miniaturization, lightweighting, high performance, and multifunctionality. Consequently, printed circuit boards (PCBs) are also gradually progressing towards higher density and surface mount technology (SMT) of components. Currently, many technologies manufacture PCBs as multi-layered circuit structures to increase the internal space for circuit layout. The manufacturing process of multi-layered PCBs involves repeatedly stacking and bonding layers of copper foil or other suitable conductive materials and semi-solid film (PP, prepreg) or other suitable dielectric materials onto a core board to increase the internal wiring space. Electroplating is then used to fill the vias or blind holes in each layer with conductive material to connect the layers.

Polyimide resins possess excellent heat resistance and mechanical properties, making them widely used in various fields, primarily the electronics industry. During the manufacturing process of printed circuit boards (PCBs), protective films or resin coatings, primarily composed of polyimide, epoxy resin, or acrylic resin, are applied to the PCB to prevent oxidation of metal traces and corrosion from acidic or alkaline solutions. These coatings provide protection and support during high-temperature lamination. In recent years, with the development of multilayer PCBs, recesses have been incorporated into the PCBs to reduce the overall thickness of PCBs containing electronic components. These recesses allow the electronic components to be placed within the PCB and embedded within it. The method of forming grooves on multilayer circuit boards is to remove part of the stacked structure through machining methods such as laser drilling or CNC drilling to form grooves. However, the residual resin on the surface of the grooves is removed through a desmear process, including sulfuric acid method, plasma method, chromic acid method, potassium permanganate method, and the use of various alkaline degreasing reagents to remove the residual resin left on the circuit board in the grooves. However, after undergoing a high-temperature lamination process, the chemical resistance of typical polyimide protective films or resin coatings increases, and the resin may even react with other thermosetting resins in the laminate. This makes it impossible to remove the residue completely using the aforementioned descaling agents or alkaline degreasing reagents, thus affecting subsequent metal surface treatment processes, such as browning, lead-free tinning, nickel immersion gold plating, and nickel electroplating.

In view of this, the present invention provides a polyamide resin composition, the resin coating of which can be removed by an alkaline solution, making it ideal for use in multilayer circuit boards.

For the purposes described above, the present invention provides the following polyamide resin composition and resin coating.

Item 1. A polyamide resin composition comprising: (a) a polyamide resin, the content of which is 40% to 95% by weight based on the total weight of the solid content of the polyamide resin composition, and the polyamide resin comprising the unit shown in formula (I): (I) and (b) ester compounds, the content of which is 3% to 50% by weight of the total solid content of the polyamide resin composition, and the ester compounds include the compounds shown in formula (II): (II), (c) a free radical scavenger, the content of which is 0.1% to 15% by weight of the total solid content of the polyamide resin composition; (d) a lubricant, the content of which is 0.1% to 15% by weight of the total solid content of the polyamide resin composition; and (e) a solvent, wherein A is a tetravalent organic group containing an aliphatic ring group or an aromatic ring group; B is a divalent organic group containing an aromatic ring group; X and Z are each independently a divalent organic group containing an aliphatic ring group or an aromatic ring group; Y is a divalent organic group derived from a glycol; ^R1 and ^R2 are each independently an alkyl or hydroxyalkyl group; m is a positive integer; and p is any integer from 0 to 10.

Item 2. A composition as described in Item 1, wherein A is a tetravalent organic group derived from a dianhydride containing an aliphatic or aromatic ring group.

Item 3. The composition as described in Item 1, wherein B is a divalent organic group derived from a diamine containing an aromatic ring group.

Item 4. The composition as described in Item 1, wherein X and Z are each independently a divalent organic group derived from a dicarboxylic acid containing an aliphatic ring group or an aromatic ring group.

Item 5. The composition as described in Item 4, wherein X and Z are each phthalic acid, isophthalic acid, terephthalic acid, 2,6-dicarboxytoluene, 4-methylphthalic acid, biphenyl-4,4'-dicarboxylic acid, 1,1'-biphenyl-3,3'-dicarboxylic acid, 1,1'-biphenyl-3,4-dicarboxylic acid, 1,1'-biphenyl-3,4'-dicarboxylic acid, 1,1'-biphenyl-3,5-dicarboxylic acid, 1,2-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 4-(carboxymethyl)cyclohexanecarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid.

Item 6. The composition as described in Item 1, wherein Y is a straight-chain or branched alkyl group having 1 to 10 carbon atoms.

Item 7. The composition as described in Item 1, wherein ^R1 and ^R2 are each independently a straight-chain or branched hydroxyalkyl group having 1 to 10 carbon atoms or a straight-chain or branched alkyl group having 1 to 10 carbon atoms.

Item 8. A composition as described in Item 6, wherein the compound represented by formula (II) is , or .

Item 9. The composition as described in Item 1, wherein X and Z are each independently an enylphenyl group.

Item 10. A resin coating formed from the composition as described in claim 1.

According to the present invention, a polyamide resin composition capable of forming an alkaline solution removable resin coating can be provided.

The polyamide resin composition provided by this invention comprises (a) a polyamide resin; (b) an ester compound; (c) a free radical scavenger; (d) a lubricant; and (e) a solvent.

The polyamide resin includes the unit shown in formula (I): (I).

In formula (I), A is a tetravalent organic group containing an aliphatic ring group or an aromatic ring group; B is a divalent organic group containing an aromatic ring group; m is a positive integer, such as 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100.

When formula (I) contains multiple A's, these A's may be the same as or different from each other. A may be a tetravalent organic group derived from a dianhydride containing an aliphatic or aromatic ring group. Examples of such dianhydrides include, but are not limited to: pyromellitic anhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic anhydride (BPDA), 3,3',4,4'-benzophenone tetracarboxylic anhydride (BTDA), 4,4'-oxodiphthalic anhydride (ODPA), bis(3,4-dicarboxyphenyl)methane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 1 3-Bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA), 4,4-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), hydroquinone bis(triphenylamine) (TAHQ), Ethylene glycol bis(triphenyltriacrylic anhydride) (TMEG), Propylene glycol bis(triphenyltriacrylic anhydride) (TMPG), Butylene glycol bis(triphenyltriacrylic anhydride), 2-Methyl-1,3-propanediol bis(triphenyltriacrylic anhydride), Dipropylene glycol bis(triphenyltriacrylic anhydride), 2-Methyl-2,4-pentanediol bis(triphenyltriacrylic anhydride), Diethylene glycol bis(triphenyltriacrylic anhydride), Tetramethylbenzene Glycol bis(triphenyltrihydric anhydride), hexaethylene glycol bis(triphenyltrihydric anhydride), neopentyl glycol bis(triphenyltrihydric anhydride), hydroquinone bis(2-hydroxyethyl) ether bis(triphenyltrihydric anhydride), 2-phenyl-5-(2,4-tanyl)-1,4-hydroquinone bis(triphenyltrihydric anhydride), 2,3-dicyanohydroquinone cyclobutane-1,2,3,4-tetracarboxylic acid dianhydride, 1,2,3,4 - Cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA), bicyclic [2.2.1]heptane-2,3,5,6-tetracarboxylic dianhydride, bicyclic [2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (COeDA), bicyclic [2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, 2, 3,5-Tricarboxy-cyclopentylacetic dianhydride, bicyclo[2.2.1]heptane-2,3,5-tricarboxy-6-acetic dianhydride, decahydro-1,4,5,8-dimethylnaphthalene-2,3,6,7-tetracarboxylic dianhydride, but-1,2,3,4-tetracarboxylic dianhydride (CBDA), and 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride (HBPDA). These dianhydrides can be used alone or in combination of two or more.

When formula (I) contains multiple Bs, these Bs may be the same as or different from each other. B may be a divalent organic group derived from a diamine containing an aromatic ring group. Examples of such diamines include, but are not limited to: m-phenylenediamine, p-phenylenediamine (pPDA), diaminodiphenyl ether (ODA), p-methylenediphenylamine (MDA), m-methylenediphenylamine, diaminophenoxybenzene, diaminophenoxybenzene, bis(4-aminophenyl) phenoxide (4,4’-DDS), bis(3-aminophenyl) phenoxide (3,3’-DDS), bis[4-(4-aminophenoxy)phenyl] phenoxide (BAPS), 9,9-bis(4-aminophenyl)fluorene, and 2,2'-dimethylbiphenyl. Amine (m-Tolidine), 1,3-bis(3-aminophenoxy)benzene (TPE-M), 1,3-bis(4-aminophenoxy)benzene (TPE-R), 1,4-bis(3-aminophenoxy)benzene (143BAPB), 1,4-bis(4-aminophenoxy)benzene (TPE-Q), 2,2'-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), bis(4-aminophenyl)terephthalate (BPTP), 3,3'-dihydroxybenzidine (HAB), 5,5'-methylenebis(2-aminobenzoic acid) (MBAA), 5-amino-2-(p-aminophenyl)benzoxazole (5ABO), 6-amino-2-(p-aminophenyl)benzoxazole (6ABO), 9,9-di(4-amino-3-fluorophenyl)fluorene, 2-(trifluoromethyl)phenyl-1,4-diamine, 2,3-bis(trifluoromethyl)-1,4-phenylenediamine, 2,6-bis(trifluoromethyl)-1,4-phenylenediamine, 2,5-bis(trifluoromethyl)- 1,4-Phenylenediamine, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), 2,2'-bis(trifluoromethyl)benzidine (TFMB), 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether (6-FODA), 3,3'-bis(trifluoromethyl)benzidine, 2,2'-bis-trifluoromethoxy-biphenyl-4,4'-diamine, 3,3'-bis-trifluoromethoxy-biphenyl-4,4'-diamine, 3,3'-bis(trifluoromethyl)- [1,1':4',1''-terphenyl]-4,4''-diamine, 2,2''-bis(trifluoromethyl)-[1,1':4',1''-terphenyl]-4,4''-diamine, 2-fluorophenyl-1,4-diamine, 2,5-difluorophenyl-1,4-diamine, 2,4,5,6-tetrafluorophenyl-1,3-diamine, 4,4'-diamino-octafluorobiphenyl, 4,4'-diamino-2,2'-difluorobiphenyl, 2,2',5,5'-tetrafluoro- [1,1'-Biphenyl]-4,4'-diamine, 4-(4-amino-2,6-difluorophenyl)-3,5-difluoroaniline, 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane. These diamines can be used alone or in combination of two or more.

From the viewpoint of providing good lamination support and alkali-soluble removal properties, the polyamide resin content is 40% to 95% by weight, preferably 50% to 90% by weight, relative to the total weight of the solids in the polyamide resin composition. In some embodiments, the polyamide resin content is 51% to 81% by weight, relative to the total weight of the solids in the polyamide resin composition.

In this invention, the ester compound includes the compound represented by formula (II): (II).

In this invention, X and Z are each independently a divalent organic group containing an aliphatic ring group or an aromatic ring group; Y is a divalent organic group derived from a diol; p is any integer from 0 to 10, for example: 1, 2, 3, 4, 5, 6, 7, 8, 9.

When formula (II) contains multiple Xs, these Xs may be the same as or different from each other. X may be a divalent organic group derived from a carboxylic acid containing an aliphatic ring group or an aromatic ring group. Examples of the dicarboxylic acid include, but are not limited to: phthalic acid, isophthalic acid, terephthalic acid, 2,6-dicarboxytoluene, 4-methylphthalic acid, biphenyl-4,4'-dicarboxylic acid, 1,1'-biphenyl-3,3'-dicarboxylic acid, 1,1'-biphenyl-3,4-dicarboxylic acid, 1,1'-biphenyl-3,5-dicarboxylic acid, 1,2-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 4-(carboxymethyl)cyclohexanecarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. In some embodiments, X is an exenphenyl group.

When formula (II) contains multiple Ys, these Ys may be the same or different from each other. Y may be a straight-chain or branched alkyl group with 1 to 10 carbons (e.g., 2, 3, 4).

Examples of compounds represented by formula (II) include, but are not limited to: , or .

In formula (II), Z can be a divalent organic group derived from a dicarboxylic acid containing an aliphatic ring group or an aromatic ring group. In some embodiments, Z is an exenylphenyl group.

In formula (II), ^R1 and ^R2 may be the same or different. ^R1 and ^R2 are each independently an alkyl or hydroxyalkyl group, for example: a straight-chain or branched alkyl group having 1 to 10 carbon atoms (e.g., 2, 3, 4), or a straight-chain or branched hydroxyalkyl group having 1 to 10 carbon atoms (e.g., 2, 3, 4). In some embodiments, ^R1 and ^R2 are each independently hydroxyethyl. In some embodiments, ^R1 and ^R2 are each independently methyl.

From the viewpoint of providing good alkali-soluble removal properties, the content of ester compounds is 3% to 50% by weight, preferably 5% to 40% by weight, relative to the total weight of the solids in the polyamide resin composition. In some embodiments, the content of the ester compounds is 10% to 35% by weight, relative to the total weight of the solids in the polyamide resin composition.

In this invention, examples of the free radical scavenger may include, but are not limited to, free radical polymerization inhibitors and light stabilizers. Examples of free radical polymerization inhibitors include, but are not limited to, hydroquinone, orthomethyl hydroquinone, p-hydroxyanisole, 2,3,5-trimethylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, p-tert-butylhydroquinone, 2,6-dibutyl-p-cresol, p-benzoquinone, tert-butyl-p-benzoquinone, phenothiazine, and tetramethylpiperidine oxide. Examples of photostabilizers include, but are not limited to, Eversorb 60, Eversorb 61, Eversorb 90, Eversorb 91FD, Eversorb 93, Eversorb 94FD, Eversorb 95, Eversorb 765, CHISORB 292, CHISORB 523, CHISORB 519, CHISORB 622LD, CHISORB 770, CHISORB 944, CHISORB 945, CHISORB 2959, and CHISORB 5144. These free radical scavengers can be used alone or in combination of two or more.

From the viewpoint of inhibiting reactions with other thermosetting resins, the content of the free radical scavenger is 0.1% to 15% by weight, preferably 0.5% to 10% by weight, relative to the total weight of the solids in the polyamide resin composition. In some embodiments, the content of the free radical scavenger is 3% to 8% by weight, relative to the total weight of the solids in the polyamide resin composition.

In this invention, examples of lubricants include, but are not limited to, acrylic silicone lubricants, specifically including SAC-342, SACT 3050D, SACN 3100D, SAC 3400 D, SAC-3010D, SAC-3025D, SAC-3050D, SAC-3100D, SAC-3800, SAC-3000A, SAC-3098, SAC-3208D, SAC-3150D, SAC-3101D, SAC-30152D, SAC 35154D, SAC 3806E, S10191, SF-OH7C, SF-OH10B, and SF-OHACR7C (Anfeng Industrial Co., Ltd.). OPTOOL DAC-100 (Daikin Industries, Ltd.). These lubricants can be used alone or in combination of two or more.

From the viewpoint of inhibiting adhesion to other resins, the content of the lubricant is 0.1% to 15% by weight, preferably 0.5% to 10% by weight, relative to the total weight of the solid content of the polyamide resin composition. In some embodiments, the content of the lubricant is 2% to 7% by weight, relative to the total weight of the solid content of the polyamide resin composition.

In this invention, the solvent can be used as long as it can dissolve polyamide resins. Examples of such solvents include, but are not limited to, aprotic solvents such as N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, γ-butyrolactone, dimethyl sulfoxide, and dimethylimidazolinone.

The polyamide resin composition of this invention can be mixed with other solvents, various thixotropic agents, defoamers, leveling agents, coupling agents, antioxidants, anti-aging agents, ultraviolet absorbers, sedimentation inhibitors, rheology control agents, flame retardants and other additives as needed.

In this invention, the polyamide resin composition can be obtained by mixing and stirring a polyamide resin solution with an ester compound, a free radical scavenger, and a lubricant at 30°C to 80°C (with further solvent added as needed). In this invention, the polyamide resin can be prepared by polymerizing dianhydride monomers and diamine monomers. Specifically, the polyamide resin can be prepared by polymerizing at least two dianhydride monomers and at least two diamine monomers. An exemplary polymerization method involves dissolving the dianhydride monomers and diamine monomers in a solvent, and then mixing and reacting the dissolved dianhydride monomers and diamine monomers to obtain the aforementioned polyamide resin solution. According to one embodiment of the present invention, the solvent content is 78% by weight of the total weight of the polyamide resin solution, thus forming a polyamide resin solution with a solid content of 22% by weight.

The present invention also provides a resin coating formed from the aforementioned composition. According to one embodiment of the present invention, a method for manufacturing the resin coating includes: forming a coating with the aforementioned polyamide resin composition; and drying the coating.

To highlight the effectiveness of this invention, the inventor has completed embodiments and comparative examples in accordance with the methods described below. The following embodiments and comparative examples will further illustrate the invention; however, these embodiments and comparative examples are not intended to limit the scope of the invention. Any modifications and alterations made by those skilled in the art without departing from the spirit of the invention are within the scope of the invention.

The meanings of the abbreviations used in the embodiments are as follows:

The components related to polyamide resin solutions are as follows:

PMDA: Pyromellitic anhydride

ODPA: 4,4'-Oxydiphthalic anhydride

BPDA: 3,3',4,4'-Biphenyltetracarboxylic acid dianhydride

TAHQ: Hydroquinone Bis(Trimeric Trihydric Anhydride)

COeDA: Bicyclic [2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride

CBDA: Butyl-1,2,3,4-tetracarboxylic dianhydride

TFMB: 2,2'-bis(trifluoromethyl)benzidine

6-FODA: 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether

BPTP: Bis(4-aminophenyl) terephthalate

pPDA: p-phenylenediamine

3,3'-DDS: Bis(3-aminophenyl) sulfonium

HAB: 3,3'-Dihydroxybenzidine

ODA: Diaminodiphenyl ether

DMAc: N,N-dimethylacetamide

The following components are examples of ester compounds.

B1: Dimethyl isophthalate

B2: 1,2-bis[p-(2-hydroxyethoxycarbonyl)benzoyloxy]ethane (CAS No. 2144-69-6)

B3: Linear trimer of polyethylene terephthalate (CAS No. 16033-73-1)

The following are examples of free radical scavengers.

C1: p-Benzoquinone

C2: CHISORB 292

The following are examples of lubricants.

D1: SAC-342

Implementation Example 1

16.01 g (0.05 mol) of 2,2'-bis(trifluoromethyl)benzidine (TFMB), 17.42 g (0.05 mol) of bis(4-aminophenyl) terephthalate (BPTP), and 212.18 g of N,N-dimethylacetamide (DMAc) were placed in a three-necked flask. After stirring at 30°C until completely dissolved, 10.91 g (0.05 mol) of pyromellitic anhydride (PMDA) and 15.51 g (0.05 mol) of 4,4'-oxodiphthalic anhydride (ODPA) were added. The mixture was then stirred continuously and reacted at 25°C for 24 hours to obtain a polyamide resin solution with a solid content of 22% by weight.

Take 59.85 g of the above polyamide resin solution, then add 23.02 g of dimethyl isophthalate, 7.37 g of p-benzoquinone, and 1.84 g of SAC-342, and stir at 30°C for 2 hours to obtain the polyamide resin composition. The total solid weight of the polyamide resin, ester compounds, free radical scavenger, and lubricant (i.e., the total solids of the polyamide resin composition) is 100% by weight. The contents of polyamide resin, ester compounds, free radical scavenger, and lubricant are 65% by weight, 25% by weight, 8% by weight, and 2% by weight, respectively.

Examples 2-9 and Comparative Examples 1-6: Preparation of polyamide resin compositions

Based on the components and dosages listed in Table 1, the polyamide resin solutions used in Examples 2-9 and Comparative Examples 1-6 can be prepared according to the method of Example 1. Next, based on the dosages listed in Table 1, ester compounds, free radical scavengers, and lubricants are added to the polyamide resin solutions to prepare the polyamide resin compositions of Examples 2-9 and Comparative Examples 1-6.

Evaluation Method

<Chemical Resistance>

A polyamide resin composition was screen-printed onto a copper foil substrate and dried at 120°C to form a 25-micron thick coating. The coating was then immersed in a 4% (w/w) sodium hydroxide aqueous solution at 50°C for 1 minute, and the film thickness was measured to determine if it decreased. No decrease in film thickness: ○ Decrease in film thickness: ╳

<High-temperature lamination heat resistance properties>

A polyamide resin composition was screen-printed onto the surface of a copper foil substrate and dried at 120°C to form a 25-micron-thick resin coating. Next, PP (prepreg, a semi-solid film) was placed on top of the coating, and the substrate was subjected to a high-temperature lamination process at 230°C for 5 hours using a press. No bulging or bubbles in the coating area: ○ Bulging or bubbles in the coating area: ╳

<Coating Peelability After High Temperature Lamination>

Peel off the PP (prepreg, semi-solid film) layer on top of the resin coating after high-temperature lamination to expose the coating and test its peelability. PP can be peeled off from above the coating: ○ PP cannot be peeled off from above the coating: ╳

<Coating Removability After High Temperature Lamination>

After removing the PP (Prepreg) coating, immerse the exposed coating in a 6% (w/w) sodium hydroxide aqueous solution at 50°C for 20 minutes and observe whether the coating has been completely removed. Completely removed coating: ○ Coating thickness reduced: △ No reduction in coating thickness: ╳

Table 1 mole Implementation Examples Comparative example 1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 Polyamide resin composition Polyamide resin solution PMDA 0.05 0.05 0.05 0.05 0.05 0.05 ODPA 0.05 0.05 0.05 0.05 0.05 0.05 BPDA 0.05 0.05 0.05 0.05 0.05 0.05 0.05 TAHQ 0.05 0.05 0.05 0.05 0.05 COeDA 0.05 0.05 CBDA 0.05 0.05 0.05 0.05 TFMB 0.05 0.05 0.05 0.10 0.05 0.05 0.05 0.05 6-FODA 0.02 0.02 0.02 0.05 BPTP 0.05 0.05 0.05 0.08 pPDA 0.05 0.05 0.02 3,3'-DDS 0.05 0.08 0.08 0.05 HAB 0.08 0.02 ODA 0.05 0.05 0.05 0.08 Solid content % twenty two% twenty two% twenty two% twenty two% twenty two% twenty two% twenty two% twenty two% twenty two% twenty two% twenty two% twenty two% twenty two% twenty two% twenty two% Solid weight % 65% 66% 61% 80% 81% 76% 55% 56% 51% 86% 51% 43% 91% 65% 57% Polyester B1 weight % 25% 25% 25% 0% 45% 35% 30% B2 weight % 10% 10% 10% 40% B3 weight % 35% 35% 35% 7% Free radical scavengers C1 weight % 8% 3% 7% 8% 3% 7% 2% 1% 0% 2% C2 weight % 8% 3% 7% 7% 15% Lubricant D1 weight % 2% 6% 7% 2% 6% 7% 2% 6% 7% 7% 2% 2% 1% 0% 11% Evaluation Method Chemical resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ╳ ○ ○ ○ ○ High-temperature lamination heat resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ╳ ○ ○ ╳ High-temperature lamination coating peelability ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ╳ ○ Post-lamination coating removeability ○ ○ ○ ○ ○ ○ ○ ○ ○ ╳ ○ △ ╳ — ○

As shown in Table 1, the polyamide resin composition of this invention exhibits excellent performance in terms of chemical resistance, high-temperature lamination heat resistance, high-temperature lamination coating peelability, and post-lamination coating removeability. In contrast, Comparative Example 1, lacking the addition of (b) ester compounds, is not conducive to dissolution after sodium hydroxide hydrolysis, making its post-lamination coating impossible to remove. Comparative Example 2, on the other hand, contains excessive amounts of (b) ester compounds, resulting in poor chemical resistance (especially alkali resistance) of the coating before lamination. Comparative Example 3, due to (a) insufficient polyamide resin content and excessive free radical scavenger, resulted in bulging and bubbling of the coating after high-temperature lamination, indicating poor heat resistance during high-temperature lamination. Comparative Example 4, due to (a) excessive polyamide resin content, had insufficient content of (b) ester compounds to aid in the dissolution of the coating after lamination, resulting in the same phenomenon as Comparative Example 1, where the coating could not be removed. Comparative Example 5, lacking (c) free radical scavenger and (d) lubricant, exhibited a coating that adhered tightly to the PP (Prepreg) after lamination, making it difficult to peel off and hindering subsequent coating removal operations. In Comparative Example 6, excessive lubricant (d) caused the coating to bulge and bubble after high-temperature lamination. The lubricant reduced the adhesion between the coating and PP (Prepreg) interface, resulting in poor heat resistance of the coating lamination.

In summary, the polyamide resin composition of this invention exhibits excellent performance in terms of chemical resistance, high-temperature lamination heat resistance, high-temperature lamination coating peelability, and post-lamination coating removeability.

However, the above description is merely a preferred embodiment of the present invention and should not be used to limit the scope of the present invention. Any simple equivalent changes and modifications made in accordance with the scope of the patent application and the description of the present invention shall still fall within the scope of the present invention.

Claims (10)

A polyamide resin composition comprising: (a) a polyamide resin, the content of which is 40% to 95% by weight of the total solid content of the polyamide resin composition, and the polyamide resin comprising the unit shown in formula (I): (I) and (b) ester compounds, the content of which is 3% to 50% by weight of the total solid content of the polyamide resin composition, and the ester compounds include the compounds shown in formula (II): (II), (c) a free radical scavenger, the content of which is 0.1% to 15% by weight of the total solid content of the polyamide resin composition; (d) a lubricant, the content of which is 0.1% to 15% by weight of the total solid content of the polyamide resin composition; and (e) a solvent, wherein A is a tetravalent organic group containing an aliphatic ring group or an aromatic ring group; B is a divalent organic group containing an aromatic ring group; X and Z are each independently a divalent organic group containing an aliphatic ring group or an aromatic ring group; Y is a divalent organic group derived from a glycol; ^R1 and ^R2 are each independently an alkyl or hydroxyalkyl group; m is a positive integer; and p is any integer from 0 to 10. The composition as described in claim 1, wherein A is a tetravalent organic group derived from a dianhydride containing an aliphatic or aromatic cyclic group. The composition as described in claim 1, wherein B is a divalent organic group derived from a diamine containing an aromatic ring group. The composition as described in claim 1, wherein X and Z are each independently a divalent organic group derived from a dicarboxylic acid containing an aliphatic ring group or an aromatic ring group. The composition as described in claim 4, wherein X and Z are each independently phthalic acid, isophthalic acid, terephthalic acid, 2,6-dicarboxytoluene, 4-methylphthalic acid, biphenyl-4,4'-dicarboxylic acid, 1,1'-biphenyl-3,3'-dicarboxylic acid, 1,1'-biphenyl-3,4-dicarboxylic acid, 1,1'-biphenyl-3,4'-dicarboxylic acid, 1,1'-biphenyl-3,5-dicarboxylic acid, 1,2-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 4-(carboxymethyl)cyclohexanecarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. The composition as described in claim 1, wherein Y is a linear or branched alkyl group having 1 to 10 carbon atoms. The composition as described in claim 1, wherein ^R1 and ^R2 are each independently a straight-chain or branched hydroxyalkyl group having 1 to 10 carbon atoms, or a straight-chain or branched alkyl group having 1 to 10 carbon atoms. The composition as described in claim 6, wherein the compound represented by formula (II) is , or . The composition as described in claim 1, wherein X and Z are each independently an enylphenyl group. A resin coating formed from the composition as described in claim 1.