Epoxy composition, composition, prepreg, laminated board and manufacturing method thereof

Abstract

An epoxy composition is provided according to the present disclosure. The epoxy composition includes a non-carbonic ester curing agent, an epoxy resin and a polycarbonate oligomer. The epoxy resin has at least two functional groups. The polycarbonate oligomer has a structure represented by formula (I), of which each symbol is defined in the specification. Therefore, the product made of the epoxy composition has great material physical properties and degradability.

Description

[Technical Field]

[0001] This disclosure relates to an epoxy resin composition, a composition, a prepreg, a laminate and a method for manufacturing the same, and particularly to an epoxy resin composition and a composition thereof, wherein the prepreg and laminate prepared therefrom have good material properties and biodegradability. [Previous Technology]

[0002] Printed Circuit Boards (PCBs) are indispensable components in electronic devices. Due to the high heat resistance required for PCBs, the copper-clad laminates (CCLs), the base material for PCBs, mostly use structurally stable thermosetting resins as their main raw material. Therefore, after PCBs are discarded, only the precious metals can be extracted and reused; the laminates, with thermosetting resins as the main raw material, are still disposed of through incineration or landfill. With the booming development and rapid iteration of the electronics industry, the conventional waste PCB disposal process will cause considerable damage to the environment.

[0003] To address the environmental pollution problem caused by waste printed circuit boards, degradation methods for laminates made primarily of thermosetting resins have been developed. However, the degradation process involves the use of large amounts of solvents and extremely high temperatures, making it difficult to implement widely in the industry. Furthermore, there are thermosetting materials with modified formulations, but these materials have poor physical properties, with insufficient heat resistance or processability, which limits their practical applications. [Summary of the Invention]

[0004] The purpose of this disclosure is to provide an epoxy resin composition, a method for manufacturing the composition, a prepreg, a laminate, and a laminate, wherein the epoxy resin composition has a specific formulation and chemical structure, which enables the products prepared to have good material properties and biodegradability.

[0005] One embodiment of this disclosure provides an epoxy resin composition comprising a non-carbonate curing agent, an epoxy resin, and a polycarbonate oligomer. The epoxy resin has at least two functional groups. The polycarbonate oligomer has a structure as shown in formula (I): Formula (I); wherein R1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, an alkoxy group having 1 to 6 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or a halogen atom, and R2 is an alkyl group having 1 to 10 carbon atoms, an ether group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or a structure shown in formula (1), formula (2), formula (3), formula (4), formula (5), formula (6), or formula (7): Equation (1), Equation (2), Equation (3), Equation (4), Equation (5), Equation (6), Equation (7); Wherein, X is a single bond, a cycloalkyl chain having 3 to 12 carbon atoms, an extended cycloalkyl chain having 3 to 12 carbon atoms, or a structure shown in formula (8), formula (9), formula (10), formula (11), formula (12), formula (13), formula (14), formula (15), or formula (16): Equation (8), Equation (9), Equation (10), Equation (11), Equation (12), Equation (13), Equation (14), Equation (15), Equation (16); Wherein, R3 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, an alkoxy group having 1 to 6 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or a halogen atom; R4 is a hydrogen atom or a methyl group; X1 and X2 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aromatic group having 6 to 12 carbon atoms; a is an integer from 0 to 4; b is an integer from 0 to 5; n is any number from 0 to 60; and m and p are each independently any number from 0 to 50.

[0006] According to the aforementioned epoxy resin composition, the epoxy resin may be bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, naphthol type epoxy resin, isocyanate modified epoxy resin, phenolic type epoxy resin, alicyclic epoxy resin, brominated epoxy resin, phosphorus-based epoxy resin, resorcinol type epoxy resin, polyethylene glycol type epoxy resin, dicyclopentadiene type epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, ester modified epoxy resin, or a mixture thereof.

[0007] According to the aforementioned epoxy resin composition, the non-carbonate curing agent may be a phenolic curing agent, an amine curing agent, an acid anhydride curing agent, an ester curing agent without a carbonate group, or a mixture thereof.

[0008] Another embodiment of this disclosure provides an epoxy resin composition comprising an epoxy resin and a polycarbonate oligomer. The epoxy resin has at least two functional groups. The polycarbonate oligomer has a structure as shown in formula (I): Formula (I); wherein R1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, an alkoxy group having 1 to 6 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or a halogen atom, and R2 is an alkyl group having 1 to 10 carbon atoms, an ether group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or a structure shown in formula (1), formula (2), formula (3), formula (4), formula (5), formula (6), or formula (7): Equation (1), Equation (2), Equation (3), Equation (4), Equation (5), Equation (6), Equation (7); Wherein, X is a single bond, a cycloalkyl chain having 3 to 12 carbon atoms, an extended cycloalkyl chain having 3 to 12 carbon atoms, or a structure shown in formula (8), formula (9), formula (10), formula (11), formula (12), formula (13), formula (14), formula (15), or formula (16): Equation (8), Equation (9), Equation (10), Equation (11), Equation (12), Equation (13), Equation (14), Equation (15), Equation (16); Wherein, R3 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, an alkoxy group having 1 to 6 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or a halogen atom; R4 is a hydrogen atom or a methyl group; X1 and X2 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aromatic group having 6 to 12 carbon atoms; a is an integer from 0 to 4; b is an integer from 0 to 5; n is any number from 5 to 25; and m and p are each independently any number from 0 to 50.

[0009] According to the aforementioned epoxy resin composition, the epoxy resin may be bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, naphthol type epoxy resin, isocyanate modified epoxy resin, phenolic type epoxy resin, alicyclic epoxy resin, brominated epoxy resin, phosphorus-based epoxy resin, resorcinol type epoxy resin, polyethylene glycol type epoxy resin, dicyclopentadiene type epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, ester modified epoxy resin, or a mixture thereof.

[0010] Another embodiment of this disclosure provides a composition comprising, with a total weight of 100 parts by weight, the aforementioned epoxy resin composition, an inorganic filler, and an organic solvent. The epoxy resin composition has a content of 30 to 80 parts by weight. The inorganic filler has a content of more than 0 to 40 parts by weight. The organic solvent has a content of 20 to 50 parts by weight.

[0011] The aforementioned composition may further include a curing accelerator and a flame retardant. The curing accelerator may have an amount of 0.0001 parts by weight to 0.02 parts by weight. The flame retardant may have an amount of more than 0 parts by weight to 0.3 parts by weight.

[0012] According to the aforementioned composition, the curing accelerator may be an imidazole compound, a pyridine compound, triphenylphosphine, a quaternary amine salt, a quaternary phosphate salt, or a mixture thereof.

[0013] According to the aforementioned composition, the inorganic filler may be aluminum hydroxide, silicon dioxide, barium sulfate, calcium carbonate, silicon carbide, boron nitride or a mixture thereof.

[0014] According to the aforementioned composition, the organic solvent may be cyclohexanone, acetone, butanone, dimethylformamide, dimethylacetamide, toluene, xylene, N-methylpyrrolidone or a mixture thereof.

[0015] Another embodiment of this disclosure provides a prepreg comprising the aforementioned epoxy resin composition and a reinforcing material, wherein the epoxy resin composition is attached to the reinforcing material.

[0016] According to the aforementioned prepreg, the reinforcing material may include an organic fiber woven fabric, an inorganic fiber woven fabric, an organic fiber nonwoven fabric, an inorganic fiber nonwoven fabric, or a combination thereof.

[0017] Another embodiment of this disclosure provides a method for manufacturing a laminate, comprising the following steps: providing a plurality of the aforementioned prepregs; stacking the prepregs; and heating and curing the stacked prepregs under a curing pressure and a curing temperature to form a laminate.

[0018] According to the aforementioned method for manufacturing laminate, the curing pressure can be from 10 kg / cm² to 60 kg / cm², and the curing temperature can be from 150°C to 250°C.

[0019] Another embodiment of this disclosure provides a laminate, which is obtained by the aforementioned method for manufacturing a laminate.

[0020] Accordingly, the epoxy resin composition disclosed herein contains polycarbonate oligomers, which have specific chemical structures. The finished products made from them can undergo alcoholysis, ammonolysis, or alcohol-amine hydrolysis under specific conditions, thus enabling recycling and reducing waste. Furthermore, the epoxy resin composition disclosed herein can be further formulated into biodegradable prepregs and laminates, which can be applied in the printed circuit board field to solve the circuit board waste problem.

Implementation Method

[0021] The various embodiments of this disclosure will be discussed in more detail below. However, this embodiment can be an application of various disclosed concepts and can be implemented in various different specific scopes. The specific embodiments are for illustrative purposes only and are not limited to the scope of the disclosure.

[0022] In this disclosure, the compound structure is sometimes represented by a skeleton formula, which can omit carbon atoms, hydrogen atoms, and carbon-hydrogen bonds. If the functional groups are clearly shown in the structural formula, the one shown shall prevail.

[0023] In this disclosure, the "polycarbonate oligomer having a structure as shown in formula (I)" is sometimes expressed as polycarbonate oligomer as shown in formula (I) or polycarbonate oligomer (I) for the sake of brevity and fluency. The representation of other compounds or groups follows the same pattern.

[0024] <Epoxy Resin Composition>

[0025] One embodiment of this disclosure provides an epoxy resin composition comprising an epoxy resin and a polycarbonate oligomer. Furthermore, another embodiment of this disclosure provides an epoxy resin composition further comprising a non-carbonate curing agent; the components are described in further detail below.

[0026] The epoxy resin has at least two functional groups, and may be bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, naphthol type epoxy resin, isocyanate modified epoxy resin, phenolic type epoxy resin, alicyclic epoxy resin, brominated epoxy resin, phosphorus-based epoxy resin, resorcinol type epoxy resin, polyethylene glycol type epoxy resin, dicyclopentadiene type epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, ester modified epoxy resin or mixtures thereof.

[0027] The polycarbonate oligomer has a structure as shown in formula (I): Formula (I); wherein, R1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, an alkoxy group having 1 to 6 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or a halogen atom, and R2 is an alkyl group having 1 to 10 carbon atoms, an ether group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or a structure as shown in formula (1), formula (2), formula (3), formula (4), formula (5), formula (6), or formula (7): Equation (1), Equation (2), Equation (3), Equation (4), Equation (5), Equation (6), Equation (7); Wherein, X is a single bond, a cycloalkyl chain having 3 to 12 carbon atoms, an extended cycloalkyl chain having 3 to 12 carbon atoms, or a structure shown in formula (8), formula (9), formula (10), formula (11), formula (12), formula (13), formula (14), formula (15), or formula (16): Equation (8), Equation (9), Equation (10), Equation (11), Equation (12), Equation (13), Equation (14), Equation (15), Equation (16); In this system, R3 is a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, an allyl group, an alkoxy group with 1 to 6 carbon atoms, an aromatic group with 6 to 12 carbon atoms, or a halogen atom; R4 is a hydrogen atom or a methyl group; X1 and X2 are each independently a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, or an aromatic group with 6 to 12 carbon atoms; a is an integer from 0 to 4; b is an integer from 0 to 5; n is any number from 0 to 60; and m and p are each independently any number from 0 to 50. Furthermore, n can be any number from 5 to 25.

[0028] The non-carbonate curing agent may be a phenolic curing agent, an amine curing agent, an acid anhydride curing agent, an ester curing agent without a carbonate group, or a mixture thereof. The weight ratio of the non-carbonate curing agent to the polycarbonate oligomer may be 0 to 1.

[0029] Accordingly, the epoxy resin composition disclosed herein has a carbonate structure, and the finished products made from it can be subjected to alcoholysis, ammonolysis, or alcohol-amine hydrolysis under specific conditions, thus enabling recycling and reducing waste.

[0030] <Composition>

[0031] Another embodiment of this disclosure provides a composition comprising the aforementioned epoxy resin composition, an inorganic filler, and an organic solvent. Specifically, based on a total weight of 100 parts by weight, the epoxy resin composition has a content of 30 to 80 parts by weight, the inorganic filler has a content of greater than 0 to 40 parts by weight, and the organic solvent has a content of 20 to 50 parts by weight. Therefore, the composition of this disclosure can, for example, be used as a prepreg for forming laminates.

[0032] The inorganic filler may be aluminum hydroxide, silicon dioxide, barium sulfate, calcium carbonate, silicon carbide, boron nitride or a mixture thereof.

[0033] The organic solvent may be cyclohexanone, acetone, butanone, dimethylformamide, dimethylacetamide, toluene, xylene, N-methylpyrrolidone or a mixture thereof.

[0034] The composition may further include a curing accelerator and a flame retardant. The curing accelerator may have an amount of 0.0001 parts by weight to 0.02 parts by weight. The flame retardant may have an amount of greater than 0 parts by weight to 0.3 parts by weight. The curing accelerator may be an imidazole compound, a pyridine compound, triphenylphosphine, a quaternary amine salt, a quaternary phosphate salt, or a mixture thereof.

[0035] <Prepreg>

[0036] Another embodiment of this disclosure provides a prepreg that is biodegradable. The prepreg comprises the aforementioned epoxy resin composition and a reinforcing material, wherein the epoxy resin composition is attached to the reinforcing material.

[0037] In detail, the epoxy resin composition can be adhered to the reinforcing material by impregnation and drying treatment. A drying temperature in the impregnation and drying treatment can be from 100°C to 250°C, and a drying time can be from 1 minute to 15 minutes.

[0038] The reinforcing material may comprise an organic fiber woven fabric, an inorganic fiber woven fabric, an organic fiber nonwoven fabric, an inorganic fiber nonwoven fabric, or a combination thereof. The organic fiber may comprise aramid fiber, and the inorganic fiber may comprise glass fiber or carbon fiber, but this disclosure is not limited to the aforementioned materials.

[0039] <Manufacturing Method of Laminates and Laminates>

[0040] Please refer to Figure 1, which is a flowchart of the steps of a method 100 for manufacturing a laminate according to another embodiment of the present disclosure. The method 100 for manufacturing a laminate includes steps 110, 120 and 130, wherein step 110 is to provide a plurality of the aforementioned prepregs. Step 120 is to stack the prepregs.

[0041] Step 130 involves heating and curing the stacked prepregs under a curing pressure and a curing temperature to form a laminate. The curing pressure can be from 10 kg / cm² to 60 kg / cm², and the curing temperature can be from 150°C to 250°C.

[0042] Another embodiment of the present disclosure provides a laminate, which is obtained by the aforementioned laminate manufacturing method 100, and the laminate is biodegradable.

[0043] <Degradation Methods>

[0044] Please refer to Figure 2, which is a flowchart of a degradation method 200 for the prepreg or laminate disclosed herein. The degradation method 200 includes steps 210 and 220.

[0045] Step 210 involves mixing the aforementioned prepreg or laminate with an aliphatic amine to form a mixture to be degraded. The aliphatic amine may be ethanolamine, aliphatic monoamine having 2 to 10 carbon atoms, aliphatic diamine having 2 to 10 carbon atoms, polyetheramine (e.g., Jeffamine polyetheramine), diethanolamine, diethylenetriamine (DETA), triethylenetetramine (TETA), or a mixture thereof.

[0046] Step 220 involves placing the mixture to be degraded at a degradation temperature, wherein the degradation temperature can be from 20°C to 160°C.

[0047] The following specific embodiments further illustrate the present disclosure, so as to enable those skilled in the art to fully utilize and practice the present disclosure without excessive interpretation. These embodiments should not be regarded as a limitation on the scope of the present disclosure, but are used to illustrate how to implement the materials and methods of the present disclosure.

[0048] <Synthesis Example 1>

[0049] The reaction formula of Synthesis Example 1 is shown in Formula (A): Formula (A).

[0050] The preparation method of Synthesis Example 1 is as follows: 100 g (4×10⁻³ moles, calculated as Mn) of polycarbonate granules (purchased from Chi Mei Industrial Co., Ltd., product code PC-122, Mn=24400, Mw=45488) was dissolved in 150 g of N,N-dimethylacetamide (DMAc) solvent, heated to 150°C and maintained at the temperature while stirring. After dissolution, 18.3 g of benzyl alcohol (0.17 moles) was added and reacted for 9 hours. After the reaction was completed, the mixture was cooled, washed in methanol, and filtered under vacuum to obtain a white powder, which is the polycarbonate oligomer of Synthesis Example 1, and its code is OPC1. OPC1 was dried in a vacuum oven at 110°C, and the yield was estimated to be about 75%. GPC analysis showed that Mn=2391 and Mw=3532. According to formula (A), n1 is about 8 and the ester equivalent is 135 g / eq.

[0051] <Synthesis Example 2>

[0052] The reaction formula of Synthesis Example 2 is shown in the aforementioned formula (A), and the preparation method is as follows: 100 g (4.1 × 10⁻³ mole, calculated as Mn) of polycarbonate particles (purchased from Chi Mei Industrial Co., Ltd., product code PC-122, Mn=24400, Mw=45488) was dissolved in 150 g of N,N-dimethylacetamide solvent, heated to 150°C and maintained at the temperature while stirring. After dissolution, 6.87 g of benzyl alcohol (0.06 mole) was added, and the reaction was carried out for 9 hours. After the reaction was completed, the mixture was cooled, poured into methanol for washing, and filtered under vacuum to obtain a white powder, which is the polycarbonate oligomer of Synthesis Example 2, and its code is OPC2. OPC2 was dried in a vacuum oven at 110°C, and the yield was estimated to be about 88%. GPC analysis showed that Mn=6854 and Mw=10289. According to formula (A), n1 is about 26 and the ester equivalent is 127 g / eq.

[0053] <Synthesis Example 3>

[0054] The reaction formula of Synthesis Example 3 is shown in the aforementioned formula (A), and the preparation method is as follows: 100 g (4.1 × 10⁻³ mole, calculated as Mn) of polycarbonate particles (purchased from Chi Mei Industrial Co., Ltd., product code PC-122, Mn=24400, Mw=45488) was dissolved in 150 g of N,N-dimethylacetamide solvent, heated to 150°C and maintained at the temperature while stirring. After dissolution, 25.19 g (0.22 mole) of benzyl alcohol (0.22 mole) was added, and the reaction was carried out for 9 hours. After the reaction was completed, the mixture was cooled, washed in methanol, and filtered under vacuum to obtain a white powder, which is the polycarbonate oligomer of Synthesis Example 3, and its code is OPC3. OPC3 was dried in a vacuum oven at 110°C, and the yield was estimated to be about 60%. GPC analysis showed that Mn=1134 and Mw=1732. According to formula (A), n1 is about 3, and the ester equivalent is 137 g / eq.

[0055] <Synthesis Example 4>

[0056] The reaction formula of Synthesis Example 4 is shown in Formula (B): Formula (B).

[0057] The preparation method of Synthesis Example 4 is as follows: 100 g (4 × 10⁻³ moles, calculated as Mn) of polycarbonate granules (purchased from Chi Mei Industrial Co., Ltd., product code PC-122, Mn=24400, Mw=45488) was dissolved in 150 g of N,N-dimethylacetamide solvent. The temperature was raised to 150°C and maintained while stirring. After dissolution, 16.00 g of phenol (0.17 moles) was added, and the reaction was carried out for 9 hours. After the reaction was completed, the mixture was cooled, washed in methanol, and filtered under vacuum to obtain a white powder, which is the polycarbonate oligomer of Synthesis Example 4, designated as OPC4. OPC4 was dried in a vacuum oven at 110°C. The yield was estimated to be about 85%, and GPC analysis showed that Mn=2230 and Mw=3708. According to formula (B), its n² is approximately equal to 7, and the ester equivalent is 127 g / eq.

[0058] <Examples 1 to Examples 4>

[0059] Examples 1 to 4 involved mixing epoxy resin, polycarbonate oligomer OPC1 of Synthetic Example 1, non-carbonate curing agent, curing accelerator, inorganic filler, phosphorus-based flame retardant, and organic solvent in the weight ratios shown in Table 1 below to prepare a liquid composition. Fiberglass cloth (model: 7628) was then immersed in the composition for coating, and baked in an oven at 170°C for approximately 3 minutes to obtain a prepreg. Next, multiple prepregs were stacked together, with one 35 μm ultra-low profile (HVLP2) copper foil placed on each side. The layers were then hot-pressed in a vacuum press at a pressure of 142 psi and a temperature of 180°C for two hours to produce a double-sided copper-clad laminate.

[0060] <Examples 5 to 8>

[0061] Examples 5 to 8 respectively involved mixing epoxy resin, polycarbonate oligomers (OPC2 to OPC4) from Synthetic Examples 2 to 4, non-carbonate curing agents, curing accelerators, inorganic fillers, phosphorus-based flame retardants, and organic solvents according to the weight ratios shown in Table 2 below. After preparing the adhesive solution, fiberglass cloth (model: 7628) was immersed in the solution for coating, and baked in an oven at 170°C for about 3 minutes to obtain a prepreg. Next, multiple prepregs were stacked together, with one 35 μm ultra-low profile (HVLP2) copper foil on each side, and hot-pressed in a vacuum press at a pressure of 142 psi and a temperature of 180°C for two hours to produce a double-sided copper foil laminate.

[0062] <Comparative Examples 1 to 3>

[0063] The manufacturing methods of Comparative Examples 1 to 3 are the same as those of Examples 1 to 8, except that the components used are proportioned according to the proportions shown in Table 3 below. Table 1 Example 1 Example 2 Example 3 Example 4 OPC1 0.7181 0.6924 0.8804 0.4846 DDS - - 0.0794 - PF8110 - - - 0.2738 BE188 1 - - - CNE195 - 1 0.25 0.7 ELM-434 - - 0.75 0.3 2pz 0.007 0.004 0.012 0.004 PQ-60 0.7246 0.4372 0.5082 0.4542 FB-3SDC 1.0824 0.9143 1.0628 0.95 Cyclohexanone 2.8059 1.8773 2.5598 2.2624 Table 2 Example 5 Example 6 Example 7 Example 8 OPC2 0.4449 - - - OPC3 - 0.4799 - - OPC4 - - 0.4449 0.6755 PF8110 0.2738 0.2738 0.2738 - BE188 - - - 1 CNE195 0.7 0.7 0.7 - ELM-434 0.3 0.3 0.3 - 2pz 0.004 0.004 0.004 0.007 PQ-60 0.4542 0.4542 0.4542 0.7246 FB-3SDC 0.95 0.95 0.95 1.0824 Cyclohexanone 2.2624 2.2624 2.2624 2.8059 Table 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 OPC2 - 0.6755 - OPC3 - - 0.7287 PF8110 0.6174 - - BE188 - 1 1 CNE195 0.7 - - ELM-434 0.3 - - 2pz 0.004 0.007 0.007 PQ-60 0.4175 0.7246 0.7246 FB-3SDC 0.8738 1.0824 1.0824 Cyclohexanone 1.7857 2.8059 2.8059

[0064] The material codes listed in Tables 1 to 3 above are detailed below:

[0065] (A) Epoxy resins: BE188: Changchun Artificial Resin, bisphenol A type epoxy resin, epoxy equivalent of 188 g / eq; CNE195: Changchun Artificial Resin, cresol novolac epoxy resin, epoxy equivalent of 195 g / eq; and ELM-434: Sumitomo Chemical, tetraglycidyl diaminodiphenylmethane (TGDDM), epoxy equivalent of 119 g / eq.

[0066] (B) Non-carbonate curing agents: DDS: TCI, 4,4'-sulfonyldianiline, with an activity equivalent of 62.08 g / eq; and PF8110: Changchun Artificial Resin, phenolic resin, with an activity equivalent of 105 g / eq.

[0067] (C) Curing accelerator: 2pz, Shikoku Chemical.

[0068] (D) Flame retardant: PQ-60, Jin Yi Chemical.

[0069] (E) Inorganic filler: FB-3SDC, Hongju Industrial.

[0070] <Performance Testing>

[0071] According to Tables 1-3 above, it can be observed that when there is no non-carbonate hardener in the composition (Examples 1-2, Example 8, Comparative Examples 2-3), there will be serious solubility problems in the preparation of the composition.

[0072] Taking Comparative Example 2 as an example, the polycarbonate oligomer OPC2 needs to be heated to 100°C during the mixing process with the solvent and epoxy resin. After cooling to room temperature, it will exhibit precipitation and atomization, and the prepared composition cannot remain clear. When it is necessary to continue to produce prepregs and laminates, its application will be limited. In other words, based on the composition of Comparative Example 2 and related experimental results, it can be seen that when the molecular weight of the polycarbonate oligomer (e.g., OPC2) is too large, for example, n1 and n2 are greater than 25, its composition cannot be used in the subsequent production of prepregs and laminates due to its poor solubility. However, when polycarbonate oligomers and non-carbonate curing agents are combined to form a composition (Example 5), the non-carbonate curing agent PF8110 can be used to supplement the reaction equivalent with epoxy resin CNE195 / ELM-434, thereby reducing the proportion of polycarbonate oligomers in the overall formulation and overcoming the solubility problem, so that it can be further applied to, for example, the production of prepregs and laminates.

[0073] Performance tests were performed on Examples 1 to 8 and Comparative Examples 1 and 3, and the test results are shown in Tables 4 to 6 below: Table 4 Example 1 Example 2 Example 3 Example 4 Dk (10 GHz) 4.48 4.49 4.54 4.62 Df (10 GHz) 0.0095 0.0148 0.0122 0.0125 Tg (°C) 151 190 210 181 T d5 (°C) 389 402 378 389 CTE α1 (μm / (m°C)) 35 30 twenty four 29 α2 (μm / (m°C)) 205 189 234 210 Z-axis (%) 2.61 2.16 2.41 2.31 Tensile strength (kgf / cm) 0.74 0.83 0.83 0.84 Water absorption rate (%) 0.068 0.112 0.118 0.115 Thermal stress test (288°C / 10 s) Pass Pass Pass Pass Flame retardancy test V0 V0 V0 V0 Degradability test Fiberglass is separated from copper foil, and there is no resin adhering to the surface. The fiberglass separated from the copper foil, and some resin adhered to the surface of the fiberglass. The fiberglass separated from the copper foil, and some resin adhered to the surface of the fiberglass. The fiberglass separated from the copper foil, and some resin adhered to the surface of the fiberglass. Table 5 Example 5 Example 6 Example 7 Example 8 Dk (10 GHz) 4.58 4.64 4.60 4.50 Df (10 GHz) 0.0112 0.0134 0.0122 0.0097 Tg (°C) 185 178 183 156 T d5 (°C) 394 380 394 392 CTE α1 (μm / (m°C)) 27 32 29 34 α2 (μm / (m°C)) 205 220 208 207 Z-axis (%) 2.32 2.41 2.34 2.61 Tensile strength (kgf / cm) 0.84 0.78 0.86 0.78 Water absorption rate (%) 0.116 0.124 0.114 0.072 Thermal stress test (288°C / 10 s) Pass Pass Pass Pass Flame retardancy test V0 V0 V0 V0 Degradability test The fiberglass separated from the copper foil, and some resin adhered to the surface of the fiberglass. The fiberglass separated from the copper foil, and some resin adhered to the surface of the fiberglass. The fiberglass separated from the copper foil, and some resin adhered to the surface of the fiberglass. Fiberglass is separated from copper foil, and there is no resin adhering to the surface. Table 6 Comparative Example 1 Comparative Example 3 Dk (10 GHz) 4.73 4.51 Df (10 GHz) 0.0171 0.0112 Tg (°C) 221 125 T d5 (°C) 405 356 CTE α1 (μm / (m°C)) 25 46 α2 (μm / (m°C)) 189 290 Z-axis (%) 2.02 3.12 Tensile strength (kgf / cm) 0.91 0.52 Water absorption rate (%) 0.121 0.112 Thermal stress test (288°C / 10 s) Pass Pass Flame retardancy test V0 V0 Degradability test No change in the sample Fiberglass is separated from copper foil, and there is no resin adhering to the surface.

[0074] The test methods listed in Tables 4 to 6 above are described in detail below:

[0075] (1) Dielectric constant (Dk) and dielectric loss (Df): The test equipment was an AET Microwave Dielectrometer, and the electrical test was performed at a frequency of 10 GHz in accordance with the test specification ASTM D2520.

[0076] (2) Glass transition temperature (Tg): The test equipment is TA DMA850, and the test is performed in accordance with the test specification IPC-TM-650 2.4.24.4.

[0077] (3) Thermal decomposition temperature (T d5): The test equipment is TA TGA Q500, and the test is carried out in accordance with the test specification IPC-TM-650 2.4.24.6.

[0078] (4) Coefficient of thermal expansion (CTE): The test equipment is TA TMA Q400, and the test is carried out in accordance with the test specification IPC-TM-650 2.4.24C.

[0079] (5) Peeling strength: The test equipment is a SHIMADZU universal tensile testing machine, and a 90-degree pull-out test is performed in accordance with the test specification IPC-TM-650 2.4.8.

[0080] (6) Water absorption: Cut the sample into test pieces with an area of ​​50.8 mm2, dry them at 105°C to 110°C for 1 hour, and test them according to the test specification IPC-TM-650 2.6.2.1A.

[0081] (7) Thermal stress test: The test is conducted using a small tin furnace and the test specifications are evaluated according to IPC-TM-640 2.4.13.1.

[0082] (8) Flame retardancy test: evaluated using UL-94 test specifications and standard equipment.

[0083] (9) Degradability test: Take a sample with an area of ​​10 cm2 and immerse it in an alkanolamine solution, heat it to 135°C and maintain the temperature for 17 hours, visually observe the changes in the sample and record them.

[0084] As disclosed above, using polycarbonate oligomers (e.g., OPC1~OPC4) in the composition allows the electrical properties of the copper-clad laminate prepared from it to be comparable to those of conventional copper-clad laminates with added non-carbonate curing agents (phenolic resin, as shown in Comparative Example 1); and when no additional non-carbonate curing agent is added to the composition, the electrical properties of the copper-clad laminate prepared from it can be further optimized (as shown in Examples 1, 2, and 8). In other words, when a copper-clad laminate is formed using a composition containing polycarbonate oligomers, compared with a conventional composition that only adds a non-carbonate curing agent (phenolic resin), the product can have advantages in electrical properties and hydrophobicity due to the reduction of polar secondary alcohols and intermolecular hydrogen bonds in the structure after curing, while the glass transfer temperature will decrease slightly.

[0085] Furthermore, in the examples (Examples 1 and 8) where no additional non-carbonate curing agent was added, it was observed that the differences in the terminal groups of the polycarbonate oligomers did not affect the overall use and physical properties. However, when the molecular weight of the polycarbonate oligomer was too small (Examples 1 and Comparative Example 3, for example, n1 and n2 were less than 5), although it did not affect the subsequent operability of the composition (e.g., it could still be used to make prepregs and laminates), it had a significant impact on the physical properties of the laminates subsequently produced. That is, the physical properties of the laminates produced in Comparative Example 3, such as Tg, Td5, and CTE, were inferior to those in Example 1, and could not meet the application requirements for further production of printed circuit boards.

[0086] Referring further to the table above, when the composition uses an epoxy resin with at least two functional groups combined with a polycarbonate oligomer, the resin in the resulting copper-clad laminate can be decomposed and dissolved after being immersed in an alkanolamine solution at high temperature, allowing the fiberglass cloth to separate from the copper foil. Furthermore, when other non-carbonate curing agents are used in the composition, the biodegradability of the copper-clad laminate can also achieve the purpose of separating the fiberglass cloth from the copper foil, which is of considerable help for subsequent waste treatment and separation (as shown in Examples 3-7).

[0087] On the other hand, as mentioned above, it can be seen from Examples 5-6 in Table 5 that by combining polycarbonate oligomers with non-carbonate curing agents, the problem of poor solubility of the larger molecular weight polycarbonate oligomer OPC2 can be overcome, and the problem of poor physical properties when using the smaller molecular weight polycarbonate oligomer OPC3 alone to form a composition for laminate fabrication can also be solved. Therefore, both can meet the physical property requirements for subsequent application in the manufacture of printed circuit boards, and maintain biodegradability.

[0088] The above embodiments are merely illustrative of this disclosure and are not intended to limit the scope of protection of this disclosure. For example, this disclosure may also use polycarbonate oligomers with other structures, or other types of hardeners, epoxy resins, etc. Therefore, any modifications or extensions made based on the above embodiments should fall within the scope of protection of this disclosure.

[0089] In summary, the epoxy resin composition disclosed herein contains polycarbonate oligomers with specific chemical structures. The finished products made from these oligomers can undergo alcoholysis, ammonolysis, or alcohol-amine hydrolysis under specific conditions, thus enabling recycling and reducing waste. Furthermore, the epoxy resin composition disclosed herein can be further formulated into biodegradable prepregs and laminates, which can be applied in the printed circuit board (PCB) industry to solve the PCB waste problem.

[0090] Although the present disclosure has been disclosed above with reference to embodiments, it is not intended to limit the present disclosure. Any person skilled in the art may make various modifications and alterations without departing from the spirit and scope of the present disclosure. Therefore, the scope of protection of the present disclosure shall be determined by the appended claims. [Simplified Explanation of the Diagram]

[0091] Figure 1 is a flowchart of the steps of a method for manufacturing a laminate according to an embodiment of the present disclosure; and Figure 2 is a flowchart of the steps of a method for degrading a prepreg or laminate according to the present disclosure.

Claims

1. An epoxy resin composition comprising: a non-carbonate curing agent; an epoxy resin having at least two functional groups, wherein the epoxy resin is a naphthol-type epoxy resin, an isocyanate-modified epoxy resin, a brominated epoxy resin, a resorcinol-type epoxy resin, a polyethylene glycol-type epoxy resin, a trifunctional epoxy resin, a tetrafunctional epoxy resin, a tetrafunctional epoxy resin, a phenolic epoxy resin, an ester-modified epoxy resin, or a mixture thereof; and a polycarbonate oligomer having a structure as shown in formula (I): Formula (I); wherein, R1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, an alkoxy group having 1 to 6 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or a halogen atom; R2 is an alkyl group having 1 to 10 carbon atoms, an ether group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or a structure shown in formula (1), (2), (3), (4), (5), (6), or (7): Equation (1), Equation (2), Equation (3), Equation (4), Equation (5), Equation (6), Equation (7); Wherein, X is a single bond, a cycloalkyl chain having 3 to 12 carbon atoms, an extended cycloalkyl chain having 3 to 12 carbon atoms, or a structure shown in formula (8), formula (9), formula (10), formula (11), formula (12), formula (13), formula (14), formula (15), or formula (16): Equation (8), Equation (9), Equation (10), Equation (11), Equation (12), Equation (13), Equation (14), Equation (15), Equation (16); Wherein, R3 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, an alkoxy group having 1 to 6 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or a halogen atom; R4 is a hydrogen atom or a methyl group; X1 and X2 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aromatic group having 6 to 12 carbon atoms; a is an integer from 0 to 4; b is an integer from 0 to 5; n is any number from 0 to 60; and m and p are each independently any number from 0 to 50.

2. The epoxy resin composition as claimed in claim 1, wherein the non-carbonate curing agent is a phenolic curing agent, an amine curing agent, an acid anhydride curing agent, an ester curing agent without a carbonate group, or a mixture thereof.

3. An epoxy resin composition comprising: an epoxy resin having at least two functional groups; and a polycarbonate oligomer having a structure as shown in formula (I): Formula (I); wherein, R1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, an alkoxy group having 1 to 6 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or a halogen atom; R2 is an alkyl group having 1 to 10 carbon atoms, an ether group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or a structure shown in formula (1), (2), (3), (4), (5), (6), or (7): Equation (1), Equation (2), Equation (3), Equation (4), Equation (5), Equation (6), Equation (7); Wherein, X is a single bond, a cycloalkyl chain having 3 to 12 carbon atoms, an extended cycloalkyl chain having 3 to 12 carbon atoms, or a structure shown in formula (8), formula (9), formula (10), formula (11), formula (12), formula (13), formula (14), formula (15), or formula (16): Equation (8), Equation (9), Equation (10), Equation (11), Equation (12), Equation (13), Equation (14), Equation (15), Equation (16); Wherein, R3 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, an alkoxy group having 1 to 6 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or a halogen atom; R4 is a hydrogen atom or a methyl group; X1 and X2 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aromatic group having 6 to 12 carbon atoms; a is an integer from 0 to 4; b is an integer from 0 to 5; n is any number from 5 to 25; and m and p are each independently any number from 0 to 50.

4. The epoxy resin composition as claimed in claim 3, wherein the epoxy resin is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a biphenyl type epoxy resin, a naphthol type epoxy resin, an isocyanate modified epoxy resin, a phenolic type epoxy resin, an alicyclic epoxy resin, a brominated epoxy resin, a phosphorus-based epoxy resin, a resorcinol type epoxy resin, a polyethylene glycol type epoxy resin, a dicyclopentadiene type epoxy resin, a trifunctional epoxy resin, a tetrafunctional epoxy resin, an ester modified epoxy resin, or a mixture thereof.

5. A composition comprising 100 parts by weight of the total weight of the composition, the composition comprising: an epoxy resin composition as described in any one of claims 1 to 4, having an amount of 30 to 80 parts by weight; an inorganic filler having an amount of more than 0 to 40 parts by weight; and an organic solvent having an amount of 20 to 50 parts by weight.

6. The composition as claimed in claim 5 further comprises: a curing accelerator having an amount of 0.0001 parts by weight to 0.02 parts by weight; and a flame retardant having an amount of greater than 0 parts by weight to 0.3 parts by weight.

7. The composition as claimed in claim 6, wherein the curing accelerator is an imidazole compound, a pyridine compound, triphenylphosphine, a quaternary amine salt, a quaternary phosphate salt, or a mixture thereof.

8. The composition as claimed in claim 5, wherein the inorganic filler is aluminum hydroxide, silicon dioxide, barium sulfate, calcium carbonate, silicon carbide, boron nitride, or a mixture thereof.

9. The composition as claimed in claim 5, wherein the organic solvent is cyclohexanone, acetone, butanone, dimethylformamide, dimethylacetamide, toluene, xylene, N-methylpyrrolidone, or a mixture thereof.

10. A prepreg comprising: an epoxy resin composition as described in any one of claims 1 to 4; and a reinforcing material to which the epoxy resin composition is attached.

11. The prepreg as claimed in claim 10, wherein the reinforcing material comprises an organic fiber woven fabric, an inorganic fiber woven fabric, an organic fiber nonwoven fabric, an inorganic fiber nonwoven fabric, or a combination thereof.

12. A method of manufacturing a laminate, comprising: providing a plurality of prepregs as described in claim 10; stacking the prepregs; and heating and curing the stacked prepregs at a curing pressure and a curing temperature to form a laminate.

13. The method of manufacturing a laminate as claimed in claim 12, wherein the curing pressure is from 10 kg / cm² to 60 kg / cm², and the curing temperature is from 150°C to 250°C.

14. A laminate obtained by the method of manufacturing a laminate as described in claim 12.

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