Modified polyphenylene ether resin, method for producing the same, and resin composition containing the same

Abstract

To provide a modified polyphenylene ether resin that can be applied to electronic components or electronic products (e.g., circuit boards or copper clad laminates), and a preparation method therefor.SOLUTION: A modified polyphenylene ether resin has a structure represented by Formula 1, where R1-R8 are each selected from a hydrogen group or a C1-C6 alkyl group, P1-P4 are each selected from a single bond or a ketone group, Q1-Q4 are each selected from a benzene ring group, a styryl group, a phenylethynyl group, an ethynyl group, a vinyl group, a methyl vinyl group, a naphthalene ring group, or hydrogen, and X is a linking group selected from a single bond or the following chemical formula.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a modified resin and a method for producing the same, and more particularly to a modified polyphenylene ether resin and a method for producing the same.

Background Art

[0002] With the popularization of the fifth-generation mobile communication network (5G), the printed circuit board (PCB) industry has shifted to higher-speed and high-frequency substrates, which has promoted the continuous development and improvement of copper clad laminate (CCL) materials. Copper clad laminates are usually composed of copper foil, glass fiber cloth, and resin, and polyphenylene ether resin is a commonly used insulating material.

Summary of the Invention

Problems to be Solved by the Invention

[0003] However, industrial polyphenylene ether has a large molecular weight and high viscosity, which may reduce the quality and / or productivity of the manufactured copper clad laminate. Furthermore, it is difficult to adapt to corresponding standards to meet various requirements. Therefore, modifying the polyphenylene ether resin (e.g., terminal functional group modification, adjustment of molecular weight and distribution) to facilitate the production of copper clad laminates and maintain the high quality of the obtained products has become an important research topic in this field currently.

Means for Solving the Problems

[0004] The present invention provides a modified polyphenylene ether resin, a method for producing the same, and a resin composition containing the modified polyphenylene ether resin.

[0005] The method for producing the modified polyphenylene ether resin of the present invention is as follows: An unmodified polyphenylene ether is provided. The unmodified polyphenylene ether is reacted with a phenol compound and a radical initiator to obtain the corresponding product. The product is subjected to alkaline washing and solvent recrystallization to obtain a modified polyphenylene ether resin.

[0006] The modified polyphenylene ether resin of the present invention has a structure represented by formula (1) as herein.

[0007] The resin composition of the present invention includes the modified polyphenylene ether resin described above.

[0008] The electronic component of the present invention includes a film layer formed from the resin composition described above. [Effects of the Invention]

[0009] As described above, the modified polyphenylene ether resin of the present invention is relatively easy to manufacture and can be applied to electronic components or electronic products (for example, circuit boards or copper-clad laminates). [Brief explanation of the drawing]

[0010] [Figure 1] This is a schematic flowchart of a method for producing a modified polyphenylene ether resin according to one embodiment of the present invention. [Modes for carrying out the invention]

[0011] The following detailed description outlines exemplary embodiments that disclose specific details for illustrative purposes, not limitation, to provide a complete understanding of the various principles of the present invention. However, it will be obvious to those skilled in the art that the present invention can be carried out in other embodiments different from the specific details disclosed herein. Furthermore, descriptions of well-known apparatus, methods, and materials may be omitted to avoid obscuring the description of the various principles of the present invention.

[0012] The range expressed here can be understood as "approximately" from a particular value to "approximately" another particular value, and can therefore also be expressed directly as a particular value and / or another particular value. When expressing a range, another embodiment includes that particular value and / or another particular value. Similarly, when expressing a value as an approximate value using the antecedent "approximately," it is understood that such a particular value forms another embodiment. For example, when expressing a value using the antecedent "approximately," it can be expressed directly as that particular value. Furthermore, when expressing a value using the antecedent "approximately," it may be within ±3% of that value, or even within ±1% of that value. It should also be understood that each endpoint of a range is clearly related to or unrelated to the other endpoints.

[0013] Here, non-restrictive terms (e.g., “may,” “can,” “for example,” or other similar terms) refer to optional or selective implementation, inclusion, addition, or presence.

[0014] Here, derivatives of the compound may include substituting the unreactive hydrogen atoms in the compound with isotopes or unreactive alkyl groups having 1 to 5 carbon atoms (also known as C1 to C5).

[0015] Unless otherwise specified, all terms used herein (including technical and scientific terms) have the same meaning as those commonly understood by ordinary articulators in the field to which this invention pertains. Furthermore, terms (for example, those defined in commonly used dictionaries) should be interpreted in a way that is consistent with their meanings in the relevant technical context, and should not be interpreted in an idealized or overly formal sense unless explicitly defined herein.

[0016] Referring to Figure 1, the method for producing a modified polyphenylene ether resin may include the following steps: Step S10: Provide unmodified polyphenylene ether. Step S20: Modify the polyphenylene ether by reacting it with a phenol compound and a radical initiator. Step S30: Purify the product after the reaction by alkaline washing and solvent recrystallization. Step S40: Obtain the modified polyphenylene ether.

[0017] Modification of polyphenylene ether resin

[0018] In one embodiment, the corresponding product can be obtained or manufactured and the corresponding modification can be performed by appropriately reacting an unmodified polyphenylene ether, a phenol compound, and a radical initiator.

[0019] In one embodiment, the unmodified polyphenylene ether may be a polyphenylene ether in which the corresponding phenyl group is substituted only with hydrogen atoms, or the corresponding phenyl group is substituted with an alkyl group having 1 to 5 carbon atoms (also known as C1 to C5). For example, the unmodified polyphenylene ether may be poly(2,6-dimethyl-1,4-phenylene ether) (CAS number: 25134-01-4), but the present invention is not limited thereto.

[0020] In one embodiment, the phenolic compound includes, for example, a bisphenol compound. In one embodiment, the bisphenol compound includes, for example, bisphenol A (BPA), tetramethyl bisphenol (TMBP), tetramethyl bisphenol A (TMBPA), tetramethyl bisphenol F (TMBPF), bisphenol S (BPS), dicyclopentadiene bisphenol (e.g., DCPD-DIDMP, see the chemical formula below), or a derivative thereof. [Chemical formula]

[0021] In one embodiment, the phenolic compound includes, for example, a tetraphenol compound. In one embodiment, the tetraphenol compound includes, for example, 1,1,2,2-tetrakis(p-hydroxyphenyl)ethane (TPE, CAS number: 7727-33-5), or a derivative thereof.

[0022] In one embodiment, the radical initiator includes, for example, a peroxide, and preferably, the radical initiator may be a peroxide having a corresponding benzene ring. In one embodiment, the radical initiator can include benzoyl peroxide (BPO) or a derivative thereof (e.g., benzoyl peroxide having an alkyl substitution). The "alkyl substitution" above or below may be an alkyl substitution in which at least one hydrogen is substituted with an alkyl group having 1 to 5 carbon atoms (also referred to as C1 to C5).

[0023] In one embodiment, a reaction in which an unmodified polyphenylene ether, a phenol compound, and a radical initiator are used as the product may be analogous to a rearrangement reaction. The reaction mechanism may include a radical initiator that forms a radical by a suitable method (e.g., heating). The radical can then attack the terminal end of the phenol compound to form a corresponding radical, and / or the radical can attack the terminal end of the polyphenylene ether to form a corresponding radical. Between the polyphenylene ether having a terminal radical and the phenol compound having a terminal radical, the reaction is terminated by the interaction / combination of the radicals, so that a corresponding molecule / polymer having at least two hydroxyl groups can be formed. Furthermore, the aforementioned radicals can also react with the benzene ring and / or structures on the polyphenylene ether, thereby shortening the chain length of the polyphenylene ether and, accordingly, reducing its molecular weight. Thus, in the reaction described above, the relationship between the polyphenylene ether and the radical initiator may be related to the molecular weight or polydispersity index (PDI) of the product. For example, when the proportion of radical initiators is high (e.g., high molar amount), the molecular weight of the product may be low and / or the polydispersity index may be high. Conversely, when the proportion of radical initiators is low (e.g., low molar amount), the molecular weight of the product may be high and / or the polydispersity index may be low. The polydispersity index, also known as the molecular weight distribution, refers to the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn) (i.e., Mw / Mn).

[0024] In one embodiment, the equivalent amount of the radical initiator is approximately 0.05 to 2 times the phenol equivalent amount of the phenol compound. That is, the ratio of phenol equivalent of the phenol compound to the equivalent amount of the radical initiator is approximately 100:5 to 100:200. In this way, the average number of hydroxyl groups per modified polyphenylene ether molecule in the modified polyphenylene ether obtained after the reaction is approximately 2.0 or more.

[0025] In one embodiment, preferably, the equivalent amount of the radical initiator is about 0.1 to about 1.5 times the phenol equivalent amount of the phenol compound. That is, phenol equivalent amount of phenol compound : equivalent amount of radical initiator ≈ 100:10 to 100:150.

[0026] In one embodiment, preferably, the equivalent amount of the radical initiator may be less than the phenol equivalent amount of the phenol compound. In this way, the possibility of side reactions can be reduced (however, this does not mean that they can be completely avoided under the natural conditions of the chemical reaction).

[0027] In one embodiment, more preferably, the phenol equivalent of the phenol compound is about 1.5 to about 20 times the equivalent of the radical initiator. In one embodiment, more preferably, the phenol equivalent of the phenol compound is 1.5 times or more (e.g., about 1.75 times, about 1.8 times, or about 2 times) to about 10 times the equivalent of the radical initiator.

[0028] In one embodiment, a catalyst may be further added (however, the present invention is not limited thereto). The catalyst can accelerate the reaction rate of the rearrangement reaction. The catalyst may be added together with the phenol compound. The catalyst may include water-soluble catalysts suitable for dissolving in water, such as tertiary amines, quaternary ammonium salts, phosphates, or combinations thereof. For example, catalysts include tetraalkylammonium halides (e.g., tetramethylammonium chloride (TMAC), CAS number: 75-57-0), tetraethylammonium chloride (TEAC, CAS number: 56-34-8), tetramethylammonium bromide (TMAB, CAS number: 64-20-0), tetraethylammonium bromide (TEAB, CAS number: 71-91-0), tetrapropylammonium bromide (TPAB, CAS number: 1941-30-6), tetrabutylammonium bromide (TBAB, CAS number: 1643-19-2), and benzylalkylammonium halides (e.g., benzyltrimethylammonium chloride, This may include BTMAC (CAS No.: 56-93-9), benzyltriethylammonium chloride (BTEAC, CAS No.: 56-37-1), or benzyldimethyldecylammonium chloride (CAS No.: 965-32-2). In one embodiment, based on the unmodified polyphenylene ether used in the reaction, the amount of catalyst added is about 1 wt% or less of the weight of the unmodified polyphenylene ether used in the reaction.

[0029] In one embodiment, the average number of hydroxyl groups per modified polyphenylene ether molecule can be estimated by dividing the total molar amount of hydroxyl groups by the total molar amount of modified polyphenylene ether molecules (i.e., total molar amount of hydroxyl groups ÷ total molar amount of modified polyphenylene ether molecules). The total molar amount of hydroxyl groups can be determined by commonly used standards for the standardization of hydroxyl value (e.g., ISO 4629-2:2016, ASTM D1959, GB / T 12008.3, and CNS 6681, but not limited to these). The total molar amount of polymer molecules can be converted by measuring the corresponding average molecular weight using gel permeation chromatography (GPC).

[0030] In one embodiment, the modification reaction described above can be carried out in a hydrophobic or lipophilic solvent. In one embodiment, the modification reaction can be carried out in toluene, xylene, or a cosolvent thereof.

[0031] In one embodiment, the denaturation reaction described above can be carried out in an environment higher than room temperature (e.g., higher than 25°C). In one embodiment, the reaction can be carried out in an environment of about 80°C or higher.

[0032] In one embodiment, the denaturation reaction described above can be carried out in an environment below the boiling point temperature of the corresponding solvent.

[0033] In one embodiment, the above-described denaturation reaction can be carried out for approximately 0.5 to 6 hours. In one embodiment, the above-described denaturation reaction can be carried out for approximately 1 to 5 hours. In one embodiment, the above-described denaturation reaction can be carried out for approximately 2 to 4 hours. In one embodiment, the above-described denaturation reaction can be carried out for approximately 3 hours.

[0034] In one embodiment, the modified polyphenylene ether after the reaction can be further subjected to alkaline washing. In this way, the phenol equivalent of the modified polyphenylene ether can be increased. In one embodiment, after alkaline washing of the modified polyphenylene ether after the reaction, the average number of hydroxyl groups per molecule of modified polyphenylene ether can be made greater than 2.2.

[0035] In one embodiment, the alkaline cleaning described above can be carried out using a corresponding alkaline solution. In one embodiment, the alkaline solution may include a solution containing alkali metal ions or alkaline earth metal ions, preferably a solution containing alkali metal ions. Cationic ions with a valency of +3 or higher may cause undesirable side reactions. For example, the alkaline solution may include sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, sodium alkoxides (e.g., sodium methoxide (MeONa), sodium ethoxide (EtONa), sodium propoxide, sodium butoxide), potassium alkoxides (e.g., potassium methoxide (MeOK), potassium ethoxide (EtOK), potassium propoxide, potassium butoxide), or mixtures thereof, which can be dissolved in a suitable solvent (e.g., water, alcohol, alcohol-water mixture).

[0036] In one embodiment, the alkaline equivalent of the alkaline solution used for alkaline cleaning may be equal to about 10 wt% to about 60 wt% aqueous sodium hydroxide solution.

[0037] In one embodiment, the alkaline cleaning step described above can be carried out in an environment higher than room temperature (e.g., higher than 25°C). In one embodiment, the reaction can be carried out in an environment of about 40°C or higher.

[0038] In one embodiment, the alkaline cleaning step described above can be carried out in an environment lower than the boiling point temperature of the corresponding solvent.

[0039] In one embodiment, the alkaline cleaning step described above can be carried out for about 0.5 to 4 hours. In one embodiment, the modification reaction described above can be carried out for about 0.5 to 3 hours. In one embodiment, the modification reaction described above can be carried out for about 1 to 2 hours.

[0040] In one embodiment, after the modified polyphenylene ether molecules described above are formed, unreacted or unreactive large polyphenylene ether molecules can be removed by solvent purification and / or recrystallization. For example, unreacted or unreactive large polyphenylene ether molecules with a molecular weight of 40,000 or more may have low solubility in some low-polarity solvents (e.g., tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone). Therefore, by adding the low-polarity solvents described above, unreacted or unreactive large polyphenylene ether molecules can be precipitated and removed. Alternatively, the modified polyphenylene ether may be recrystallized by adding a corresponding high-polarity solvent (e.g., methanol, ethanol, or isopropanol). In this way, the purity and / or quality of the modified polyphenylene ether can be improved.

[0041] In one embodiment, a modified polyphenylene ether having a number-average molecular weight (Mn) of approximately 500 g / mol to 4,000 g / mol can be obtained by the solvent purification method and recrystallization described above, and the degree of dispersion index (PDI) of the modified polyphenylene ether is approximately 2.5 or less.

[0042] In one embodiment, a modified polyphenylene ether having a number-average molecular weight (Mn) of approximately 1,000 g / mol to 3,000 g / mol can be obtained by the solvent purification method and recrystallization described above, and the degree of dispersion index (PDI) of the modified polyphenylene ether is approximately 1.8 or less.

[0043] In one embodiment, the solvent used for recrystallization may include toluene, xylene, tetrahydrofuran (THF), methyl ethyl ketone (MEK), cyclohexanone, methyl isobutyl ketone (MIBK), or a co-solvent thereof.

[0044] In one embodiment, a modified polyphenylene ether can be represented by the following formula (1).

[0045] [ka]

[0046] In equation (1), k is a non-negative integer. i, i', j, and j' may be the same or different from each other, i and j may be integers between 0 and 200, and i' and j' may be integers between 1 and 200. Furthermore, the value of i + i' + j + j' + k is between 2 and 400.

[0047] In equation (1), preferably, k is 0 or 1, and i, i', j, and j' may be the same or different from each other, and each may be an integer from 1 to 200. Also, the value of i + i' + j + j' + k is from 4 to 200.

[0048] In formula (1), R1 to R8 may be the same or different, and each can be selected from a hydrogen group or an alkyl group having 1 to 6 carbon atoms (also known as C1 to C6).

[0049] In formula (1), P1 to P4 may be the same or different, and each can be selected from a single bond (─) or a ketone group (see chemical formula below). [ka]

[0050] In formula (1), Q1 to Q4 may be the same or different from each other, and each can be selected from a benzene ring group, a styryl group, a phenylethynyl group, an etynyl group, a vinyl group, a methyl vinyl group, a naphthalene ring group, or hydrogen.

[0051] In equation (1), X can be selected from a single bond (─) or the following linking groups. [ka]

[0052] In one embodiment, after the solvent purification and recrystallization described above, the proportion of large molecular weight polyphenylene ethers with a molecular weight of 20,000 g / mol or more, based on the total weight of the dried product, may be basically 1.5 wt% or less, preferably about 1.0 wt% or less.

[0053] In one embodiment, the number-average molecular weight (Mn) of the modified polyphenylene ether resin may be about 500 g / mol to 4,000 g / mol, preferably about 1,000 g / mol to 3,000 g / mol.

[0054] In one embodiment, the dispersion index of the modified polyphenylene ether resin is about 2.5 or less, preferably about 1.8 or less.

[0055] In one embodiment, the hydroxyl equivalent of the modified polyphenylene ether resin is about 1,300 g / eq or less, and the number of corresponding hydroxyl groups per molecule is about 2.0 to 4.0.

[0056] <Applications of Modified Polyphenylene Ether Resins>

[0057] The modified polyphenylene ether resin represented by formula (1) is suitable for application in electronic products.

[0058] Modified polyphenylene ether resins represented by formula (1) are suitable for applications in electronic products because they can have lower dielectric properties, higher glass transition temperature (Tg), better heat resistance, and / or better fluidity.

[0059] The modified polyphenylene ether resin represented by formula (1) is convenient to use because it is readily soluble in common organic solvents (e.g., toluene or methyl ethyl ketone (MEK)).

[0060] In one embodiment, when a modified polyphenylene ether resin represented by formula (1) is applied to an electronic product, it exhibits superior heat resistance, a higher glass transition temperature, and / or superior fluidity compared to other known resins used in electronic products.

[0061] In one embodiment, when a modified polyphenylene ether resin represented by formula (1) is applied to an electronic product, it can exhibit superior heat resistance, a higher glass transition temperature, and better fluidity compared to other known resins used in electronic products. In this way, its application (e.g., to copper-clad laminates) can be made relatively easy.

[0062] In one embodiment, the resin composition may include the modified polyphenylene ether resin of the embodiment described above. In one embodiment, when the total weight of the resin composition is a weight percentage, the modified polyphenylene ether resin is in the range of 30 wt% to 60 wt%, preferably about 40 wt%.

[0063] In one embodiment, the resin composition may further contain a crosslinking agent. In one embodiment, when the total weight of the resin composition is 100 wt%, the amount of the crosslinking agent may be in the range of 10 wt% to 20 wt%, preferably about 15 wt%.

[0064] In one embodiment, the degree of crosslinking between the resin and / or the corresponding polymer can be improved by adding a crosslinking agent. In one embodiment, the crosslinking agent may include an allyl group. In one embodiment, the crosslinking agent may include triallyl cyanurate (TAC), trially isocyanurate (TAIC), trimethallyl isocyanurate (TMAIC), diallyl phthalate, divinylbenzene, triallyl trimellitate, or a combination thereof.

[0065] In one embodiment, the resin composition may include a filler. In one embodiment, when the total weight of the resin composition is 100 wt%, the filler may be in the range of 5 wt% to 15 wt%, preferably about 10 wt%.

[0066] In one embodiment, the viscosity of the resin composition can be improved by adding an inorganic filler. For example, the inorganic filler may be silicon dioxide, titanium dioxide, aluminum hydroxide, aluminum oxide, magnesium hydroxide, magnesium oxide, calcium carbonate, boron oxide, calcium oxide, strontium titanate, barium titanate, calcium titanate, magnesium titanate, boron nitride, aluminum nitride, silicon carbide, cerium oxide, or a combination thereof.

[0067] In one embodiment, the silicon dioxide added as an inorganic filler may include molten or crystalline silicon dioxide. In one embodiment, molten silicon dioxide is more preferred when considering the dielectric properties when applied to a copper-clad laminate.

[0068] In one embodiment, the titanium dioxide added as an inorganic filler may include rutile, anatase, or brookite type titanium dioxide. In one embodiment, rutile type titanium dioxide is more preferred when considering the dielectric properties when applied to a copper-clad laminate.

[0069] In one embodiment, the resin composition may further contain a crosslinking accelerator. In one embodiment, when the total weight of the resin composition is 100 wt%, the amount of the crosslinking accelerator may be in the range of 0.5 wt% to 1.5 wt%, preferably about 1.0 wt%.

[0070] In one embodiment, a crosslinking accelerator can improve system reactivity. The accelerator may include a catalyst and a peroxide.

[0071] In one embodiment, the catalyst used as a crosslinking accelerator may include, but is not limited to, 2-phenyl-1H-imidazole-1-propionitrile (2PZCN; CAS No.: 23996-12-5), 1-benzyl-2-phenyl-1H-imidazole (1B2PZ; CAS No.: 37734-89-7), thiabendazole (TBZ; CAS No.: 148-79-8), or a combination thereof.

[0072] In one embodiment, the peroxide used as a crosslinking accelerator is tert-butylcumyl peroxide, dicumyl peroxide (DCP), benzoyl peroxide, BPO), 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne, 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, di(tert-butylperoxyisopropyl)benzene, Luperox® F series peroxide formulations (e.g., 1,3(4)-bis(tert-butylperoxyisopropyl)benzene) The present invention may include, but is not limited to, bis(tert-butylperoxyisopropyl)benzene), see the chemical formula below, LuF), or combinations thereof. [ka]

[0073] In one embodiment, the resin composition may further contain a flame retardant. In one embodiment, when the total weight of the resin composition is 100 wt%, the flame retardant may be in the range of 5 wt% to 15 wt%, preferably about 10 wt%.

[0074] In one embodiment, the flame resistance or flame retardancy of a resin composition can be improved by adding a flame retardant. Here, "flame resistance" or "flame retardancy" means that the object being referred to (e.g., a film, layer, or structure) can meet the flame retardancy criteria of a standard test method. For example, the UL94 plastic flammability standard for Test for Flammability of Plastic Materials for Parts in Devices and Appliances, issued by UL (Underwriters Laboratories) in the United States, has a standard value of at least HB grade.

[0075] In one embodiment, the flame retardant may include a brominated flame retardant, a phosphorus-based flame retardant, or a combination thereof, but the present invention is not limited thereto.

[0076] In one embodiment, the brominated flame retardant may include Saytex BT93W (ethylene bistetrabromophthalimide), Saytex BT93, Saytex 120 (tetradecabromodiphenoxybenzene), Saytex 8010 (ethane-1,2-bis(pentabromophenyl)), Saytex 102 (decabromo diphenoxy oxide), or a combination thereof, all manufactured by Albemarle, Inc., USA.

[0077] In one embodiment, the phosphorus-based flame retardant may include sulfosuccinic acid ester, phosphazene, ammonium polyphosphate, melamine polyphosphate, melamine cyanurate, or a combination thereof. For example, it may include triphenyl phosphate (TPP), resorcinol bis(diphenyl phosphate), RDP, bisphenol A bis(diphenyl phosphate), BPAPP, resorcinol bis(diphenyl phosphate) (e.g., CR-733S from Nippon Daihachi Chemical Co., Ltd.), 1,3-phenylenyltrachys(2,6-dimethylphenyl) phosphate (e.g., PX-200 from Nippon Daihachi Chemical Co., Ltd.), SPB-100 phosphorus-based flame retardant from Nippon Otsuka Chemical Co., Ltd., or a combination thereof.

[0078] In one embodiment, a resin composition comprising a modified polyphenylene ether resin according to one embodiment of the present invention can be used in the manufacture of electronic components (for example, copper-clad laminates or printed circuit boards, but the present invention is not limited thereto).

[0079] In one embodiment, a resin composition comprising a modified polyphenylene ether resin in one embodiment of the present invention is suitable for forming insulating films for electronic products, and its application to electronic products may have the following specifications: dielectric constant (Dk) of about 4.0 or less (e.g., about 3.3 to 4.0), dielectric loss tangent (Df) of about 0.0050 or less (e.g., about 0.0035 to 0.0050), glass transition temperature (Tg) of about 210°C to 235°C, peel strength greater than about 6.0 lb / in (e.g., even greater than 6.5 lb / in), and / or water absorption of about 0.5% or less (e.g., water absorption of about 0.5% or less over 2 hours).

[0080] Most commercially available resins used in the manufacture of copper-clad laminates (e.g., Sabic's SA-9000 resin, but the present invention is not limited to this) are produced by oxidative polymerization. However, the oxidative polymerization method described above requires the introduction of oxygen. During the process of introducing oxygen, it is necessary to control the flow rate, velocity, and / or concentration of oxygen to prevent the possibility of strong oxidation reactions (e.g., combustion, flashover, or explosion) occurring due to the coexistence of solvent and oxygen. Furthermore, reaction tanks suitable for the oxidative polymerization described above must be equipped with gas detectors, fire protection devices, and / or explosion prevention devices, which increases production costs accordingly. In addition, oxidative polymerization often requires the addition of a metal catalyst (mainly a metal or transition metal with a valency of +3 or higher). Separating the metal catalyst from the product usually requires purification, making the corresponding reaction process more complex. Furthermore, because oxidative polymerization must be carried out in a specific environment (e.g., a specific solvent), it is not suitable for customized modifications. For the reasons stated above, the modified polyphenylene ether resin in one embodiment of the present invention provides a simpler manufacturing process compared to commercially available resins used in the production of copper-clad laminates. Furthermore, the modified polyphenylene ether resin in one embodiment of the present invention is suitable for the production of copper-clad laminates, and / or copper-clad laminates produced using it meet general standards.

[0081] <Manufacturing of copper-clad laminates>

[0082] By dissolving the modified polyphenylene ether resin of the above-described embodiment in a suitable solvent and mixing it with other components, a resin varnish can be formed, and therefore it can be used in the production of copper-clad laminates using known methods. For example, since the resin composition of the above-described embodiment can be dissolved in a suitable solvent to form a resin varnish, it can be used in the production of copper-clad laminates.

[0083] The method for manufacturing copper-clad laminates can be as follows.

[0084] The 2116 fiberglass cloth is impregnated with the resin varnish described above, and then dried for several minutes at approximately 170°C (including the temperature of the impregnation machine). By adjusting and controlling the drying time, a post-dried prepreg with a melting point viscosity of approximately 4,000 to 12,000 poise is obtained. Next, four prepregs are stacked layer by layer between two copper foils with a thickness of approximately 35 μm to form a copper-clad laminate according to one embodiment (details are as follows).

[0085] The conditions / procedures for the lamination process are as follows:

[0086] Step 1: Increase the temperature from approximately 80°C to approximately 195°C over a period of about 0.5 hours (indicated as 85→195°C, 0.5 hours).

[0087] Step 2: Apply pressure of approximately 7 kg / cm² for about 0.5 hours. 2 ~Approx. 25kg / cm 2 Raise it up to (7 → 25 kg / cm 2 (Write 0.5 hours).

[0088] Step 3: Temperature of approximately 195°C and approximately 25 kg / cm² 2 Laminate at this pressure for approximately 2.0 hours (195℃ / 5kg / cm²). 2 (To be written as 2.0 hours).

[0089] <Examples and comparative examples>

[0090] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the examples below. It should be noted that, for the sake of brevity, certain numerical values ​​in the examples or comparative examples (such as those recorded in tables) may be given without the modifier "approximately". Furthermore, each value may include values ​​and mean values ​​within the tolerance range of a particular value determined by an expert in the art, and have a range of ±3% of that value, and even a range of ±1% of that value, taking into account the specific amount of error of the measurement and measurement-related errors being discussed (i.e., limitations of the measurement system).

[0091] <Examples of modified polyphenylene ether resin preparation and corresponding comparative examples>

[0092] <Example 1>

[0093] Approximately 600 grams of toluene, approximately 100 grams of commercially available polyphenylene ether (product name: XYRON) TM Approximately 0.5 grams of tetramethylammonium chloride and approximately 8.25 grams of tetramethylbisphenol A (S203A, manufactured by Asahi Kasei Engineering Plastics Co., Ltd.) were added to the reaction vessel and heated to 90°C to dissolve.

[0094] Next, approximately 3.7 grams of approximately 75 wt% benzoyl peroxide was added dropwise over approximately 60 minutes (for example, in at least 4 parts). Continuous stirring was maintained throughout this process, and a constant temperature (above approximately 70°C, e.g., approximately 70°C to 90°C) was maintained.

[0095] After the above-mentioned dropwise addition was complete, the mixture was stirred continuously at a constant temperature (approximately 70°C to 90°C) for about 3 hours to allow the reaction to proceed.

[0096] After the reaction, the reaction solution was subjected to alkaline washing with an appropriate amount of 20 wt% sodium hydroxide aqueous solution (for example, the total volume ratio of the sodium hydroxide aqueous solution used to the reaction solution may be approximately 1:1 to 1:5) at a constant temperature (approximately 70°C) for about 1 hour. The aqueous layer was then removed.

[0097] Then, tetrahydrofuran was added to the organic solvent layer after removing the aqueous layer, and unreacted or non-reactive polyphenylene ether was recrystallized and removed at approximately 15°C or below. Subsequently, methanol was added to precipitate the resin, and a drying process was carried out.

[0098] In Example 1, the number-average molecular weight of the resin may be approximately 2,772 g / mol, the molecular weight distribution may be approximately 1.47, the hydroxyl group equivalent of the resin may be approximately 1260 g / eq, and the number of hydroxyl groups per molecule (i.e., number-average molecular weight / resin hydroxyl group equivalent) may be approximately 2.2. Furthermore, the ratio of the total weight of polymer monomers with molecular weights exceeding 20,000 g / mol to the total weight of the resin was approximately 0.5 wt%.

[0099] <Example 2>

[0100] Approximately 600 grams of toluene, approximately 100 grams of commercially available polyphenylene ether (product name: Xylon S202A, manufactured by Asahi Kasei Engineering Plastics Co., Ltd.), approximately 0.5 grams of benzyltrimethylammonium chloride, and approximately 11.6 grams of tetramethylbiphenol were added to a reaction vessel and heated to approximately 100°C to dissolve.

[0101] Next, approximately 5.2 grams of approximately 75 wt% benzoyl peroxide was added dropwise over approximately 120 minutes (for example, to at least 8 parts). Continuous stirring was maintained throughout this process, and a constant temperature (above approximately 70°C, for example, approximately 70°C to 100°C) was maintained.

[0102] After the above-mentioned dropwise addition was completed, the mixture was stirred continuously at a constant temperature (approximately 70°C to 100°C) for about 3 hours to allow the reaction to proceed.

[0103] After the reaction, the reaction solution was subjected to alkaline washing with an appropriate amount of sodium methoxide at a constant temperature (approximately 50°C or higher, for example, approximately 50°C to 70°C) for about 1 hour. Then, water was added for further washing, and the aqueous layer was removed.

[0104] Next, methyl ethyl ketone was added to the organic solvent layer after removing the aqueous layer, and unreacted or non-reactive polyphenylene ether was recrystallized and removed at approximately 15°C or below. Then, methanol was added to precipitate the resin, and a drying process was carried out.

[0105] In Example 2, the number-average molecular weight of the resin may be approximately 2,320 g / mol, the molecular weight distribution may be approximately 1.43, the hydroxyl group equivalent of the resin may be approximately 960 g / eq, and the number of hydroxyl groups per molecule may be approximately 2.4. Furthermore, the ratio of the total weight of polymer monomers with molecular weights exceeding 20,000 g / mol to the total weight of the resin was approximately 0.3 wt%.

[0106] <Example 3>

[0107] Approximately 600 grams of xylene, approximately 100 grams of commercially available polyphenylene ether (product name: StarAir® LXR-035, manufactured by China National BlueStar (Group)), and approximately 20 grams of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane were added to a reaction vessel and heated to approximately 110°C to dissolve.

[0108] Next, approximately 10 grams of approximately 75 wt% benzoyl peroxide was added dropwise over approximately 240 minutes (for example, in at least 12 parts). Continuous stirring was maintained throughout this process, and a constant temperature (above approximately 70°C, e.g., approximately 70°C to 110°C) was maintained.

[0109] After the dropwise addition described above was completed, the mixture was stirred continuously at a constant temperature (approximately 70°C to 110°C) for about 3 hours to allow the reaction to proceed.

[0110] After the reaction, the reaction solution was subjected to alkaline washing with an appropriate amount of sodium methoxide at a constant temperature (approximately 50°C or higher, for example, approximately 50°C to 70°C) for about 2 hours. Then, water was added for further washing, and the aqueous layer was removed.

[0111] Subsequently, cyclohexanone was added to the organic solvent layer after removing the aqueous layer, and unreacted or non-reactive polyphenylene ether was recrystallized and removed at approximately 4°C or below. Then, methanol was added to precipitate the resin, and a drying process was carried out.

[0112] In Example 3, the number-average molecular weight of the resin may be approximately 2,124 g / mol, the molecular weight distribution may be approximately 1.50, the hydroxyl group equivalent of the resin may be approximately 566 g / eq, and the number of hydroxyl groups per molecule may be approximately 3.75. Furthermore, the ratio of the total weight of polymer monomers with molecular weights exceeding 20,000 g / mol to the total weight of the resin was approximately 0.9 wt%.

[0113] <Example 4>

[0114] Approximately 600 grams of toluene, approximately 100 grams of commercially available polyphenylene ether (product name: Xylon S203A), approximately 0.5 grams of tetramethylammonium chloride, and approximately 19 grams of tetramethylbiphenol were added to a reaction vessel and heated to 90°C to dissolve.

[0115] Next, approximately 6 grams of approximately 75 wt% benzoyl peroxide was added dropwise over approximately 120 minutes (for example, in at least 6 parts). Continuous stirring was maintained throughout this process, and a constant temperature (above approximately 70°C, for example, approximately 70°C to 90°C) was maintained.

[0116] After the above-mentioned dropwise addition was complete, the mixture was stirred continuously at a constant temperature (approximately 70°C to 90°C) for about 3 hours to allow the reaction to proceed.

[0117] After the reaction, the reaction solution was subjected to alkaline washing with an appropriate amount of 8 wt% sodium bicarbonate aqueous solution at a constant temperature (approximately 70°C) for about 1 hour. The aqueous layer was then removed.

[0118] Then, methyl isobutyl ketone was added to the organic solvent layer after removing the aqueous layer, and unreacted or non-reactive polyphenylene ether was recrystallized and removed at a temperature of approximately 25°C or below. Subsequently, methanol was added to precipitate the resin, and a drying process was carried out.

[0119] In Example 4, the number-average molecular weight of the resin may be approximately 1,750 g / mol, the molecular weight distribution may be approximately 1.60, the hydroxyl group equivalent of the resin may be approximately 670 g / eq, and the number of hydroxyl groups per molecule may be approximately 2.60. Furthermore, the ratio of the total weight of polymer monomers with molecular weights exceeding 20,000 g / mol to the total weight of the resin was approximately 0.1 wt%.

[0120] <Example 5>

[0121] Approximately 600 grams of toluene, approximately 100 grams of commercially available polyphenylene ether (product name: Xylon S202A), approximately 0.5 grams of tetramethylammonium chloride, and approximately 42 grams of tetramethylbiphenol were added to a reaction vessel and heated to 80°C to dissolve.

[0122] Next, approximately 10 grams of approximately 75 wt% benzoyl peroxide was added dropwise over approximately 120 minutes (for example, to at least 6 parts). Continuous stirring was maintained throughout this process, and a constant temperature (above approximately 70°C, e.g., approximately 70°C to 80°C) was maintained.

[0123] After the dropwise addition described above was completed, the mixture was stirred continuously at a constant temperature (approximately 70°C to 80°C) for about 3 hours to allow the reaction to proceed.

[0124] After the reaction, the reaction solution was subjected to alkaline washing with an appropriate amount of 49.5 wt% sodium hydroxide aqueous solution at a constant temperature (approximately 70°C) for about 1 hour. The aqueous layer was then removed.

[0125] Then, cyclohexanone was added to the organic solvent layer after removing the aqueous layer, and unreacted or non-reactive polyphenylene ether was recrystallized and removed at approximately 25°C or below. Subsequently, methanol was added to precipitate the resin, and a drying process was carried out.

[0126] In Example 5, the number-average molecular weight of the resin may be approximately 1,260 g / mol, the molecular weight distribution may be approximately 1.5, the hydroxyl group equivalent of the resin may be approximately 360 g / eq, and the number of hydroxyl groups per molecule may be approximately 3.50. Furthermore, the ratio of the total weight of polymer monomers with molecular weights exceeding 20,000 g / mol to the total weight of the resin was approximately 0.05 wt%.

[0127] <Comparative Example 1>

[0128] Approximately 600 grams of toluene, approximately 100 grams of commercially available polyphenylene ether (product name: Xylon S202A), approximately 0.5 grams of tetramethylammonium chloride, and approximately 8 grams of tetramethylbiphenol were added to a reaction vessel and heated to 80°C to dissolve.

[0129] Next, approximately 19 grams of approximately 75 wt% benzoyl peroxide was added dropwise over approximately 120 minutes (for example, to at least 6 parts). Continuous stirring was maintained throughout this process, and a constant temperature (above approximately 70°C, for example, approximately 70°C to 80°C) was maintained.

[0130] After the dropwise addition described above was completed, the mixture was stirred continuously at a constant temperature (approximately 70°C to 80°C) for about 3 hours to allow the reaction to proceed.

[0131] After the reaction, the reaction solution was directly washed with water at a constant temperature (approximately 70°C). Then, the aqueous layer was removed.

[0132] Subsequently, methanol was added to the organic solvent layer after removing the aqueous layer to precipitate the resin, and a drying process was carried out.

[0133] The number-average molecular weight of the resin in <Comparative Example 1> may be approximately 1,815 g / mol, the molecular weight distribution may be approximately 4.50, the hydroxyl group equivalent of the resin may be approximately 1,215 g / eq, and the number of hydroxyl groups per molecule may be approximately 1.5. Furthermore, the ratio of the total weight of polymer monomers with molecular weights exceeding 20,000 g / mol to the total weight of the resin was approximately 6.5 wt%.

[0134] <Comparative Example 2>

[0135] Approximately 600 grams of toluene, approximately 100 grams of commercially available polyphenylene ether (product name: Xylon S202A), approximately 0.5 grams of tetramethylammonium chloride, and approximately 6 grams of tetramethylbiphenol were added to a reaction vessel and heated to 80°C to dissolve.

[0136] Next, approximately 30 grams of approximately 75 wt% benzoyl peroxide was added dropwise over approximately 120 minutes (for example, to at least 6 parts). Continuous stirring was maintained throughout this process, and a constant temperature (above approximately 70°C, for example, approximately 70°C to 80°C) was maintained.

[0137] After the dropwise addition described above was completed, the mixture was stirred continuously at a constant temperature (approximately 70°C to 80°C) for about 3 hours to allow the reaction to proceed.

[0138] After the reaction, the reaction solution was directly washed with water at a constant temperature (approximately 70°C). Then, the aqueous layer was removed.

[0139] Subsequently, methanol was added to the organic solvent layer after removing the aqueous layer to precipitate the resin, and a drying process was carried out.

[0140] The number-average molecular weight of the resin in <Comparative Example 2> may be approximately 1,292 g / mol, the molecular weight distribution may be approximately 3.8, the hydroxyl group equivalent of the resin may be approximately 685 g / eq, and the number of hydroxyl groups per molecule may be approximately 1.9. Furthermore, the ratio of the total weight of polymer monomers with molecular weights exceeding 20,000 g / mol to the total weight of the resin was approximately 4.2 wt%.

[0141] Table 1 shows the corresponding adjustments and results for Examples 1 to 5 and Comparative Examples 1 to 5.

[0142] [Table 1]

[0143] <Evaluation Method>

[0144] Specific molecular weight distribution ratios: The corresponding distribution ratio for a specific molecular weight can be estimated by integrating the corresponding molecular weight distribution curve. For example, distribution ratios with molecular weights of 20,000 g / mol or more can be obtained by dividing the integral value of the curve for molecular weights of 20,000 g / mol or more by the integral value of all curves in the molecular weight distribution.

[0145] Number-average molecular weight (Mn): The prepared modified polyphenylene ether resin was dissolved in tetrahydrofuran (THF) to prepare a 1 wt% test solution. Next, the number-average molecular weight of the test solution was measured by gel permeation chromatography (GPC).

[0146] Weight-average molecular weight (Mw): The prepared modified polyphenylene ether resin was dissolved in tetrahydrofuran (THF) to prepare a 1 wt% test solution. Next, the weight-average molecular weight of the test solution was measured by gel permeation chromatography (GPC).

[0147] The dispersion index (PDI) was calculated by dividing the measured weight-average molecular weight by the measured number-average molecular weight (i.e., Mw / Mn). A smaller PDI indicates a more concentrated molecular weight distribution. Under conditions where the initial reactants, catalyst, and their corresponding amounts are the same or similar, a smaller PDI indicates a less likely corresponding side reaction, thus leading to a more concentrated molecular weight distribution. Therefore, a concentrated molecular weight distribution (i.e., a small PDI) indicates a more homogeneous functional group, shape, and / or structure, and can be said to indicate a more homogeneous reaction / synthesis. Furthermore, a concentrated molecular weight distribution (i.e., a small PDI) may indicate a reduced relative proportion of byproducts from side reactions (e.g., large polymer molecules formed by repolymerization). As a result, in terms of product application, subsequent processing and application can be more stable, and product quality or yield can be improved during further processing.

[0148] Hydroxyl group equivalent: Determined by commonly used standards (e.g., ISO 4629-2:2016, ASTM E222-10, GB / T 12008.3, and CNS 6681, but the present invention is not limited thereto).

[0149] The number of hydroxyl groups per molecule is calculated from the corresponding hydroxyl group equivalent and the corresponding molecular weight (e.g., number-average molecular weight).

[0150] As shown in Table 1, the degree of dispersion index (PDI; i.e., Mw / Mn) of the modified polyphenylene ether resins (which may be the modified polyphenylene ether resins in one embodiment of the present invention) of Examples 1 to 5 is lower compared to Comparative Examples 1 and 2. Therefore, subsequent processing or application can be made more stable, and the subsequent processed products can have better quality or yield.

[0151] As shown in Table 1, the number-average molecular weight of the resins of Comparative Example 1 and Comparative Example 2 (which may be referred to as unmodified polyphenylene ether resins rather than modified polyphenylene ether resins in one embodiment of the present invention) was equivalent to that of Examples 1 to 5. However, the proportion of molecules with a molecular weight of 20,000 g / mol or more was high. This may be because the corresponding alkaline washing step was not performed, making it difficult or impossible to separate and remove large polyphenylene ether molecules. Therefore, the resins of Comparative Example 1 and Comparative Example 2 may have low applicability to subsequent processes.

[0152] As shown in Table 1, the modified polyphenylene ether resins of Examples 1 to 5 (which may also be the modified polyphenylene ether resins in one embodiment of the present invention) had a greater number of hydroxyl groups per molecule compared to Comparative Examples 1 and 2. This may be because the method for producing the modified polyphenylene ether resin in one embodiment of the present invention includes a corresponding alkaline washing step, which increased the number of hydroxyl groups per molecule.

[0153] <Examples and comparative examples of applications to copper-clad laminates>

[0154] A resin varnish composition was prepared by mixing the materials according to the composition ratios shown in Table 2, and a copper-clad laminate was fabricated using the method described above.

[0155] In Examples 6 to 10, the modified polyphenylene ether used may be the modified polyphenylene ether obtained in Examples 1 to 5, respectively. In Comparative Example 3, the polyphenylene ether used may be a type of resin commonly used in the manufacture of general copper-clad laminates (for example, SA-9000 resin manufactured by Savic Corporation; that is, it may be referred to as an unmodified polyphenylene ether resin rather than a modified polyphenylene ether resin in one embodiment of the present invention). In Comparative Example 4, the polyphenylene ether used may be the resin of Comparative Example 1 (that is, it may be referred to as an unmodified polyphenylene ether resin rather than a modified polyphenylene ether resin in one embodiment of the present invention).

[0156] In Examples 6 to 10 and Comparative Examples 3 and 4, the crosslinking agent used was triallyl isocyanurate, which is sold by Mitsubishi Chemical Corporation.

[0157] In Examples 6 to 10 and Comparative Examples 3 and 4, the filler used was a silicon dioxide filler commercially available under the trademark name 525ARI series.

[0158] In Examples 6 to 10 and Comparative Examples 3 and 4, the crosslinking accelerator used was a peroxide-based crosslinking accelerator commercially available from Arkema SA under the trademark name Luperox F series.

[0159] In Examples 6 to 10 and Comparative Examples 3 and 4, the flame retardant used was a phosphorus-based flame retardant commercially available from Nippon Otsuka Chemical Co., Ltd. under the trademark name SPB-100.

[0160] In Examples 6 to 10 and Comparative Examples 3 and 4, approximately 53 parts by weight (also known as 53 wt%) of a resin composition (containing the above-mentioned modified polyphenylene ether resin or unmodified polyphenylene ether resin, a crosslinking agent, a filler, a crosslinking accelerator, and a flame retardant) was mixed with approximately 47 parts by weight (also known as 47 wt%) of a solvent (toluene / methyl ethyl ketone cosolvent) to form a corresponding resin varnish composition used in the production of copper-clad laminates.

[0161] <Example 6>

[0162] The resin in <Example 1> was olefinized with methacrylic anhydride.

[0163] Specifically, approximately 100 grams of toluene, approximately 100 grams of the resin from Example 1, approximately 14.7 grams of methacrylic anhydride, and approximately 8.9 grams of 4-(dimethylamino)pyridine (DMAP) were added to the reaction vessel. The reaction vessel was filled with dry nitrogen and heated to approximately 85°C, and the reaction was allowed to proceed for approximately 4 hours.

[0164] After the reaction, methanol was added to precipitate the resin and wash it off.

[0165] After washing and drying, the resin exhibited an acid value of approximately 1.44 mgKOH / g, an OH value of approximately 0.5 mgKOH / g for the remaining hydroxyl groups, a number-average molecular weight of approximately 2,840 g / mol, and a molecular weight distribution of approximately 1.45.

[0166] A resin varnish composition was prepared by mixing the materials according to the composition ratios shown in Table 2, and a copper-clad laminate was fabricated using the method described above. The laminate was then evaluated.

[0167] To explain in more detail, in Example 6, when the total weight of the resin composition was 100 wt%, the resin composition consisted of approximately 40 parts by weight (also called 40 wt%) of the olefinized resin from Example 1, approximately 15 parts by weight (also called 15 wt%) of a crosslinking agent, approximately 10 parts by weight (also called 10 wt%) of a filler, approximately 1 part by weight (also called 1 wt%) of a crosslinking accelerator, and approximately 10 parts by weight (also called 10 wt%) of a flame retardant. Furthermore, approximately 53 parts by weight (also called 53 wt%) of the resin composition was mixed with approximately 47 parts by weight (also called 47 wt%) of a solvent (toluene / methyl ethyl ketone cosolvent) to obtain the resin varnish composition used in Example 6 for the production of copper-clad laminates.

[0168] <Example 7>

[0169] The resin in <Example 2> was olefinized with methacrylic anhydride.

[0170] Specifically, approximately 100 grams of toluene, approximately 100 grams of the resin from Example 2, approximately 18.7 grams of methacrylic anhydride, and approximately 11.5 grams of 4-(dimethylamino)pyridine (DMAP) were added to the reaction vessel. The reaction vessel was filled with dry nitrogen and heated to approximately 90°C, and the reaction was allowed to proceed for approximately 5 hours.

[0171] After the reaction, methanol was added to precipitate the resin and wash it off.

[0172] After washing and drying, the resin exhibited an acid value of approximately 1.34 mgKOH / g, an OH value of approximately 0.1 mgKOH / g for the remaining hydroxyl groups, a number-average molecular weight of approximately 2,460 g / mol, and a molecular weight distribution of approximately 1.41.

[0173] A resin varnish composition was prepared by mixing the materials according to the composition ratios shown in Table 2, and a copper-clad laminate was fabricated using the same method as in Example 6. The laminate was then evaluated.

[0174] To explain in more detail, in Example 7, when the total weight of the resin composition was 100 wt%, the resin composition consisted of approximately 40 parts by weight (also called 40 wt%) of the olefinized resin from Example 2, approximately 15 parts by weight (also called 15 wt%) of a crosslinking agent, approximately 10 parts by weight (also called 10 wt%) of a filler, approximately 1 part by weight (also called 1 wt%) of a crosslinking accelerator, and approximately 10 parts by weight (also called 10 wt%) of a flame retardant. Furthermore, approximately 53 parts by weight (also called 53 wt%) of the resin composition was mixed with approximately 47 parts by weight (also called 47 wt%) of a solvent (toluene / methyl ethyl ketone cosolvent) to obtain the resin varnish composition used in Example 7 for the production of copper-clad laminates.

[0175] <Example 8>

[0176] The resin in <Example 3> was olefinized with methacrylic anhydride.

[0177] Specifically, approximately 100 grams of toluene, approximately 100 grams of the resin from Example 3, approximately 27.2 grams of methacrylic anhydride, and approximately 16.6 grams of 4-(dimethylamino)pyridine (DMAP) were added to the reaction vessel. The reaction vessel was filled with dry nitrogen and heated to approximately 95°C, and the reaction was carried out for approximately 6 hours.

[0178] After the reaction, methanol was added to precipitate the resin and wash it off.

[0179] After washing and drying, the resin exhibited an acid value of approximately 1.2 mg KOH / g, an OH value of the remaining hydroxyl groups measured by titration of approximately 0.7 mg KOH / g, a number-average molecular weight of approximately 2,392 g / mol, and a molecular weight distribution of approximately 1.43.

[0180] A resin varnish composition was prepared by mixing the materials according to the composition ratios shown in Table 2, and a copper-clad laminate was fabricated using the same method as in Example 6. The laminate was then evaluated.

[0181] To explain in more detail, in Example 8, when the total weight of the resin composition was 100 wt%, the resin composition consisted of approximately 40 parts by weight (also called 40 wt%) of the olefinized resin from Example 3, approximately 15 parts by weight (also called 15 wt%) of a crosslinking agent, approximately 10 parts by weight (also called 10 wt%) of a filler, approximately 1 part by weight (also called 1 wt%) of a crosslinking accelerator, and approximately 10 parts by weight (also called 10 wt%) of a flame retardant. Furthermore, approximately 53 parts by weight (also called 53 wt%) of the resin composition was mixed with approximately 47 parts by weight (also called 47 wt%) of a solvent (toluene / methyl ethyl ketone cosolvent) to obtain the resin varnish composition used in Example 8 for the production of copper-clad laminates.

[0182] <Example 9>

[0183] The resin in <Example 4> was olefinized with methacrylic anhydride.

[0184] Specifically, approximately 100 grams of toluene, approximately 100 grams of the resin from Example 4, approximately 27.6 grams of methacrylic anhydride, and approximately 15.5 grams of 4-(dimethylamino)pyridine (DMAP) were added to the reaction vessel. The reaction vessel was filled with dry nitrogen and heated to approximately 85°C, and the reaction was carried out for approximately 6 hours.

[0185] After the reaction, methanol was added to precipitate the resin and wash it off.

[0186] After washing and drying, the resin exhibited an acid value of approximately 1.2 mg KOH / g, an OH value of the remaining hydroxyl groups measured by titration of approximately 0.2 mg KOH / g, a number-average molecular weight of approximately 1,955 g / mol, and a molecular weight distribution of approximately 1.45.

[0187] A resin varnish composition was prepared by mixing the materials according to the composition ratios shown in Table 2, and a copper-clad laminate was fabricated using the same method as in Example 6. The laminate was then evaluated.

[0188] To explain in more detail, in Example 9, when the total weight of the resin composition was 100 wt%, the resin composition consisted of approximately 40 parts by weight (also called 40 wt%) of the olefinized resin from Example 4, approximately 15 parts by weight (also called 15 wt%) of a crosslinking agent, approximately 10 parts by weight (also called 10 wt%) of a filler, approximately 1 part by weight (also called 1 wt%) of a crosslinking accelerator, and approximately 10 parts by weight (also called 10 wt%) of a flame retardant. Furthermore, approximately 53 parts by weight (also called 53 wt%) of the resin composition was mixed with approximately 47 parts by weight (also called 47 wt%) of a solvent (toluene / methyl ethyl ketone cosolvent) to obtain the resin varnish composition used in Example 9 for the production of copper-clad laminates.

[0189] <Example 10>

[0190] The resin in <Example 5> was olefinized with methacrylic anhydride.

[0191] Specifically, approximately 100 grams of toluene, approximately 100 grams of the resin from Example 5, approximately 51.3 grams of methacrylic anhydride, and approximately 27.1 grams of 4-(dimethylamino)pyridine (DMAP) were added to the reaction vessel. The reaction vessel was filled with dry nitrogen and heated to approximately 85°C, and the reaction was allowed to proceed for approximately 4 hours.

[0192] After the reaction, methanol was added to precipitate the resin and wash it off.

[0193] After washing and drying, the resin exhibited an acid value of approximately 1.5 mg KOH / g, an OH value of the remaining hydroxyl groups measured by titration of approximately 0.1 mg KOH / g, a number-average molecular weight of approximately 1,417 g / mol, and a molecular weight distribution of approximately 1.45.

[0194] A resin varnish composition was prepared by mixing the materials according to the composition ratios shown in Table 2, and a copper-clad laminate was fabricated using the same method as in Example 6. The laminate was then evaluated.

[0195] To explain in more detail, in Example 10, when the total weight of the resin composition was 100 wt%, the resin composition consisted of approximately 40 parts by weight (also called 40 wt%) of the olefinized resin from Example 5, approximately 15 parts by weight (also called 15 wt%) of a crosslinking agent, approximately 10 parts by weight (also called 10 wt%) of a filler, approximately 1 part by weight (also called 1 wt%) of a crosslinking accelerator, and approximately 10 parts by weight (also called 10 wt%) of a flame retardant. Furthermore, approximately 53 parts by weight (also called 53 wt%) of the resin composition was mixed with approximately 47 parts by weight (also called 47 wt%) of a solvent (toluene / methyl ethyl ketone cosolvent) to obtain the resin varnish composition used in Example 10 for the production of copper-clad laminates.

[0196] <Comparative Example 3>

[0197] SA-9000 resin (manufactured by Sabic Co., Ltd.) was olefinized with methacrylic anhydride.

[0198] Specifically, approximately 100 grams of toluene, approximately 100 grams of the resin from <Comparative Example 1>, approximately 15.2 grams of methacrylic anhydride, and approximately 8.5 grams of 4-(dimethylamino)pyridine (DMAP) were added to the reaction vessel. The reaction vessel was filled with dry nitrogen and heated to approximately 85°C, and the reaction was carried out for approximately 4 hours.

[0199] After the reaction, methanol was added to precipitate the resin and wash it off. Then, centrifugation was performed using toluene as the solvent to remove the insoluble product (which may contain the corresponding resin).

[0200] The dried product (which may contain the corresponding resin) exhibited an acid value of approximately 2.2 mg KOH / g, an OH value of the remaining hydroxyl groups measured by titration of approximately 0.1 mg KOH / g, a number-average molecular weight of approximately 1,452 g / mol, and a molecular weight distribution of approximately 1.8.

[0201] A resin varnish composition was prepared by mixing the materials according to the composition ratios shown in Table 2, and a copper-clad laminate was fabricated using the same method as in Example 6. The laminate was then evaluated.

[0202] To explain in more detail, in Example 3, when the total weight of the resin composition was 100 wt%, the resin composition consisted of approximately 40 parts by weight (also known as 40 wt%) of olefinized SA-9000 resin, approximately 15 parts by weight (also known as 15 wt%) of crosslinking agent, approximately 10 parts by weight (also known as 10 wt%) of filler, approximately 1 part by weight (also known as 1 wt%) of crosslinking accelerator, and approximately 10 parts by weight (also known as 10 wt%) of flame retardant. Furthermore, approximately 53 parts by weight (also known as 53 wt%) of the resin composition was mixed with approximately 47 parts by weight (also known as 47 wt%) of solvent (toluene / methyl ethyl ketone cosolvent) to obtain the resin varnish composition used in Comparative Example 3 for the production of copper-clad laminates.

[0203] <Comparative Example 4>

[0204] The resin of <Comparative Example 1> was olefinized with methacrylic anhydride.

[0205] Specifically, approximately 100 grams of toluene, approximately 100 grams of the resin from <Comparative Example 4>, approximately 15.2 grams of methacrylic anhydride, and approximately 8.5 grams of 4-(dimethylamino)pyridine (DMAP) were added to the reaction vessel. The reaction vessel was filled with dry nitrogen and heated to approximately 85°C, and the reaction was carried out for approximately 4 hours.

[0206] After the reaction, methanol was added to precipitate the resin and wash it off. Then, centrifugation was performed using toluene as the solvent to remove the insoluble product (which may contain the corresponding resin).

[0207] The dried product (which may contain the corresponding resin) exhibited an acid value of approximately 2.2 mg KOH / g, an OH value of the remaining hydroxyl groups measured by titration of approximately 0.1 mg KOH / g, a number-average molecular weight of approximately 1,452 g / mol, and a molecular weight distribution of approximately 1.8.

[0208] A resin varnish composition was prepared by mixing the materials according to the composition ratios shown in Table 2, and a copper-clad laminate was fabricated using the same method as in Example 6. The laminate was then evaluated.

[0209] To explain in more detail, in Comparative Example 4, when the total weight of the resin composition was 100 wt%, the resin composition consisted of approximately 40 parts by weight (also known as 40 wt%) of the olefinized resin of Comparative Example 1, approximately 15 parts by weight (also known as 15 wt%) of a crosslinking agent, approximately 10 parts by weight (also known as 10 wt%) of a filler, approximately 1 part by weight (also known as 1 wt%) of a crosslinking accelerator, and approximately 10 parts by weight (also known as 10 wt%) of a flame retardant. Furthermore, approximately 53 parts by weight (also known as 53 wt%) of the resin composition was mixed with approximately 47 parts by weight (also known as 47 wt%) of a solvent (toluene / methyl ethyl ketone cosolvent) to obtain the resin varnish composition used in the production of copper-clad laminates in Comparative Example 3.

[0210] <Examples and comparative examples of applications to copper-clad laminates>

[0211] A resin varnish composition was prepared by mixing the materials according to the composition ratios shown in Table 2, and a copper-clad laminate was fabricated using the method described above.

[0212] [Table 2]

[0213] <Evaluation Method>

[0214] a. Dynamic viscosity test

[0215] Using a 2116 glass fiber cloth prepreg with a resin content (RC) of 53% (also known as 2116RC53%), the following evaluations were performed. Method: The prepreg was rubbed to produce powder, and approximately 0.45 grams of the powder was placed in a commercially available rheometer (e.g., TA Instruments or Hitachi) to measure its dynamic viscosity. Measurement conditions: The heating rate was approximately 2.5°C / min, and the measurement temperature range was 50°C to 180°C. The minimum viscosity value (in Pa·s), the lowest temperature at which the minimum viscosity value was obtained (also known as the "lowest point"; in °C), and the corresponding temperature range (also known as the "range"; in °C) were recorded. The temperature range (also known as the "range"; in °C) represents the temperature range at which the viscosity of the resin composition is 10,000 Pa·s or less. By comparing the temperature ranges, differences in the operability of the corresponding resins can be shown. For example, a wider temperature range suggests better operability.

[0216] b.Water absorption rate

[0217] A 5cm x 5cm square test specimen was placed in an oven at approximately 105°C for an appropriate period (e.g., approximately 2 hours), and then transferred to a pressure cooker. The conditions inside the pressure cooker were approximately 2 atm x 120°C. After approximately 120 minutes in the pressure cooker, the water absorption rate was calculated using the following formula: difference in weight of the test specimen before and after placing it in the pressure cooker ÷ initial weight of the test specimen × 100%.

[0218] c. Heat resistance

[0219] The test method involved immersing the pressure cooker test specimen described above in a soldering furnace at 288±5℃ and observing the results. The time required for the specimen to peel off was recorded. Generally, if no peeling was observed within 60 minutes, the specimen passed the heat resistance test.

[0220] d. Peel strength

[0221] Similar to the method described above, the peel strength of films made from the above-mentioned resin composition was measured using a universal tensile testing machine according to IPC-TM-650, Method 2.4.8.

[0222] e. Dielectric constant (Dk)

[0223] Dielectric constant test: The test method involved baking a copper-clad laminate test specimen, approximately 5 cm x 5 cm square with the copper foil removed, in an oven at approximately 105°C for approximately 2 hours. The thickness was measured with a thickness gauge, and then the test specimen was placed in an impedance analyzer (Agilent E4991A) to measure the dielectric constant Dk data at three points, and the average value was calculated.

[0224] f. Dielectric loss tangent (Df)

[0225] Dielectric Loss Tangent Test: The test method involved baking a copper-clad laminate test specimen, approximately 5cm x 5cm square with the copper foil removed, in an oven at approximately 105°C for approximately 2 hours. The thickness was measured with a thickness gauge, and then the test specimen was placed in an impedance analyzer (Agilent E4991A) to measure the dielectric loss tangent Df data at three points, and the average value was calculated.

[0226] g. Glass transition temperature (Tg)

[0227] Similar to the method described above, the glass transition temperature (Tg) of films made from the above-mentioned resin composition was measured using a dynamic mechanical analyzer (DMA).

[0228] <Evaluation Method>

[0229] According to the experimental results in Table 2, copper-clad laminates can be fabricated using the modified polyphenylene ether resin in one embodiment of the present invention. Furthermore, the electrical properties and / or glass transition temperature of the fabricated copper-clad laminates are equal to or better than those of conventional resins (e.g., polyphenylene ether resins commonly used in the manufacture of copper-clad laminates).

[0230] Furthermore, Dk and Df can still meet the dielectric levels of typical copper-clad laminates (e.g., very low loss levels with Df of 0.0030 to 0.0065).

[0231] Furthermore, other properties are equivalent to or within corresponding standards when compared to using traditional resins (for example, polyphenylene ether resin used in the manufacture of common copper-clad laminates).

[0232] As described above, compared to commercially available resins used in the manufacture of copper-clad laminates, the modified polyphenylene ether resin in one embodiment of the present invention provides a simpler manufacturing process. Furthermore, the modified polyphenylene ether resin in one embodiment of the present invention is suitable for the manufacture of copper-clad laminates, and / or copper-clad laminates manufactured using it meet general standards.

[0233] Furthermore, by adjusting the method for producing the modified polyphenylene ether resin in one embodiment of the present invention and / or the corresponding ratios, the resin composition applied to the corresponding copper-clad laminate can meet customized specifications. For example, the glass transition temperature can be changed by changing the corresponding number of hydroxyl groups (for example, there is a basically positive relationship between the number of hydroxyl groups per molecule and the glass transition temperature). For example, the smaller the molecular weight, the higher the fluidity may be. As another example, the larger the molecular weight, the higher the corresponding peel strength may be. [Industrial applicability]

[0234] Furthermore, the modified polyphenylene ether resin in the above-described embodiments of the present invention can be applied directly or indirectly to copper-clad laminates, and can also be processed into other electronic components or electronic products (e.g., circuit boards or copper-clad laminates) for use in daily life, industry, or suitable applications. [Explanation of Symbols]

[0235] S10, S20, S30, S40 Step

Claims

1. To provide unmodified polyphenylene ether, The unmodified polyphenylene ether is reacted with a phenol compound and a radical initiator to obtain the corresponding product. The aforementioned product is purified by alkaline washing and solvent recrystallization to obtain a modified polyphenylene ether resin. Includes, The alkaline equivalent of the alkaline solution used for alkaline cleaning is equal to that of a 10 wt% to 60 wt% sodium hydroxide aqueous solution. The aforementioned alkaline cleaning process is carried out for 0.5 to 4 hours in a temperature environment of 40°C or higher. The aforementioned solvent recrystallization is performed Adding a low-polarity solvent, The precipitate is removed after adding the low-polarity solvent, The process includes removing the precipitate and then adding a highly polar solvent to precipitate the modified polyphenylene ether resin, The modified polyphenylene ether resin has a structure represented by the following formula (1): 【Chemistry 1】 Formula (1) In formula (1), k is an integer greater than 0, i, i', j, and j' are either the same or different from each other, i and j are integers between 0 and 200, and i' and j' are integers between 1 and 200. The value of i + i' + j + j' + k is between 2 and 400. R １ ~R ８ However, they may be the same or different from each other, and each is selected from a hydrogen group or a C1-C6 alkyl group. P １ ~P ４ However, they are either the same or different from each other, and are selected from single bonds or ketone groups, Q １ ~Q ４ However, they are either the same or different from each other, and each is selected from a benzene ring group, a styryl group, a phenylethynyl group, an ethynyl group, a vinyl group, a methyl vinyl group, a naphthalene ring group, or hydrogen. X is a single bond or a linking group selected from the following chemical formulas: 【Chemistry 2】 A method for producing a modified polyphenylene ether resin, wherein the modified polyphenylene ether resin has an average number of hydroxyl groups per molecule of 2.2 or more, a number-average molecular weight of 1,000 g / mol to 3,000 g / mol, and a molecular weight distribution of less than 1.

8.

2. The method for producing a modified polyphenylene ether resin according to claim 1, wherein the unmodified polyphenylene ether contains poly(2,6-dimethyl-1,4-phenylene ether).

3. A method for producing a modified polyphenylene ether resin according to claim 1, wherein the equivalent amount of the radical initiator is about 0.05 to about 2 times the phenol equivalent amount of the phenol compound.

4. A method for producing a modified polyphenylene ether resin according to claim 1, further comprising adding a catalyst when reacting the unmodified polyphenylene ether with the phenol compound and the radical initiator.

5. It has a structure represented by the following formula (1), 【Transformation 3】 Formula (1) In formula (1), k is an integer greater than 0, i, i', j, and j' are either the same or different from each other, i and j are integers between 0 and 200, and i' and j' are integers between 1 and 200. The value of i + i' + j + j' + k is between 2 and 400. R １ ~R ８ However, they may be the same or different from each other, and each is selected from a hydrogen group or a C1-C6 alkyl group. P １ ~P ４ are the same as or different from each other and are each selected from a single bond or a ketone group, Q １ ~Q ４ However, they are either the same or different from each other, and each is selected from a benzene ring group, a styryl group, a phenylethynyl group, an ethynyl group, a vinyl group, a methyl vinyl group, a naphthalene ring group, or hydrogen. X is a single bond or a linking group selected from the following chemical formulas: 【Chemistry 4】 A modified polyphenylene ether resin, The modified polyphenylene ether resin has an average number of hydroxyl groups per molecule of 2.2 or more, a number-average molecular weight of 1,000 g / mol to 3,000 g / mol, and a molecular weight distribution of less than 1.

8. Modified polyphenylene ether resin.

6. To provide unmodified polyphenylene ether, The unmodified polyphenylene ether is reacted with a phenol compound and a radical initiator to obtain the corresponding product. The aforementioned product is purified by alkaline washing and solvent recrystallization to obtain the modified polyphenylene ether resin. A modified polyphenylene ether resin according to claim 5, produced by a method comprising the above.

7. The property is that the total weight of the composition with a molecular weight greater than 20,000 g / mol accounts for less than 1.5 wt% based on the total weight of the modified polyphenylene ether resin. A modified polyphenylene ether resin according to claim 5, having the following characteristics:

8. The modified polyphenylene ether resin having the structure represented by the following formula (1) comprises 【Transformation 5】 Formula (1) In formula (1), k is an integer greater than 0, i, i', j, and j' are either the same or different from each other, i and j are integers between 0 and 200, and i' and j' are integers between 1 and 200. The value of i + i' + j + j' + k is between 2 and 400. R １ ~R ８ However, they may be the same or different from each other, and each is selected from a hydrogen group or a C1-C6 alkyl group. P １ ~P ４ However, they are either the same or different from each other, and are selected from single bonds or ketone groups, Q １ ~Q ４ However, they are either the same or different from each other, and each is selected from a benzene ring group, a styryl group, a phenylethynyl group, an ethynyl group, a vinyl group, a methyl vinyl group, a naphthalene ring group, or hydrogen. X is a single bond or a linking group selected from the following chemical formulas: 【Transformation 6】 The modified polyphenylene ether resin has an average number of hydroxyl groups per molecule of 2.2 or more, a number-average molecular weight of 1,000 g / mol to 3,000 g / mol, and a molecular weight distribution of less than 1.

8. Resin composition.

9. The resin composition includes a film layer formed from a resin composition containing a modified polyphenylene ether resin having a structure represented by the following formula (1): 【Transformation 7】 Formula (1) In formula (1), k is an integer greater than 0, i, i', j, and j' are either the same or different from each other, i and j are integers between 0 and 200, and i' and j' are integers between 1 and 200. The value of i + i' + j + j' + k is between 2 and 400. R １ ~R ８ However, they may be the same or different from each other, and each is selected from a hydrogen group or a C1-C6 alkyl group. P １ ~P ４ However, they are either the same or different from each other, and are selected from single bonds or ketone groups, Q1-Q ４ However, they are either the same or different from each other, and each is selected from a benzene ring group, a styryl group, a phenylethynyl group, an ethynyl group, a vinyl group, a methyl vinyl group, a naphthalene ring group, or hydrogen. X is a single bond or a linking group selected from the following chemical formulas: 【Transformation 8】 The modified polyphenylene ether resin has an average number of hydroxyl groups per molecule of 2.2 or more, a number-average molecular weight of 1,000 g / mol to 3,000 g / mol, and a molecular weight distribution of less than 1.

8. Electronic components.

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