TW201035168A - Aromatic polyester amide copolymer, polymer film, prepreg, prepreg laminate, metal clad laminate and printed circuit board - Google Patents

Abstract

An aromatic polyester amide copolymer, a polymer film, a prepreg, a prepreg laminate, a metal clad laminate, and a printed circuit board. The aromatic polyester amide copolymer including 20 to 25 mol% of a repeat unit A derived from an aromatic diol based on the total repeat units therein, wherein the repeat unit A comprises a repeat unit RCN derived from resorcinol and a repeat unit HQ derived from at least one of biphenol and hydroquinone.

Description

201035168 J342ipif.doc VI. Description of the invention: [Related application] This application claims the rights of Korean Patent Application No. 1〇_2〇〇8-〇138702, filed on December 31, 2008 by the Korea Intellectual Property Office. The full text of this case is incorporated into this case for reference. TECHNICAL FIELD OF THE INVENTION The present invention relates to an aromatic polyester guanamine copolymer, a polymer film, a prepreg, a prepreg, a metal clad laminate, and a printed circuit board, and in particular An aromatic polyester guanamine copolymer, a polymer film comprising the aromatic polyester guanamine copolymer, a prepreg and a prepreg, and the prepreg or the prepreg layer a metal clad laminate of a board and a printed circuit board, wherein the aromatic polyester guanamine copolymer comprises repeating units A based on all of the repeating units comprising from about 20 mole percent to about 25 mole percent, the repeating unit A is derived from an aromatic diol, and the repeating unit A includes a repeating unit RCN derived from resorcinol and a repeating unit HQ derived from at least one of diphenol and hydroquinone. [Prior Art] According to recent miniaturization and multifunctionalization of electronic devices, high densification and miniaturization of printed circuit boards have been actively studied. Copper clad laminates are commonly used as printed circuit boards for electronic devices because of the excellent stamping processability, drill processability, and low cost of copper clad laminates. Base 201035168 xpif.doc material. In ladle laminates for printed circuit boards, the prepregs used should have the following important characteristics to achieve good semiconductor performance and compliance with package manufacturing conditions (1) Relative to the coefficient of thermal expansion of the metal (integrated circuit (1C) wafer), which has a low coefficient of thermal expansion; (2) it has low dielectric properties® and dielectric stability in the high frequency range of 1 GHz or more; (3) Heat resistance for a reflow process at about 270 °C. The precursor is impregnated with a glass fabric by using a resin derived from an epoxy resin (ep〇Xy) or a bismaieimidetriazine (bismaieimidetriazine). And then prepared by semi-hardening the resin. Then, a copper clad layer was stacked on the prepreg and the resin was completely hardened to form a copper clad laminate. The copper clad laminate will be formed into a thin layer and then subjected to a high temperature process, such as a reflow soldering process at 27 (TC). When the copper clad laminate in the form of a thin layer is subjected to a high temperature process, the prepreg is used. The coefficient of thermal expansion is different from the coefficient of thermal expansion of the copper clad laminate, so the copper clad laminate may be thermally deformed to cause a decrease in yield. Further, it is derived from an epoxy resin or bismuthimide and trisodium sulfoxide. The hygroscopicity of the resin of the heterobenzene is lowered. In particular, the resin has poor dielectric properties at a high frequency range of 1 GHz or more (i.e., has a 咼 dielectric constant in a frequency range). Since the printed circuit board needs 201035168 ^*^42 ipif.doc for the frequency and idle process, it is difficult. (4) This purpose should be applied to the printed circuit board of the semiconductor package. Therefore, it is necessary to develop a pre-dielectric constant. Dip. Recently, a prepreg has been prepared using an aromatic polyacetate (as a derivative derived from an epoxy resin or a double:, butene diimine-triazole). The body can be touched by the 四(四)族(四) It is prepared by impregnating organic or inorganic fabrics. In particular, the aromatic polyacetal prepreg can be prepared by using a scented silk and a (four) family of fabrics to prepare the aromatic poly The ester resin is dissolved in a granule containing a halogen element (such as C1) to prepare a liquid composition c〇mp 〇 〇 )), and then the lyophilized product is used to impregnate the (four) group poly g | fabric, The resulting product is dried to prepare an aromatic polyester prepreg. However, in the "in this side", it is difficult to completely remove the solvent containing the tooth element, and thus the halogenated itin will rot the copper cladding. Therefore, there is a need to develop a process for preparing an aromatic polyester prepreg using a non-halogen solvent. SUMMARY OF THE INVENTION The present invention provides an aromatic polyester guanamine copolymer having a low coefficient of thermal expansion, a low dielectric constant, and a low dielectric loss. The present invention also provides a prepreg and a prepreg laminate comprising the aromatic polyester guanamine copolymer. The invention also provides a metal clad laminate and a printed circuit board. The prepreg or the prepreg layer. According to an aspect of the invention, there is provided an aromatic polyglycol amine copolymer. The aromatic polyester guanamine copolymer is based on all repeats & = j^Hzipif*d〇c 201035168 comprising from about 20 mole percent to about 25 mole percent of repeating unit a, said repeating unit A being derived from an aromatic diol (ar〇matic diol), and said repeating unit A A repeating unit HQ derived from resorcin〇i and a repeating unit HQ derived from at least one of biphenol and hydroquinone. The repeating unit RCN and the repeat The amount of the unit HQ may satisfy the following conditions: 〇 < n(RCN) / [n(RCN) + n(HQ)] < 1 , 〇 where n(RCN) and n(HQ) respectively represent the aromatic poly g The number of moles of the repeating unit RCN of the amine copolymer and the repeating unit HQ. The amine copolymer may further comprise from about 2 mole percent to about 25 mole percent of repeating unit b based on all repeating units derived from aromatic ar 〇 hydroxy carboxylic acid ° aromatic The polyester guanamine copolymer may further comprise at least one repeating unit based on all repeating units from about 20 mole percent to about 25 mole percent. The at least one repeating unit is selected from the group consisting of repeating unit C and repeating unit c. a group of constituents wherein the repeating unit C is derived from an aromatic amine having a phenolic hydroxyl group, and the repeating unit C' is derived from an aromatic diamine. The family polyester guanamine copolymer may further comprise from about 35 mole percent to about 48 mole percent of repeating unit D derived from aromatic dicarboxylic acid. 201035168 334Zlpif.doc In another aspect of the invention, there is provided a polymer film comprising the aromatic polyester guanamine copolymer. According to another aspect of the invention, a prepreg is provided It comprises a substrate impregnated with the aromatic polyester guanamine copolymer. According to another aspect of the invention, there is provided a prepreg layer comprising at least two of said prepregs. In one aspect, a metal clad laminate is provided that includes a prepreg and at least one metal film disposed on at least one surface of the prepreg. According to another aspect of the present invention, there is provided a printed circuit board prepared by casting the metal thin film of the metal clad laminate. According to another aspect of the present invention, a printed circuit board is provided which is prepared by printing a metal circuit pattern on at least one surface of the polymer film. The above described features and advantages of the present invention will become more apparent from the description of the appended claims. [Embodiment] Hereinafter, an aromatic polyester phthalamide copolymer according to an embodiment of the present invention and a prepreg comprising a substrate impregnated with an aromatic polyester decylamine copolymer will be described in detail. According to an embodiment of the present invention, the aromatic polyester guanamine copolymer is based on repeating unit A in which the S repeating unit comprises, about 20 mole percent to about μ molar percentage, and repeating unit A is derived from aromatic diol And Caofu unit A includes a repeating unit rcn derived from resorcinol and a money unit derived from ipif.doc ❹ ❹ 201035168 I phenol and benzene-at least

The solubility of the substance in the (four) ear formula, the aromatic IS tincture will be reduced. In another aspect, the saponin is based on the content of all repeating units greater than 25% by mole. The melting point of the steroidal poly-amine copolymer may become too high. In addition, 'in the fragrant aromatic vinegar copolymerization: ear one and repeating unit Η rotating ear number two: = 〇 < n (RCN) / [n (RCN) + n (HQ)] < \. — The polymer is based on its f repeating single B weight correction 25 percent material (four) repeating single = repeating early TO B derived from aromatic hydroxycarboxylic acid. The fractional ratio of 5 is based on the fact that the content of all repeating units is less than 2 moles. The mechanical strength of the square aromatic polyacetamide copolymer is lowered. In the aspect, when the repeating unit B is based on the content of all the repeating units being greater than the U, = ratio, the thermal properties of the aromatic polyester decylamine copolymer may be lowered. Park Yuan B may include a derivative derived from a tortophenone benzoic acid coffee::2=ΐ formic acid (2_hyd~^^) The heteropolypolymer may be further packaged based on all repeating units, ', ', ear percentage to about 25 mole percentage At least one repeating unit composition - repeating unit is selected from the group consisting of 4 complex units C and repeating unit C' group, wherein the repeating single μ is derived from a square aromatic amine having a decrease in hope, and the repeating single it C is derived. From aromatic diamines 201035168 334/ipif.doc Human 曰, repeat unit C and repeat unit C, based on the total content of all repeat units less than 20 mole percent, aromatic polyester guanamine copolymer in solvent The solubility in the medium will decrease. On the other hand, when the repeating unit c and the repeating unit C' are based on the total content of all the repeating units being more than 25 mol%, the melting point of the aromatic polyester guanamine copolymer becomes The repeating unit C may include a group derived from a group selected from the group consisting of 3-aminophenol, 4-aminophenol, and 2-amino-6-naphthol. a repeating unit of at least one compound. The repeating unit C may be derived from Choose from the group consisting of 1,4 phenylene diamine, 1,3-phenylene diamine and 2,6-naphthalene diamine a repeating unit of at least one compound. The aromatic polyester guanamine copolymer may further comprise from about 35 mole percent to about 48 mole percent of repeat unit D based on all repeat units, and repeat unit D is derived from aromatic dicarboxyl Acid. When the repeating unit D is based on the content of all repeating units less than % Mohr%, the solubility of the Fangxiang polyacetic acid amine copolymer in the solvent is reduced. On the other hand, when the unit is repeated D. The heat resistance, low thermal expansion characteristics, and low dielectric properties of the 'aromatic polyester decylamine copolymer' may be destroyed based on the content of all repeating units being greater than 48 mole percent. The repeating unit D may include derivatization Repeat units of one compound less than 10 201035168 ipif.doc in the group consisting of isophthalic acid, naphthalene acid and terephthalic acid. Yes, aromatic Each repeating unit of the polyester amide amine copolymer can be represented by one of the following formulas: (1) Repeating unit A derived from an aromatic diol: <Formula 1>

Ο <式2>

〇—

Ri <式3>

<Formula 4>

11 201035168 ipif.doc (2) Repeating unit B derived from aromatic hydroxycarboxylic acid &lt;Formula 5&gt; -C- Ο &lt;Formula 6&gt; -0 - &lt;Formula 7&gt;

12 201035168 ο Ο &lt;式9&gt;•ο—

Rt R2 -C-IIο (3) a repeating unit derived from an aromatic amine having a phenolic hydroxyl group C &lt; Formula 10&gt; -HN- &lt; Formula 11&gt; -HN- &lt;Formula 12&gt;

Ri ——0- R1 R2 13 201035168 (4) Repeating unit C' derived from aromatic diamine: <Formula 13>

HN

NH Ri <Formula 14> -HN- -NH- <Formula 15>

R2 (5) Repeating unit D derived from aromatic dicarboxylic acid: <Formula 16> -C-II 0 €--

Ri

II 0 14 201035168 ipif.doc

15 201035168 ipn.doc &lt; Equation 21&gt;

<Formula 22>

The center and R2 are each a halogen atom, a fluorenyl group, an amino group, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted crC2 nonyloxy group, a substituted or unsubstituted C2_C2 Decyl, substituted or unsubstituted CVC alkynyl, substituted or unsubstituted CVQo isoalkyl, substituted or unsubstituted q_C3g aryl, substituted or unsubstituted CVQo aryl An aryiaikyi group, a substituted or unsubstituted Cs-C3. A heteroaryl group, or a substituted or unsubstituted CVCso heteroaryl group. The term "substituted" as used herein means that a hydrogen atom is substituted with at least two of a halogen group, a hydroxyl group, an alkyl group, an alkoxy group, a hydroxy group, an alkoxy group, a radical, or a group of the above-mentioned radicals. The amine copolymer can be polymerized by the following =) including 卩 silk reading, benzoquinone diol or diol diol or its ( 何 organism (four) 赖 四 (four) fine gift (four): (7) aromatic by acid t Brewing::: ΐ:: (3) at least one selected from the group consisting of an aromatic amine or a cut organism having a desired hydroxyl group, and an aromatic diamine or a guanamine derivative thereof; and (4) an aromatic diwei or Vinegar

Open &gt; into a creature. In the _ forming derivative of the scented diol, the carbyl group can react with the carboxylic acid to form an ester bond. Further, the ester-forming derivative of the aromatic hydroxycarboxylic acid or the aromatic dicarboxylic acid may be a highly reactive derivative such as an acid chloride and an acid anhydride, or an aromatic hydroxycarboxylic acid or an aromatic dicarboxylic acid. The ester-forming derivative can form an ester bond with an alcohol or ethylene glycol (ethyleneglyc〇1). In the amide-forming derivative of an aromatic amine or an aromatic diamine, the amine group may form a guanamine bond with the carboxylic acid. The aromatic polyester guanamine copolymer prepared as described above may be dissolved in a solvent' and may be a heat-oriented liquid crystal polyester guanamine copolymer, in particular, it may be at 400. An optically anisotropic melt is formed at a temperature range of (or lower). In particular, the melting point of the 'aromatic polyester guanamine copolymer may range from about 25 〇 to about 400 ° C. And, the number average molecular weight thereof may range from about 1, 〇〇〇 to about 2 〇, 〇〇〇. The aromatic polyester guanamine copolymer can be prepared by using a method for preparing a general aromatic polyester. For example, an excess of fat 17 201035168 ipif.doc anhydride can be used to phenolic hydroxyl groups of aromatic diols (corresponding to repeating unit RCN and/or repeating unit HQ), phenolic hydroxyl groups of aromatic hydroxycarboxylic acids (corresponding Deuteration is carried out in repeating unit B) together with the phenolic hydroxyl or amine group of the aromatic amine (corresponding to repeating unit c) and/or the amine group of the aromatic diamine (corresponding to repeating unit C') to obtain a mercapto group. The compound, and then the transesterification of the obtained mercapto compound with an aromatic dicarboxylic acid, is melted and polymerized (melt_P〇lymerized). In the brewing reaction, 'chemical equivalent' (lu) Content can be greater than The content of the divalent base and the amine group is from about 1.0 to about 1.2 times, such as in the range of from about 1⁄4 to about 107 times. When the amount of the fatty acid anhydride is higher than the above range, the aromatic polyester decylamine is altogether. The coloring of the polymer may be significant. On the other hand, when the amount of the fatty acid anhydride is lower than the above range, some of the monomers used may sublime or may generate a large amount of phenolic gas. The oximation reaction may be about 130. From °C to about 170. (: a temperature range of from 30 minutes to about 8 hours, such as from about 14 Torr to about 16 〇〇c for about 2 hours to about 4 hours. In the oximation reaction Examples of the fatty acid anhydride to be used include, but are not limited to, acetic anhydride, propionic anhydride, isobutyric anhydride, valeric anhydride, Pivalic anhydride, butyric anhydride, or a combination thereof. Acetic anhydride can be used in terms of cost and convenience of handling. The transesterification and transamination can be carried out at a temperature of about 13 Torr, and when the reaction temperature is increased by about (U_2t:/min, for example, at about 14 〇 _35 〇 〇. (: temperature, when When the temperature is increased by about _3_rc/min, in order to promote the chemical equilibrium state, when the fatty acid vinegar and the carboxylic acid are trans-acetated or transaminated, the fatty acid by-products are produced. And the unreacted fatty acid anhydride can be excluded from the reaction system by evaporation or distillation. The brewing reaction, the transesterification reaction and the transamidation reaction can be carried out in the presence of a catalyst. The catalyst can be any used for the preparation of polyester. Catalyst. For example, the catalyst may be magnesium acetate, tin acetate, tetrabutyl titanate, lead acetate, sodium acetate, Potassium acetate, antimony trioxide, N,N-dimethylaminapyridine, and N-methylimidazole. The catalyst and the monomer are usually added at the same time, and the deuteration reaction and the transesterification reaction are carried out in the presence of a catalyst. The polymerization condensation reaction by transesterification and transamination can be carried out by a melt polymerization reaction, or a melt polymerization reaction and a subsequent s〇lid state polymerization reaction. . The reactor used in the melt polymerization reaction is not particularly limited, and the reactor may be a reactor equipped with a stirring device generally used for a high viscosity reaction. In this regard, the same reactor or a different reactor may be used in the acidification reaction and the melt polymerization reaction. The solid phase polymerization can be carried out by subjecting a prepolymer obtained by a melt polymerization reaction to an image forming sheet or a polymer like a powder, followed by polymerization by solid phase polymerization. The solid phase polymerization can be carried out in the following manner, at about 20 (TC to about 35 (the temperature range of TC lasts for about i 19 201035168 33421 pif. doc hours to 'about 30 hours), under the solid phase and in the atmosphere The polymerization of the milled prepolymer and the menstrual phase under the inert atmosphere can be carried out under the conditions of mixing or unstraining; solidification and solid phase polymerization of the σ When the scrambling equipment is carried out in the reactor, the reaction can be equipped with a suitable expansion coefficient of 3 ppm/K or less for the aromatics. The milk has the thermal expansion (four) riding. The _transformer can be shaped and then molded by known methods, or the ball can be double-dimensionalized _latiGn). Alternatively, the aromatic polysamine can be dissolved in the solvent, and the solution can be dissolved to the metal axis. Adding money to the material (4) fresh film. Further, \t or non-fabric towel makes the eutectic copolymer. The woven fabric is prepreg polyester according to the embodiment of the present invention. A substrate of a guanamine copolymer. The scented aromatic scented aromatic amine compound is in solution, Dipping or recording onto woven fabrics and/or non-woven fabrics and removing solvents to prepare prepregs.; impregnation method (solution impregnati〇n) or paint immersion, main g 'combination, = impregnation) for dip Crush. X. (varnish ^ in parts by weight (4) amine copolymer, the range of 100-100, _ $ parts of the solvent used to dissolve the scented polyester phthalamide copolymer. Based on (10) weight = Amidoxime copolymer, when the content of the solvent is less than 1. Weight 20 201035168 ipif.doc Viscosity will increase and there may be problems in handling. On the other hand, based on 100 parts by weight of aromatic polyester amide When the content of the solvent is more than 100,000 parts by weight, the content of the aromatic polyester guanamine copolymer is too small to lower the productivity of the prepreg. The solvent for dissolving the aromatic polyester guanamine copolymer can be It is a non-halogen solvent, but is not limited thereto. For example, 'the solvent may be a polar non-piOton based compound, a hal〇genated phenol, an o-dichlorobenzene, or a triclosan. (chloroform), methylene chloride, tetrachloroethane, or a combination thereof. In particular, since the scented polyacetal amine copolymer can be dissolved even in a non-halogen solvent. Solvent, therefore, the use of solvents containing halogens can be avoided. Since the use of halogen-containing solvents may corrode the metal cladding, avoiding the use of halogen-containing solvents can avoid metal clad laminates or printed circuit boards including prepregs. The layer is etched. The substrate may be woven and/or non-woven, such as aramid fiber, glass woven, carbon woven, cellophane, or combinations thereof. When used in the preparation of prepregs In the impregnation method, the substrate is impregnated with a composition solution of the aromatic polyester guanamine copolymer in a solvent, wherein the impregnation time is usually from about 0.001 minutes to about i hours. At ι min, the aromatic ride g|_copolymer may not be uniformly impregnated. On the other hand, when the impregnation time is more than 1 hour, the productivity of the prepreg may be lowered. In the case of a material, the impregnation temperature may be in the range of about 201035168 33421 pii.doc 20 ° C to about 190 ° C, such as room temperature. In addition, when the substrate has a thickness of about 5 m to about 2 Å, each Base per unit area The amount of the copolymer can be from about 0.1 g/m2 to about 1, _g/m2. When aromatic vinegar is brewed, the amount of impregnation of the copolymer is less than (U coffee) At 2 o'clock, the prepreg_productivity may be lowered. On the other hand, when the impregnation S of the aromatic polyglycol amine copolymer is greater than 1, GGGg/m2, it is not suitable for miniaturization of printed circuit boards. In the case of deviating from the scope of the present invention, in order to control the dielectric constant and the coefficient of thermal expansion, the combined solution prepared by dissolving the dissolved family of polylysine copolymers may further comprise: an inorganic filler such as a dioxide dioxide ( Silica), aluminum hydroxide (aiuminum) or calcmm carbonate; or an organic filler such as a cured epoxy or a parent-linked acrylic resin (acryiic). In particular, an inorganic filler having a high dielectric constant can be added to the combined solution. The inorganic filler may be a titanate such as bariumtitanate or strontium titanate, or a filler obtained by substituting a part of titanium or lanthanum of barium titanate with other metals. The content of the aromatic polyamine amine copolymer 'inorganic filler or organic filler based on 1 part by weight may be in the range of from about 1 part by weight to about 100 parts by weight. Based on 100 parts by weight Aromatic polyester guanamine copolymer, when the content of inorganic filler or organic filler is less than α_ι weight, it is difficult to increase the dielectric constant or reduce the thermal expansion coefficient of the prepreg. In other respects, based on 1〇 〇 By weight of the aromatic "melamine copolymer, when the content of the money filler or organic filler is greater than the weight, the aromatic poly-alcoholic copolymer may be 22 201035168 ipif.doc can not be used as a binder (binder). Embodiments of the invention, since the prepreg comprises an aromatic polyester guanamine copolymer having low hygroscopicity and low dielectric constant, and an organic or inorganic woven fabric and/or non-woven fabric having excellent mechanical strength. Therefore, the pre-form has excellent dimensional stability (dimensi〇nai stability), is not easily deformed when heated, and is hard. These characteristics make the prepreg suitable for through-hole ❹

G-drilling treatment (Via-h〇le drill processing) and stacking treatment (4) processing) ° &amp; a preparation of prepreg impregnation process towel, in the substrate is dissolved in the solvent by aromatic polyamine The hydrazine prepared from the polymer is then subjected to solution impregnation or smearing followed by 'solvent removal. The method of removing the solvent is not particularly limited, and the removal may be carried out by immersion, such as heat, vacuum evaporation = evaporation. _Yes, the use of thermal evaporation, especially the ventilating thermal evaporation, in the process of solvent removal, the aromatic polyester deciduous to about 19. . . Temperature range: Hold "1:: can be used first, the money makes the composition of the active ingredient 1 hour to carry out the temperature range of the hot rrc and lasts about 1 minute to about the thickness of the prepreg according to the invention" such as In (iv) the dip body in one direction, the coefficient of expansion of the 'prepreg body age 疋 1 (&gt; 1) 1) is extinguished or smaller, the number of tens may be 3.5 or less, and the dielectric of the prepreg 23 201035168 33421pii.doc Loss can be _ money is small. Here, the f loss table 4 is applied to the dielectric material _, the dielectric energy lost in the form of dielectric material J is ^, the expansion coefficient is greater than 丨. 狮 / κ The prepreg can be peeled off at the new moon. When the dielectric constant of the prepreg is greater than 3 5, the prepreg may not be suitable for high frequency simplicity. "Base γ in addition to the 'pre-impregnated laminate can It is prepared by stacking a predetermined number of prepregs and then heating and compressing the stacked prepregs. Further, the metal clad laminate can be prepared by positioning a metal film such as a copper film, a silver film or a lamella on at least one surface of the pre-Zhao or the board. Borrow / Gold &quot; 1 (10) board +, no special system for each body or prepreg and metal thin _ thickness, but in the range of 纟 (4) (10) to about 300 =. When the thickness of the prepreg or prepreg (4) is less than that, the prepreg or prepreg may be easily broken when performing the rolling process. When the thickness of the prepreg or prepreg is greater than 2 'The number of prepregs that can be stacked is limited. When the metal film is (U _, the metal film is stacked on the prepreg or the prepreg layer, the metal film may be more susceptible to cracking. On the other hand, when the thickness of = is greater than 3 GG, the stack can be pre-stacked The amount of the dip is carried out in a temperature range of from 50 C to about 180 C and from about 9 MPa to about 20 MPa in the preparation of the metal clad laminate 'heating and compression process. (4) The heating temperature and pressure are not limited thereto. In other words, the reactivity of the combined solution of the copolymer, the compression equipment, and the metal clad layer of the tetracycline (A), aromatic polystyrene 24 201035168 copolymer. The desired thickness or the like of the laminate is then appropriately determined by the heating temperature and pressure. According to the embodiment, the metal clad laminate further includes an adhesive layer between the prepreg and the metal film to increase the prepreg. The adhesion strength between the laminate and the metal film. The subsequent layer may be formed of a thermoplastic tree ore composite or a thermosetting resin composition. The thickness of the layer may be from about 0.1 / ΖΠ 1 to about 100. Within the range of Na. When the thickness of the adhesive layer is less than 〇.1, the adhesion strength between the prepreg and the metal film is reduced. On the other hand, when the thickness of the adhesive layer is greater than 1 〇〇, the metal package The laminated board will be too thick. 'In addition, the printed circuit board can be prepared by forming a metal film of a side metal clad laminate and forming a circuit for metal thinning. Alternatively, the printed circuit board can also be printed by printing a metal circuit pattern to Polymer film (four) one less

The compression conditions can be the same as those in the preparation of the metal clad laminate. Both the inner base and the metal clad laminate may be used as the inner base material, or may be a prepreg ply or printed circuit board ' used as an electrically insulating material, and at least one of these materials. One or more implementations of the month are not intended to be limiting. The examples will be described in detail with reference to the following examples. However, these examples are for illustrative purposes only, 25 201035168 3342ipif.doc. Example 1 138·1 g (1.00 mol) of parahydroxy benzoic acid, 245.54 g (2.3 mol) of 4-aminophenol, 185.8 g (1.7 mol) of p-phenylene 61.9 g (0.6 m) of meta-benzoic acid, 747.6 g (4.5 m) of isophthalic acid and 1,123 g (ii mol) of acetic anhydride were added to the device equipped with a scrambler and torque. A reactor (t〇rqUe meter), a nitrogen inlet, a thermometer, and a reflux condenser.

The reactor was thoroughly purged with nitrogen' and the temperature of the reactor was increased to 150 T under a nitrogen atmosphere for 30 minutes. The reactor was refluxed for 3 hours while the temperature was maintained at 150 °C.

Then, the temperature of the reactor was increased to 32 ° C for 18 minutes by removing the effluent acetic acid and unreacted acetic acid by distillation. When the torque is increased from 0.5 to 1.5 N*m, that is, when the reaction is stopped, the reaction product is obtained. The obtained solid powder was cooled to room temperature and then pulverized with a mill filler. Then, solid phase polymerization was carried out under a nitrogen atmosphere at 26 Torr. The reaction was carried out for 5 hours to obtain an aromatic polyester decylamine copolymer powder. The obtained aromatic polyacetamide copolymer powder was added to _g of N•methyl quinone (NMp), and then the mixture was stirred at room temperature for 4 hours to obtain an aromatic (tetra) 醯The composition of the amine silk compound is dissolved at room temperature (about 25 ° C) to form a solution impregnated glass woven fabric (IPC) 'recording 1 § Wei remove excess shaft material. The resulting woven fabric was then placed in a high temperature wire reduction machine (Masis 26, 2010 pp ipif. doc. Horizontal Type Dryer) to remove/treat at 150 C. The resulting structure was then heat treated for 60 minutes to obtain a prepreg prepared by glass woven cloth impregnated with an aromatic polyester phthalamide copolymer. Comparative Example 1 An aromatic polyester decylamine was prepared by the same method as in Example i except that hydroquinone as an aromatic diol was not used at all and only 253.23 g (2.3 mol) of stigma was used. Copolymer. Further, a composition solution and a prepreg of the aromatic polyester decylamine copolymer were prepared in the same manner as in Example 1. Comparative Example 2 Aromatic polyester decylamine copolymerization was carried out in the same manner as in Example except that resorcinol as an aromatic diol was not used at all and only 253.23 g (2.3 mol) of benzoquinone was used. Things. Further, a composition solution and a prepreg of the aromatic polyester decylamine copolymer were prepared in the same manner as in Example 丨. 7 Ο Comparative Example 3 In addition to the use of 138.1 g (l. mol) of p-hydroxybenzoic acid, 1 〇 9 lg (^ 〇 mol) of 4-amine phenol, 289.6 g (2.63 mol) of p-phenylene The same as in Example 1 except that phenol, 95.8 g (0.87 mol) of m-diphenol, 747·6 g (45 mol) of isophthalic acid, and 1,123 g (ll mol) of acetic anhydride were used. Method An aromatic polyester guanamine copolymer was prepared. Further, a composition solution and a prepreg of the aromatic polyester guanamine copolymer were prepared in the same manner as in Example 1. 27 201035168 33421pif.doc The surface state and electrical characteristics of the prepreg of Example 1 were evaluated in the following manner and compared with the ratio of the comparative example to the comparative example 3. + First, 'will. λ Example 1 and Comparative Example i to Comparative Example 3, Prepreg a, C, & temperature s〇idering bath three times, each 1 Gsec, and then observed for each prepreg surface condition. The pre-subfamily deformation or mechanical&apos; of Example 1 and Comparative Examples 1 to tb were deformed compared to the partial surface of each of the prepregs of Example 3. An example 1 was measured using an impedance analyzer. The dielectric constant and dielectric secret of the prepreg of Comparative Example 1 to Comparative Example 3. The measurement result is that the dielectric constant of Example 1 is 3.0 (1 GHz) and the dielectric loss is 〇〇〇5, which means that it has a low electric coefficient and low dielectric loss in the high frequency range. In comparison, the dielectric constant of the prepreg of Comparative Example i was 3.4 (1 GHz) and the dielectric loss was 〇·〇〇7, and the dielectric constant of the prepreg of Comparative Example 2 was 3 6 (1 GHz). The electrical loss is 〇._, = and the dielectric constant of the prepreg of Comparative Example 3 is 3.4 (1 GHz) and the dielectric knowance is 0.0〇7, which means that compared to the example 1 #prepreg, these pre-pregs The dip has a higher dielectric f-number and a higher dielectric loss. β further uses a thermomechanical analyzer (manufactured by ΤΜΑ, Q400) to measure only each of Example 1 and Comparative Example 1 to Comparative Example 3. The thermal expansion coefficient of the prepreg. The result of the slit is the temperature expansion range of 5Gd12Gt, and the thermal expansion coefficient of the prepreg of the example is 9.2 ppm/Κ. On the other hand, the thermal expansion coefficient of the prepreg of only the first example is compared. For the 14 5 ppm/K, the thermal expansion coefficient of the pre/texture of Comparative Example 2 was 115 ppm/K, and the coefficient of thermal expansion of the pre/seam of Comparative Example 3 was 2.4 ppm/K. Compared with the examples] 28 201035168 jJ4Zipif.doc prepreg, these prepregs and 10ppm/K) 〇X basket&quot; has a light thermal expansion coefficient (&gt; at the same time, as described above, +, Ο In the spirit and scope, when you can hang the knowledge, you can attach and modify the decoration without departing from the scope of protection of the invention. Therefore, the definition of "Picture" is subject to the definition of "Patent Circumference." [Main component symbol description] nt,

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Claims (1)

201035168 3342ipit-d〇c VII. Patent Application Range: 1. An aromatic polyester guanamine copolymer based on repeating unit a in which all repeating units 'comprise 20 mole percent to 25 mole percent, said repeating unit A is derived from an aromatic diol' and the repeating unit a comprises a repeating unit RCN derived from resorcinol and a repeating unit HQ derived from at least one of dioxon and p-diphenol. 2. The aromatic polyester guanamine copolymer according to claim 1, wherein the repeating unit RCN and the repeating unit HQ satisfy the following conditions: 〇 &lt; n(RCN)/[n (RCN)+n(HQ)] wherein n(RCN) and n(HQ) respectively represent the repeating unit RCN of the aromatic polyester guanamine copolymer and the number of moles of the repeating single sHQ . 3. The aromatic polymyramine copolymer according to claim 1, wherein the repeating unit B is derived from aroma based on all repeating units, and further comprises from 2 mole percent to 25 mole percent of repeating unit B. Family ferric acid. 4. The aromatic polyester guanamine copolymer according to claim 3, wherein the repeating unit (IV) is derived from a group selected from the group consisting of p-benzoic acid and 2-hydroxy-6-naphthoic acid. At least one compound. 5. The aromatic polyester guanamine copolymer as described in the scope of claim 2, based on all repeating units, further comprising at least a repeating unit of 2% molar percentage to Μ molar ratio, said at least A repeat unit is selected from the group consisting of repeat unit C and repeat unit c, wherein the repeat unit 30 201035168 ipif.doc element c is derived from a phenolic hydroxyl group C derived from a feed group diamine. a squaraamine' and the repeating unit compound, wherein the heavy aromatic polyester amide copolymer is exemplified by 2-amino-6-na·kg composition: Ο G combination::=====; a repeating unit of 2, which is derived from the aromatic polyacetamide copolymer described in the seventh paragraph of the patent of the second patent, wherein the repeating unit D is derived from an isophthalic acid selected from the group consisting of At least a compound of a group consisting of dicarboxylic acid, scorpion-skin acid, and terephthalic acid. The aromatic poly(tetra)amine copolymer described in claim 1 has a number average molecular weight ranging from 1,000 to 20,000, and a melting point of from 25 〇t to 400. In the range of (1), a polymer film comprising the aromatic polyester guanamine copolymer as described in any one of claims 1 to 9. U. A prepreg And a substrate for impregnating the aromatic polyester amide copolymer according to any one of claims 1 to 9. 12. The prepreg according to claim 5 Wherein the substrate has a degree of between 5 and 2 cm, and the amount of impregnation of the aromatic polyester indole copolymer per unit area of the substrate is between 0.1 g/m2 To 31 201035168 pit; doc 1,000 g/m2. The prepreg according to item 11, wherein the two ', selected from the group consisting of aromatic polyester fiber, glass woven fabric, carbon woven and cellophane At least one of the prepregs according to claim 11 of the invention, based on 100 of the aromatic polyester guanamine copolymer, further comprising adding to the weight of the G.GGG1 To the parts by weight of the organic filler or inorganic filler. 15. The prepreg according to the scope of claim 5, having an upward thermal expansion coefficient of 10 ppm/K or less. ', 16 · The prepreg according to the scope of patent application , u, the number of which is 3.5 or less' and its dielectric loss is 〇.〇1 or less π. Prepreg laminate, including At least two of the prepreg towels of the patent application scope. 18 所 18 18 — — — — — — — — — — — — — — — — 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 At least one metal sheet on at least one surface of the prepreg is as described in the above-mentioned 18-fold (four) (four) cladding layer, and the pre-substrate comprises at least two prepreg laminate sheets. The metal thin film of the metal clad laminate according to the patent application is prepared by printing a metal circuit pattern on at least the surface of the polymer film as described in the application of the first item: 32 201035168 J^HZ ipif.doC 201035168 HZ ipif.doc IV. Designation of representative drawings: (1) The representative representative of the case: No. (2) Simple description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case When revealing the chemical formula that best shows the characteristics of the invention: &lt;Formula 1&gt; 〇