TW591054B - Bifunctional phenylene ether oligomer, derivatives and process for the production thereof - Google Patents

Abstract

A bifunctional phenylene ether oligomer of the formula (1), obtained by oxidation polymerization of a bivalent phenol of the formula (2) and a monovalent phenol of the formula (3), wherein -X- is represented by the formula (2'), and Y-O- is represented by the formula (3'), R2, R3, R4, R8, R9, R10 and R11 in the formula (2') and the formula (3') being required not to be a hydrogen atom, and its use.

Description

591054 V. Description of the invention (l) The invention ^ The present invention relates to a bifunctional 彳 由 公 # 掂 your A "Λ φ 4 ± dendyl ether oligomer (hereinafter occasionally,"). … In addition, the present invention relates to a hardenable resin composition having a phenolic base, thermosetting functional groups at each end, its hardened product, its use, and its preparation method. According to the present invention, a thermosetting resin or a photo-hardenable resin and its intermediate products are manufactured, which are each suitable for use in the field of electronics requiring low dielectric constant, low dielectric loss tangent value, and high duty, and are also suitable for coating and bonding. And molding. BACKGROUND OF THE INVENTION Regarding the electrical industry or Thunder + Feng, the increase in demand requires materials that are compatible with the signal transmission speed of the M8i. β T The low dielectric constant of the delay and the importance of reducing losses ^ Lushuang Γ value to use high-frequency waves (gigahertz band). In addition, 2 (presence of micro-cracks, which are considered to be caused by thermal shock ', and to ensure a high degree of confidence. We). Ah have engineering plastics, such as polyphenylene test PPE and thermosetting resin. In terms of it, PPE is known to have a high body viscosity, which makes Yong Si η poor in plastic plate processability, and the soluble solvents are limited to fragrant W-type solvents such as toluene, benzene or xylene, and functional hydrocarbon solvents such as two Gas nail burning or gas imitation, so poor processability. In order to improve the intersected M t κ ^ valley properties, a method to improve compatibility by mixing PPE with different resins is discussed; the pseudo I PN junction of cyanic resin is also considered, and the formula 1 (JP ~ A ~ 1 1 -2 1 452, etc.). However, the problems of moldability and heat resistance have not yet been resolved. In addition, discuss the conversion of high molecular PPE into low molecular compounds

Page 7 97¾ 591054 V. Description of the invention (2) A method for improving moldability. For example, PPE and divalent phenol in the presence of a free radical catalyst / 'middle high score 9-2 9 1 1 48, etc.); and _ methods, where two = knife cloth 〇 ^ oxidative polymerization 〇 卩-: 6-8 -〇1 1 747). On the second, tenth, —Bay 4 and — the price is expected to accept υ i 1 丨 4 u. There is a high molecular substance in the description, so it is impossible to effectively obtain the double-fixed eight method towels. In addition, it has been widely used as a knife low polymer. The raw material of polymer materials, 哕 算 # _ is used as a variety of functional vibration, dental materials, electronic materials, and various polymeric materials «For these years, applications such as applications have required higher performance, and I want to be an agent. However, the physical properties of neon materials are becoming increasingly harsh. To == Health: Dielectric Constant and Low Dielectric Loss I Cut; Before Folding 2 :: Crack, Low-T Physics, "It has not been: Need to be satisfied. For example, about printed circuits: J seeking k, has Acrylic acid acrylate compounds are used in photowelding photoresists, and water-based photomasks. As for the aforementioned photoresist materials, novolac epoxy acrylate compounds disclosed in JP-AI 2 43 8 6 9 are disclosed in several ―A-3-2 0 54 1 7 bisphenol fluorene type epoxy acrylate compounds, and acid modified products of these epoxy acrylate compounds. In printed circuit board applications, the heat resistance of immersion in a solder bath is required When the heat resistance is insufficient, the photoresist film swells or tears and causes defects. Recently, in order to meet the requirements for increasing the signal transmission speed, in addition to the aforementioned heat resistance, a lower dielectric constant that can shorten the time delay and a The lower dielectric loss tangent value for reducing loss is used to use high-frequency waves (ten de Hertz band). However, the conventional epoxy acrylate compound has insufficient dielectric properties corresponding to high-frequency waves. Therefore, it is necessary to satisfy the foregoing

C: \ 2D-CODE \ 91-O9 \ 91114155.ptd Page 8 591054 V. Description of the invention (3) Requires a new epoxy acrylate compound. Lipid :: type solid resin 'known polyphenylene oxide modified epoxy tree: solid: _ and other issues :, change = Lai, no, method into the paint:' The solvent is limited due to high body pressure . At the same time, ΪΓ: ΐ Molding time requires high temperature and moldability of thermosetting two money: purpose; grease has excellent dielectric properties and excellent after-products are too hard and brittle Γ, θ; when acid and vinegar resin ' Hard problem. When cyanic acid is used; γ Α has f adhesion and solder resistance to some kind of Cheng Er sealing grease using Risi, the aforementioned defects can be masked, the demand for the lower dielectric properties of the laminate The need to coexist is difficult. In addition, the lower dielectric properties are related to semiconductor devices such as semiconductors. The aforementioned epoxy resins are usually used to seal electronic components. These types of epoxy resins are: Type 2: The epoxy resins are composed of various epoxy resins, phenol A type epoxy resin, and bifenol novolac type epoxy resin. Resin, double agent, as needed, accelerated hardening, milk, fat, hardener, inorganic fillers, etc. in response to recent size and thickness α 4, release agents, colorants, etc. The manufacturing technology is based on the requirements of conventional through-hole mounting ^, and the aforementioned electronic parts are formed by surface mounting (S0P: thin :: dual in-line package, etc.), etc.). In the surface mounting method, sealing /, QFP: four-sided flat package South temperature (for example 2 1 0 ° C ~ 2 6 0. Factory> in the limb device is under solder reflow treatment at the installation time 'so high temperature plus C: \ 2D-OODE \ 91-O9 \ 9lll4155.ptd $ 9 page v. 5. Description of the invention (4) __ Hot to 敕 彳 resin conductor device. In this case, the aforementioned loop load such as the sealing layer made by Dangwei is prone to occur. Problems such as cracks and greatly reduced moisture resistance. Flow time: easy: when the thickness of the thin sealing layer of 2.0 mm or less, the solder back. Chip circuit ^ cracks. In order to further improve physical properties and improve the sealing layer w Special transmission speed 'requires the use of a lower dielectric constant. For example, "One Tree" and ^ f sealing materials and jp-a_64_ 24825 reveal a combination of if ^ further two: phenylene ether type resin combination Sealing materials. Functional materials have used (meth) acrylic acid compounds widely as raw materials for materials and materials such as photosensitive materials; in recent years, gamma materials, electronic materials, and various polymers :; The physical properties of the material are becoming increasingly harsh. The physical properties of; are not necessarily satisfied. One of the objectives of the present invention is to provide a bifunctional resin that is excellent in electrical properties and robustness of PPE.冋 Resin compatibility and molding properties, its cocoa improvement and non-PPE structure, its terminal 酹 system is easy to modify, and the use of the class: agent 'has as well as-

591054 V. Description of the invention (5) Polymer obtained

S and a hardenable tree constant and a low dielectric loss of the present invention are another excellent dielectric loss through the composition, one and one through thermosetting of the present invention when another can obtain a sealed flow temperature The thermosetting tree of the present invention has a flexible laminate to print a wiring board. In addition, the compound of the present invention and a low dielectric constant are usually obtained according to the present invention, and another lipid composition will appear, one and one. Sexual resin. The purpose of the system is to provide the tangent value of the consumption of the lipid composition. The purpose is to use the thermosetting resin to improve the moldability of the system. It has excellent heat resistance, low-dielectric η printing cloth, and heat-resistant resin products. It is used as a sealing layer. When it has a low printing cloth that meets the above-mentioned heat and the hot-wire plate material properties, it is a printing sealing epoxy. Exposed to the high dielectric constant wiring board materials, dielectric properties, solid resins, solid resins, heat-cured products, wiring board resin group temperature, such as 0, the harsh composition composition provides a unisex resin layer, 0% Material, and another purpose of the invention provided by the solder is to obtain a -r ^ ^ ^ U novel (fluorenyl) acrylic hardenable resin composition, which has excellent heat resistance, and And low dielectric loss tangent. And /, for ;; Bifunctional phenylene of formula ⑴_oligomeric formula ⑴ of _㈣ and formula (3) of —㈣ by oxidative polymerization to obtain H + 0—Y] a — (-0-x-〇H ~ h 卜 (Ηγη HO -X -OH (2)

591054 V. Description of the invention (6) Y -0H (3) (where -X- is represented by formula (2,), R2, R4 R6 R8 (2,) R3 R5 R7 R9 where R2, R3, R4, R8 and R9 Is the same or different and is a _ atom, an alkyl group or a phenyl group containing 6 or less carbon atoms; R6 and! ^ 7 may be the same or different and are a hydrogen atom, a halogen atom, containing 6 or 6 Alkylene or phenyl group of less than carbon atoms. Y—0—represented by formula (3,), R12 R10 Q-0-- R13 R11 where R10 and R11 may be the same or different and are halogen atoms or contain 6 or Alkyl or phenyl groups with 6 or less stone antiatoms, R12 and R13 may be the same or different and are hydrogen, halogen, alkyl or phenyl groups with 6 or less carbon atoms,

However, Y-0- is a structural arrangement defined by one formula (3 '), or a random arrangement of at least two structural formulas defined by formula (3), and a and b are each an integer of 0 to 300. Is an integer from 0 to 100 and more preferably from 0 to 50, but at least a or 5 is not 0), R2, R3, R4, R8, R9, R10, and R11 requires non

591054 V. Description of the invention (7) In addition, according to the present invention 2, a thermosetting resin represented by formula (4) is provided, R1- -0-Y- -Y-0- b -R] ⑷ 0 -R1 CEN 7 —CH Or a CH ^ —C = CH2 Η where -X-, Y-0-, a and b are defined as in formula (1), Z is an organic group containing one or more carbon atoms and may contain an oxygen atom, c and d is each an integer of 0 or 1. According to the present invention 2, a thermosetting resin is provided as a preferred thermosetting resin. According to the foregoing description, -X- in the above formula is represented by formula (5), and Y-0- has a formula (6) or (7). Arrange structural formulas, or random array structural formulas of formulas (6) and (7). -X 一 -Y—0—

❿ According to the present invention 3, an epoxy acrylate compound represented by formula (8) is further provided, h2cHXch2_

C: \ 2D-CODE \ 91-O9 \ 91114155.ptd Page 13 ^^ 1054 V. Description of the Invention (8) ^^ 1054 HO: h2chch2 ο-γ- -0X0 OH -CH2CHCH2—-〇-9 and 0 —0 = 1: CH2 ⑻ where R13 is a hydrogen atom or a methyl group; —X — (] \. Ry U a ^ b is defined as too), Z, C, and d are defined as in formula (4) and n is 0 to 1 An integer of 〇. According to the present invention 3, there is provided an esterification method according to the aforementioned p @ ^ 7, * 丄 Team Pei Nian <% lactoacrylic acid, and the middle-X system is represented by the foregoing formula (5), and the right meaning is Arrangement structure formula of formula (6) or other formula (7), ^ ^ machine arrangement structure formula. / Fly type) and formula (7): Enlightenment 3'Provide-a second modification of the aforementioned epoxy acrylate compound, a modified epoxy acrylate compound, a mouthful of resin composition, and S with this temple compound May be hard product. And a hardening obtained by hardening the aforementioned composition. In addition, according to the present invention 4, there is provided a soda + man-made product comprising an oxygen-containing resin group of 3 to 2 U 2 and a type having a number average Molecular weight 700, represented by formula (9), + 1 low

CIU One X4 ⑼ Φ where -X-, γ-〇-, aAb are defined as in formula ⑴, and z (4) and n are integers from 0 to 〇. : 1 'According to the present invention 4', there is provided a resin composition for a laminate, wherein the resin composition further contains a cyanic resin. C and d are defined as

Page 14 591054 V. Description of the invention (9) grease: further provides a prepreg, a laminate or a printed wiring board obtained through the use of the aforementioned epoxy resin with a laminate. System 2 has i ^% 51-step provided / species of epoxy resin composition 'fill in ": for lipid composition and additional epoxy resin and inorganic roots: Γ, further provides a layered polymer resin composition Human ::: Benzyl ether oligomeric cyanate compound as a component, the acid is based on each end, and is represented by the formula U0).

-O-C three N (10) Formula f4); χ_, Υ ~. -, Ub is defined as formula ⑴ and Z, c and d are defined as lipid composition 'which contains a cyanate compound of formula (1), and further different cyanate resins and epoxy resins. Less a Yes According to the seventh aspect of the present invention, an acrylate compound represented by formula (11) is further provided, k τ I) propyl R15 0-Z1 σγ- ^ oxoj-Yo—

Z-C (11) group, where X-, Y-0-, a and b are defined as in formula (1), and z is organic C: \ 2D-CODE \ 9l-09 \ 91114155.ptd page 15 1 591054

5. Description of the invention (10) The branch chain does not have a warp group and there is a "multiple carbon source? ,, And C and d are defined as in Formula ⑷, and R15 is an amino group. The lactogen 2 invention 7 'further provides a hardenable resin composition containing the aforementioned (meth) acrylic acid compound. Detailed description of the inhalation The inventors are actively engaged in research on difunctional phenylene ethers and found that the bifunctional phenylene ethers of formula (1) can pass through the divalent phenol (H〇_x_〇H) It is produced by oxidative polymerization with (3) -valent phenol (Y-OH) in a ketone solvent. Based on the foregoing findings, the present invention has been completed. The details of the present invention will be described later.

One valence of the present invention represents a divalent age, which has a hard biphenyl structural formula -X- 'represented by the formula (2,) where R2, R3, R4, R8 & R9 are the same or different and are halogen atoms , A radical or benzene containing 6 or less carbon atoms, R5, R6, and R7 may be the same or different and are hydrogen atoms, _ atoms, alkyl groups containing 6 '" or less Or phenyl, and R2, R3, R4, R8, and! ^ Each require a non-hydrogen atom. The expression (2) shown by HO-X-0H is shown below.

(2)

In formula (2), 2,3,3,5,5'-pentafluorenyl- [1,1'-biphenylbiphenyl 4,4, ~ one-year-old and 2,2 ', 3,3,5, 5-Hexamethyl- [1,1'-biphenyl] -4,4'-secondary is particularly preferred. When the divalent bisphenol based on 2-position (R4 of formula (2)) is not used as a raw material, the oxidation rate of the divalent phenol itself is extremely high, so the divalent age is converted into dibenquinone and the reaction solution In precipitation.

591054 V. Description of the invention (11). As a result, the homopolymerization reaction of one valence age of formula (3) is preferentially performed. The growth of phenylene ether with a radical at one end only progresses until the reaction solution sinks. Therefore, it is not possible to synthesize a bifunctional phenylene ether which is soluble in fluorenylethylfluorenone. For example, there are 3,3,., 5,5'-tetramethyl- [1,1'-biphenyl] -4, 4'-secondary ages as bifunctional phenols without substitution based on the 2-position. The GPC pattern of the precipitate is shown in Figure 1 when this type is used for synthesis. It was confirmed that a polymer was produced. In terms of 'e.g. 2,2,3,3,5,5-Hexamethyl-biphenyl] -4,4'-diploidy as a divalent having a substitution based on the 2-position (R2 of formula (2,)) phenol. According to the change in the GPC spectrum (Figure 2) and the change in average molecular weight (Figure 3), in the reaction using the aforementioned age, the distribution of the amount of phenylene_fraction_ obtained between the beginning and the end of the reaction was almost equal, which confirmed that no polymer was produced . Therefore, the desired difunctional phenylene ether oligomer can be effectively obtained. As mentioned above, when using divalent phenols having substitutions based on 2-, 3- and 5-positions, a product is obtained which has a molecular weight that could not be expected from conventionally known raw materials having substitutions based on 3- and 5-positions. distributed. Therefore, in order to solve the object of the present invention, it is required to reduce the oxidation rate of the divalent phenol itself, and the presence of the substituent at the 2-position (R2 of formula (2)) is indispensable. The monovalent phenol of the present invention means a monovalent phenol of the formula (3) represented by Υ-0-Η. R12 RIO i VJ> -0H (3) R13 R11 In formula (3), 'R10 and R11 are the same or different and are _ atoms, alkyl groups or phenyl groups containing 6 or less carbon atoms, R1 2 and R13 is the same or different and

C: \ 2D-CODE \ 91-O9 \ 91114155.ptd page 17 591054 5. Description of the invention (12) is a hydrogen atom, a halogen atom, an alkyl group or a benzyl group having 6 or less carbon atoms. It is particularly preferred to use monovalent phenols having substitutions based on 2- and 6-positions alone or in combination with monovalent phenols having substitutions based on 3-positions or at 3-mono and 5-positions other than 2- and 6-position . Even more preferably, when used alone, 2, xylenol is preferred, and when used in combination, 2,6-xylenol and 2,3 6-dioxine are preferred. When used in combination, it is preferable that the ratio of one-valence age based on the 3-position or 3- and 5-position based on the total one-g g cent is 70% Morse ratio or less. When the ratio of monovalent phenol based on 3-position or 3- and 5-position to all monovalent phenols is higher than 70% Molar ratio, the aforementioned monovalent phenol is converted into a crystalline compound, so even if the compound has The number average molecular weight is about 1,000 and is still insoluble in fluorenylethylfluorenone. In addition, when 2,6-bisphenol is used in combination with 2,3,6-trisphenol, a lower molecular oligomer is obtained when 2,6-monophenol is used alone. The reason for this is that the 3-position methyl group at the 2,3,6-diamine age is delayed in polymerization, thereby delaying the production of the polymer. Then, the manufacturing method of the present invention 1 will be described. The difunctional phenylene ether oligomer of the present invention 1 represented by the formula (1) is obtained by the valence oxidation polymerization of a divalent phenol of the formula (2) and one of the formula (3). The oxidation method includes a method in which oxygen or air is directly used. There is also an electrode oxidation method. The oxidation method is not particularly limited, and any method can be used. In view of safety and factories and equipment, the investment cost of the equipment is low, and air oxidation is better. When oxidizing with air, the pressure from atmospheric pressure to 20 kg / cm2 is usually selected. When using oxygen or air for oxidative polymerization, the catalysts used include

Copper salts such as CuCl, CuBr, Cu2S04, CuCl2, CuBr2, CuS04 & CuI

mm

Page 18 C: \ 2D-CODE \ 91-O9 \ 91114155.ptd 7 Η'Π 591054 5. Description of the invention (13). These catalysts can be used alone or in combination. These catalysts may be used in combination of two or more amines. Amines include mono- and dimethylamines, mono- and diethylamines, mono- and dipropylamines, mono- and di-n-butylamines, and mono- and di-dipropylamines , Mono- and dibenzylamines, --- and dicyclohexylamines, mono- and diethanolamines, ethylmethylamine, methylpropylamine, / propylethylamine, fluorenylcyclohexyl Amine, morpholine, fluorenyl-n-butylamine, ethyl isopropylamine, benzylfluorenylamine, octylbenzylamine, octyl-chlorobenzyl ^, fluorenyl (phenylethyl) Amines, fluorenylethylamines, bis (phenylethyl) amines, 1-methylamine-4-pentene, pyridine, methylamidine, 4-diamylaminoamine and piperidine. The catalyst is not limited to these examples, and any other catalysts and amines can be used. In particular, di-n-butylamine is preferred as the amine. = • Mono-n-butylamine retards the homopolymerization of the monovalent phenol of the formula (3), so that almost no polymer is produced. Thus, a diguan ~ phenylene ether oligomer having a sharp molecular weight distribution was obtained. This is the solvent used in the present invention. Ketone solvents and alcohol solvents are used as a solvent for the reaction, and the conventional t 2 Luoxin agent used in the conventional m-oxidative polymerization can be used in the present invention. It is known that this reaction produces a ketone or a reaction solvent: :: in organic solvents. Therefore, it cannot be used as the product produced. The product shown in the figure above (Figure 2) is ‘the present invention! Alcohol. Therefore, a range of useful solvents; :: Dojigu Valley is easily soluble in ketones or… used alone, or combined 组合 = widened. _ Solvents and alcohol solvents: toluene, benzene, or xylene; use: aromatic hydrocarbon solvents such as, each of which is & Ketone solvents include propyl isopropyl and ethyl ethyl

C: \ 2D-CODE \ 91-O9 \ 91114155.ptd Page 19 II! 591054 Fifth invention description (14) A3 is the same, two Γ is 3 is the same, two · M · monoethyl 曱 曱 butyl 曱Ketones and fluorenyl butanone include agents such as methyl alcohol, ethyl alcohol, ethyl alcohol, ethyl alcohol, propylene glycol, diethylene glycol ether, butylendoethoxypropyl glycerol, and sharp molecular weight distribution. Low polymer? Relatively low: Second, its effect is not significant. Furthermore, I have dreams of using the solubility of keto-cold J Rishou, and the solvent is preferably a mixed solvent of the monovalent phenol 曱 1 as the raw material. Soil Soil-Same, or containing fluorenylethyl The production method of the present invention 1 is not limited to 4 X π Hu, 6 卞 丨 degrees, unless the reaction shirt enters the explosive limit range of the bath. Due to oxidative polymerization as an exothermic reaction, temperature control: 25 to 50 ° C. ^ 50 r 5 ^ r / V, it is difficult to control the loneliness. When the reaction temperature is high, 50 c / day, it is difficult to control the molecular weight. When the reaction temperature enters the explosive limit range, it cannot be manufactured safely. -Indicate it at 25 c, which illustrates the desired concentration of the method of the present invention]. The divalent value of formula (2) is based on the fact that the solvent to be added dropwise is' '' and the vehicle weight ratio. In this case, the weight is more than 20%. When the foregoing concentration is less than 2% by weight, γ In terms of human β # 丨, the rate of hydration reaction is lower than that in leaves. In addition, the concentration of the monovalent phenol is preferably from 6 to 50% by weight based on the solvent. ♦ Reduce the reaction rate of koji: When the concentration of monovalent age is less than 6% by weight, in the method of polymerization two: two, the divalent age of formula (2) and the one of formula (2) are better than ears: 1 to 1 . Range. Very good :: Because the range described below does not easily cause homopolymerization of monovalent phenols 591054 5. Description of the invention (15) The reaction can be controlled, so the molecular weight can be controlled. When the ratio between the divalent fluorene of formula (2) and the monovalent phenol of formula (3) is less than 1: 2, the remaining divalent phenol of formula (2) increases. In addition, if the foregoing ratio is more than 1:10, homopolymerization of the monovalent phenol of formula (3) occurs, so the molecular weight becomes too large, and the resulting low polymer is insoluble in methyl ethyl fluorenone. The manufacturing equipment and manufacturing method used in the present invention 1 will be explained. Copper catalysts, amines, and solvents are placed in a slim thermometer, intake pipe, and baffle. The divalent phenol and the monovalent phenol are obtained in a solvent to pass air. Dropwise addition time Dropwise addition time is not within the aforementioned range. The cloth varies greatly. Dropwise addition is complete to 5 hours. Even if it is stirred for more than 5 hours, the reaction should be terminated. Next, this invention 2 is demonstrated. The reactor, the reactor is equipped with a stirrer, etc. The materials are stirred at 40 ° C, and the solution is added to the reactor dropwise via the dissolving mixed solution, preferably 50 minutes to 210 minutes. At this time, the molecular weight fraction f of the obtained low polymer is preferably stirred for 5 minutes 4 and the molecular weight does not increase further.

20 0 1-1 9 6 5 6 9). In order to transform the first step of the aforementioned dual patent application into a highly active thermosetting resin = ^ -ether ether low polymer research, it was found that the content and properties of different resins, the inventors actively improve the formula (4 ) The thermosetting resin composition is improved and moulded, where -X- is expressed by formula (2,) and is obtained by: υ ~ is a structural structural arrangement or at least two formulas (3,) are defined by Zhishi,) a kind of difunctional phenylene ether oligomer, the end group of the oligomer is changed by random arrangement of the decaying structural formula

C: \ 2D-CODE \ 91-〇9 \ 911] 4155.ptd 21st stomach 591054

It is a thermosetting functional group. Based on the foregoing findings, the details of the present invention will be described later. Meta Cost Invention 2. The present invention is characterized in that the oxidation rate of Yuling's oxidized puppet cymbal itself can be reduced to effectively produce the dioxidative polymerization reaction. Phenol is used in addition to the 2- and 6-position substituents (believe #: phenol resin. In addition, the present invention is required for the oxidative polymerization reaction using a substituent having a 3-position to introduce it. The effect will be described later, for example. Regarding " Do not complete as a raw material, I have studied (JP-A-6 0- 1 52433) due to the presence of the emulsified couple of phenol and benzene.

@ 比 ， Luo Ye pH is adjusted to 8 ~ 9. However, since the reaction can be performed more stably by using an oxidative coupling having a substitution of 2, 3, 6-dimethylamine based on the 3-position, the production is preferably performed efficiently under highly alkaline conditions with a pH of about 13 Patent Application Nos. 2 0 1-3 1 9 0 6 4). In addition, as for the oxidative polymerization reaction, as shown in Japanese Patent Application Nos. 2 0 1-1 9 6 5 6 9, the bivalent s-fraction obtained from the above-mentioned 2,3,6-trimethylglycan is regarded as the divalent value. g and 2,6-dipyridine alone, 2,3,6-tricresol alone, or a mixture of 2,6-dipyridol and 2,3,6-trisphenol

Copolymerization as a monovalent phenol can effectively produce a bifunctional phenylene test oligomer. In addition, it is estimated that the number of fluorenyl groups is increased for thermosetting derivatives (aqueous acid compounds, epoxy compounds, propylene compounds) derived from these phenols to achieve low dielectric properties. In other words, the presence of the t-position substituent was found to be extremely important for the present invention. The intermediate product of the present invention, that is, the difunctional dibasic acid oligomer has a structural formula represented by formula (1), wherein -X- is defined by formula (2,) ', and Y: 0- is at least one formula 3,) Define the structural formula arrangement or at least two formulas (3) Define the structural formula random arrangement. In the formula, R2 to R1, a and b are defined as the formula of the invention 1.

C: \ 2D-C0DE \ 91 > 09 \ 91114155.ptd Page 22 591054 V. Description of the invention (17) 1) ° In other words, it is a phenylene ether oligomer, among which R 2, M, and R8 are important , R9, R10 and R11 are not hydrogen atoms. —X— preferably has a structural formula represented by formula (5), wherein R2, R3, R4, RJ, R8, and R9 are methyl groups, and R5 and “are hydrogen atoms; (6) Arranged structural formula, in which R 丨 〇, r 丨 丨 丨 2 are fluorenyl groups, and R13 is hydrogen atom +, or a single formula ⑺, in which R10 and Rn are methyl groups, and R12 and R13 are hydrogen atoms, or the formula (6) Randomly arranged structural formulae with formula (7). The intermediate product, that is, the difunctional phenylene oligomer will be described later. The phenylene ether oligomer represented by formula (1) may be Divalent phenol and one of the definitions of formula (3) ^ Tombfield Fei is J ^ ^ ^ ^ ^ shellfish phenol or formula (3) meaning monovalent phenol mixture; ligustriol-alcohol or ketone solvent for oxidation Efficient production by polymerization. As one of the valence ages of formula (3), special 9 j, η ^ ^ ^ special special car and good early alone use have substituted monovalent phenol based on 2_ and 6_ positions, or use in combination except Substitute based on 3-position or call at 3_ and 5 = :: and 6-position outside of the tool. It is better to replace ° based on 2- and 6_ position when alone or 2, 3, 6-three ages are preferred. When used in combination ^ = = ' 2 '6-Dimethylpan 3, 6-trisphenol is preferred. 乂 2, 6-disphenol and 2, the thermosetting phenylene ether of the present invention is shown low. In other words, -X- is represented by the formula (2,) Means-the mouth is arranged by the structural formula shown in formula (4), or at least two formulas (3 'is a column defined by formula (3,). X, Υ, a, and b are defined as formula (1). Ζ = of Randomly arranged organic groups of the structural formula, the organic group may contain at least one carbon atom number of oxygen, 3, lice atom. CAd is individually an integer of 0 or 1.

591054

-Rl -C = N -CHp or "-A. H-= There may be an organic group containing at least one carbon atom and eight at the ζ position. For example, including ch2-) —, — ^ has an oxygen atom—, (- CH2—Ar-〇 —)-. The above-mentioned organic groups are not limited to the two before, i, and the methods include those in which the organic group is directly added to the formula (1), examples. The addition method, and the use of derivatives in the synthesis The method of square addition of intermediate products is not limited to these methods. Human,: The method of sequestering. For convenience, the following description will be based on the derivative obtained from formula (1) (its intermediate product) = = early structure (Formula) indicates that the phenyl ether oligomer is used as a thermosetting product. + = (1) Bifunctional elongation intermediate product. 胄 Functional elongation phenyl ether is low: powder form of oligomeric oligomer compound, or used in reaction solution. 22. The solution can be used in the form of the cyanated human cyanide solution of the present invention in the following description. The compound is an example of the method by the above formula (1). The acid can be converted into a character φ 4 表 M Bi-monthly D compound with phenolic hydroxyl groups at both ends as an intermediate product, The presence of a base to cyanogen teeth _ dehydrogenation reaction synthesis. Tick or lice, typical examples of alkali include tertiary amines such as tris-dimethylaniline and roar, sodium hydroxide, 2, triethylamine, dipropylamine, sodium oxide, calcium hydroxide, sodium carbonate , 舻 J emulsified potassium, sodium methoxide, acetamidine are limited to this. Human & potassium and sodium bicarbonate. Although the base is not limited, the reaction solvent typically includes

C: \ 2D-CODE \ 91-O9 \ 91114155.ptd Page 24 πΐ054 V. Description of the invention (19) Stupid, gas imitation, dioxane, propane, methylbenzene, burning, tetragasification carbon, gas benzene , Shi Xiaoji benzene, Nitromethyl when using gasification ^ methyl ... hydrogen bite ° South and two. Pen burning. Click >. The reaction temperature is preferably -30 when the temperature is changed. . To + irc (both below, it will be explained that when the nitrogen is too high, Λ is -30 ° cm65 ° c. The system is exemplified by the above formula (invention of the method for the production of oxo compounds). The epoxidized compound as an intermediate surface looks like two Dehydrohalogenated trans-r 'and halogenated glycidol such as epichlorohydrin under bifunctionalization with a phenolic hydroxyl group at the end are typical examples in the presence of alkali. Sodium chloride, sodium hydroxide, potassium oxide, potassium oxide, sodium oxide Ethoxylate is limited to this. Sodium carbonate, potassium carbonate and sodium bicarbonate. Alkali is not only 囿 reaction temperature 彳 this & will be explained as: ⑶10. The compound is prepared by the above method of a compound. Propylene-based compounds are used as intermediates to produce 4-bromo-1 ~ 1-bis, long-chain difunctional bicarbons, sigma-propyl bromide or propylene chloride, or dehydrogenation under conditions. The reaction is combined with the presence of a phase transfer catalyst, and it is tested by extension. Examples of catalytic types include tertiary amines such as trimethylamine and tetramethyltetrabutylammonium chloride, and benzyl tri-n-butyl chloride: desertification ..., moth : D-butyl-n-butylammonium and quaternary scale salt. Phases include two-n-butyl-butadiene and iodine test. Typical examples include hydrogen. The oxygen ditransfer catalyst is not limited to this. &Quot; Sodium, sodium hydroxide, sodium carbonate f, potassium, sodium methoxide, ethyl milk are limited to this. Potassium rabbit acid and sodium bicarbonate. Alkali is not only 囿

C: \ 2D-O0DE \ 9J-09 \ 91JJ4J55.ptd 591054 V. Description of the invention (20) The reaction temperature is preferably -10 ° C to 60 ° C. The thermosetting phenylene ether oligomeric compound of the present invention may be hardened alone, or may be hardened as a resin composition further containing a cyanate compound, an epoxy compound, a polymerizable compound, and / or a catalyst. Any known hardening method can be used to harden the thermosetting phenylene ether oligomer compound. The cyanic acid compound includes, for example, m- or p-phenylene cyanocyanate, 1,3,5-tricyanobenzene, 4,4'-dicyanobiphenyl, 3,3 ', 5,5'- Tetrafluorenyl-4, 4'-dicyanobiphenyl, 2, 3, 3 ', 5, 5'-pentamethyl-4, 4 '-dicyanobiphenyl, 2, 2', 3, 3 ', 5, 5' -Hexamethyl-4, 4 '-dicyanobiphenyl, fluoren (4-cyanophenyl) pinene, 1- (2,3,5 -trifluorenyl-4 -cyano Acid phenyl) -1- (3,5-difluorenyl-4-phenylcyanophenyl) methane, fluorene (2, 3,5-trifluorenyl-4-dicyanophenyl) methane, 1 1,1-fluorenyl (4-cyanophenyl) ethane, 1- (2,3,5-trimethyl-4-ylphenylcyanate) -bu (3,5-difluorenyl-4-carboxylic acid) Phenyl) ethane, 1, 1-fluorenyl (2, 3, 5-trifluorenyl-4-dicyanophenyl) ethane, 2, 2-fluorenyl (4-cyanophenyl) propane, 2- (2, 3, 5-trimethylphenyl-4-cyanophenyl) -2- (3, 5-diamidino-4-phenylcyano) propane, 2, 2-pyrene (2, 3, 5 -Trimethyl-4-phenyl dicyanate) propane, fluorene (4-cyanophenyl) ether, fluorene (4-cyanophenyl), fluorene (4-phenylcyanate) sulfide, 4 , 4'-benzophenone dicyanate and ginseng (4- Phenyl cyanate) methane. In other words, a cyanate compound is a biphenol having a cyano group directly bonded to its aromatic ring, a fluorene or polycyanate compound, a cyanate compound, Prepolymers such as cyanic compounds and diamines, and cyanophenol-containing novolac-based phenolic trees derived from novolac resins, which are the reaction products of phenols such as phenol and o-phenol . These cyanic compounds may be used alone or in combination.

C: \ 2D-CODE \ 91-O9 \ 91114155.ptd page 26 591054 5. Description of the invention (21) The prepolymer of the aforementioned cyanate ester compound will be explained. A polyfunctional cyanate compound having at least two cyano groups per molecule is polymerized by tri-polymerization of cyano groups to form a tricyclic ring. A substance having a molecular weight of 2,000 to 6,000 is used as a prepolymer. The aforementioned prepolymer is obtained by polymerizing the above-mentioned polyfunctional cyanate compound monomer in the presence of a catalyst, the catalyst being selected from an acid such as an inorganic acid and a Lewis acid; a base such as sodium alkoxide and a tertiary amine; or a salt such as Sodium carbonate. The prepolymer partially contains a monomer and is in the form of a mixture of the monomer and the polymer. The prepolymer is preferably used when manufacturing a hardened product. The polymerizable compound includes fluorene-butene difluorene imine, epoxy resin, and the like. Can be used as a mixture. The cis-butene difluorene imine includes, for example, N, N'-diphenylphosphonium cis-butene difluorene imine, Ν, Ν'-phenylene cis butene difluorene imine, Ν, Ν ' -Diphenyl ether, cis butene difluorene imine, Ν, Ν '-dicyclohexyl fluorene, cis butene difluorene imine, Ν, Ν'-bis, dibenzyl cis butene difluorene imine, Ν, Ν'-diphenylsulfone cis-butene difluorene imine, Ν, Ν'-diphenylsulfonyl cis butene difluorene imine, Ν, Ν'-diphenyl phenyl cis butene difluorene Imine, Ν, Ν'-diphenylcyclohexane 贰 cis-butenedifluorene imine, Ν, N'-digas-diphenylcyclopentane 贰 cis-butenedifluorene imine, Ν, Ν'- Diphenylcyclohexane 贰 cis-butenedifluorene imine, Ν, Ν'-diphenylphosphonium fluorenylcis butene difluorene imine, Ν, Ν'-diphenyl ether fluorenylcis butene Diamidine, Ν, Ν'-diphenylsulfone methylcis-butenediamidine, Ν, Ν'-ethylidene cisbutenediamidine, Ν, Ν'-hexamethylene Fluorenyl cis-butene difluorene imine, prepolymers of these N, N′-fluorene cis-butene difluorene imine compounds, such fluorene Prepolymers of arylenediimine compounds and diamines, and cis-butadieneimine-modified compounds of aniline-formalin polycondensate or fluorenylcis-butene

C: \ 2D-CODE \ 9] -O9 \ 9]] 14] 55.ptd page 27 591054 V. Description of the invention (22) Modified compound of diamidine. The aforementioned epoxy resin includes, for example, bisphenol and 2-, 2'-, 3-, 3'-, 5-, and 5 'substituted with bisphenol by ii atom, alkyl group or phenyl group having 6 or less carbon atoms. -Resins obtained at at least one of the positions; bisphenol A and 2-, 3-, and 5-positions of bisphenol A substituted by a halogen atom, an alkyl group or a phenyl group having 6 or less carbon atoms Resin obtained at at least one position; bisphenol F and at least one of the 2-position, 3-position, and 5-position of the bisphenol F substituted by a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group Resulting resin; Derived from divalent or at least trivalent phenols such as hydroquinone, resorcinol, ginseng 4- (phenyl via) calcination and 1,1,2,2-diphenyl (4-phenyl via) Fired glycidyl ether compounds; novolac-type epoxy resins derived from novolac resins, which are the reaction products of phenols such as phenol and ortho-cresol and formaldehyde; amine-based epoxy resins, which are derived from aniline , P-aminophenol, m-aminophenol, 4-amino-m-phenol, 6-amino-m-phenol, 4, 4'-diaminodiphenylmethane, 3, 3'-di Aminodiphenylphosphonium Alkane, 4, 4'-diaminodiphenyl ether, 3, 4'-diaminodiphenyl ether, 1,4-pyrene (4-aminophenoxy) benzene, 1,4-pyrene (3-amine Phenylphenoxy) benzene, 1,3-pyrene (4-aminophenoxy) benzene, 1,3-pyrene (3-aminophenoxy) benzene, 2,2-pyrene (4-aminophenoxyphenyl) ) Propane, p-phenylene diamine, m-phenylene diamine, 2, 4-methylbenzenediamine, 2, 6-phenylene phenylene diamine, p-phenylene phenylene diamine, m-phenylene phenylene diamine Amine, 1,4-cyclohexane-fluorenyl (fluorenylamine), 5-amino-1-(4'-aminophenyl) -1,3,3-trifluorenyltetrahydroperoxide, 6-amino -1-(4, -aminophenyl) -1,3,3-trismidinotetrahydro etc .; derived from aromatic carboxylic acids such as p-hydroxybenzoic acid, m-hydroxybenzoic acid, p-benzene Glycidyl ester compounds of dibasic acid and m-phenylenedicarboxylic acid; betaines derived from 5,5-dimethylhydantoin, etc.

C: \ 2D-C0DE \ 91-09 \ 91114155.ptd Page 28 591054 V. Description of the invention (23) 醯 urea type epoxy resin; cycloaliphatic cyclohexyl) propane, 2, 2- 贰 [4- (2 , 3 dicyclohexyl dioxide and 3, 4-hexanoic acid; triglycidyl oleyl-homo-triphine. These epoxy resin resin compositions may contain epoxy resins for use in the present invention. In the case of compounds or lipids, dicyandiamide, lacquer resin, cresol novolac resin family amines can be used as the hardener. Here, the term “hard scent” refers to the aforementioned aromatic diamine resin composition containing a cyanate compound. Aromatic diamines and aliphatic diamines are added to the resin composition as a prepolymer. Blended into the resin resin composition may be used without a catalyst. Use of catalysts can reduce the molding temperature, amines can be used Such as N, bis-n-butylamine, orthopione such as 2-methylazole, phenols such as phenol and resorcinol, lead fatty acid, tin oleate, tin octoate, aluminum chloride, tin chloride and chlorine Zinc compounds, and used alone or in combination. Oxygen resins such as 2,2- (5,4-epoxy ring-epoxypropyl) cyclohexyl] propane, ethoxycyclohexyl -3,4-epoxycycloisocyanurate and 2,3,6-triglycidyl can be used alone or in combination. It should be used as a hardener for individual components. When the resin composition contains epoxy resin The four veins, aromatic amines, acidic acids, acid anhydrides, and various aliphatic amines and cycloaliphatic agents can be used alone or in combination. As for the typical. As for the use of hardeners, or cis-butene diimide Formerly, it is typical. Each hardener can be individually hard or can be made into a composition corresponding to the hardener. It can be hardened by heating in a short time. However, the hardening time can be shortened according to the degree. Ethylenediamine and imimidazole and 2-ethyl-4-fluorenimide organometallic salts such as naphthenic acid, zinc stearate and titanium butyrate, chlorides such as gas chelate metals. These catalysts can be used alone

The resin composition may contain an extender, a filler (containing

View 054 V. Description of the invention (24) 'For example, it includes silicon oxide, titanium, zinc oxide, mica, glass powder 1 :: milk-weight aluminum fiber, and shuangzai. Fabrics are used for a long time, night products are used for molding, especially when f is used alone, compounds are combined with epoxidation: prepregs obtained from resins, and additionally when epoxidized diacrylate compounds are used, organic and inorganic fillers Agent), strengthening agent or pigment, calcium acid, antimony trioxide 'kaolin, spar, carbon black, polyethylene powder, polypropylene powder, copper powder, glass fiber, carbon fiber, oxalamide fiber, glass fabric 、 Glass non-woven polyester non-fabric. These can be used alone or in combination ^, resin group adhesives or composite materials containing these additives such as copper clad compounds, epoxy compounds alone, or cyanic acid, typically The use example is a laminate obtained by semi-hardening and hardening the aforementioned prepreg.% •, a typical example is used for a semiconductor sealing material. The present invention 3 is directed to epoxy Η2〇 = 〇-〇-〇-CH2 represented by formula (8). -CH-C H2--2 | ^ V ^ OXO ^ YO-J ^ J-2-j- ·-ΟΎ- ΟΧΟί OH CH2CHCH2 where R13 is a hydrogen atom or a fluorenyl group, -X—, Y_〇_, a and b are defined as (1) Z, c, and d are defined as in formula (4) and n is an integer of 0 to 10. In addition, the present invention relates to a kind obtained by reacting an epoxy acrylic acid compound of formula (8) with an acid or a needle. Acid-modified epoxy acrylate compound. In addition, the present invention relates to a hardenable resin composition containing the aforementioned propylene oxide acrylic acid compound & The hardened product of 591054 V. Invention description (25) is obtained by hardening the aforementioned hardenable resin composition. As for the reaction method, the epoxy acrylate compound of the formula (8) is preferably produced according to a known method, for example, the method disclosed in JP-B-44-3 1 4 7 2 or JP-B-4 5- 1 46 5. In other words, typically, for example, an epoxy acrylate compound of formula (8) can be obtained by reacting an epoxy compound of formula (9) with acrylic acid, fluorenyl acrylic acid, or a mixture of acrylic acid and fluorenyl acrylic acid. The epoxy compound of the formula (9) is produced, for example, by the method disclosed in Japanese Patent Application No. 2000-1-353 1 94.

rChhth ❿ 曱 曱 曱 殊 殊 殊 殊 group limited oxygen equivalents transethanol dipropionin, alcohol monoketobenzene, formula (8) of Ming 3 or a mixture thereof is preferably 0.3 to 3 better than cyclic acid, methyl propionate Add diluted, butanol, acetic ether and diethyl fibrinolysate, and diethyl isobutyl phosphonium acetate, gas benzene, dibenzyl acrylic acid. Compared with propylene and better acetic acid, acetic acid, acetic acid, acetic acid, acetic acid, acetic acid, acetic acid, acetic acid, acetic acid, and acrylic acid, based on the epoxy resin of formula (9) 1 至 5Chemical Equivalent. Each chemical equivalent of naphthenic acid or a mixture thereof does not have a specific oxygen compound composition. Agent. Diluents include, for example, alcohols such as methanol, diols, fluorenyl lysone, ethylcellolysin, glycol monomethyl ether, and esters such as methyl cellulose acetate dipropylene glycol monomethyl ether, diethylene glycol acetate Glycol monoethyl ether, ketone solvents such as methyl ethyl ketone, and aromatic compounds such as benzene, chlorochlorobenzene, and solvent naphtha.

C: \ 2D-CODE \ 91-O9 \ 91114155.ptd Page 31 591054 V. Description of the invention (26) In addition, it is better to use a catalyst to promote the reaction. Preferred catalysts specifically include amines such as triethylamine, dimethylbutylamine and tri-n-butylamine, quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, tetrabutylammonium salt, and benzyltriamidine Ammonium salts are now quaternary scale salts, phosphines such as tribenzylphosphine, and imidazoles such as 2-methylimidazole; 2-based and 4-methylimidazole. The amount of the catalyst based on the reaction raw material mixture is relatively large (^ to ⑽ weight ratio, and better G2 · weight ratio. It is also better to prepare t1 to prevent polymerization during the reaction. Polymerization inhibitors include hydrogen brewing, methylhydrogen In addition, t f, A f 1 A, 1 T 丞 only 唧 and fenzui ′ control polymerization reactions due to unsaturated bonds, depending on the needs of j main 7, the reaction can be in Qido 笠 π, She—, Shi 1 ° ^ ^ Depending on the conditions of October, anti-oxidants such as butyl-4-fluorenol can be used for 11 days. 2, 6-Di-Third-One, although the reaction temperature ^ urge \ # = ^ due to the oxidation reaction of the line. The temperature at which the product enters the reaction as olefin without the original

To 15 (TC, and especially good 7 (rc \ = polymerization. The better reaction temperature is determined by 6 ° C temperature, but preferably = 0, although the reaction time is based on the reaction A Λ, to 15 days. After the reaction is completed, the excess (formazan with S \ and excess diluent can be removed by distillation or other methods, and materials such as% & can be used without removal. Tongue removal or the second will explain the acid modification of the invention 3 = Modified propylene oxide compound is produced through (preparation: 2 7 acid brewing compound and; acid = or mixture thereof) propylene oxide propylene oxide, preferably two; carboxylic acid is 1 or more valent acid . Overnight, the private carboxylic acid or monovalent or polyvalent aromatic carboxylic acid

C: \ 2D-CODE \ 9l-09 \ 91] M155.ptd page 32 591054 5. Description of the invention (27) Chinic acid or its anhydrides include, for example, butene-dicarboxylic acid, tetracarboxylic acid, I ~ a Samarium, succinic acid, itaconic acid, benzene &, methylhexahydrophthalic acid, chloramphenic acid,: f: Guang, -methyl add), trimellitic acid, pyromellitic tetra-turdecine ( nadxc 4, biphenyltetracarboxylic acid, cyclohexanetetramethylene 7;:, tetramethylene acid, 3,3 ', 4, 8-tetracarboxylic acid, 3, 3, 4, 4, 4 Tetracarboxylic acid, naphthalene_1,4,5 acid, cyclopentanetetracarboxylic acid and its derivatives. Diphenylamine is used for example; for example, the above-mentioned epoxy propylene = 囿 =! In the reaction, additional as needed Mu Liu Xi-thinner, etc. Although lacking in anti-sense; * ,, W households, Niu Xi species /, dagger catalysts, the aforementioned thermal polymerization reaction temperature of raw materials such as propylene oxide, etc .; preferably = not It will send 130 t, and the reaction time is based on the reaction temperature of 60 C to 80 hours. Ί— 乂 隹 is 1 to 反应 After the reaction, the known method of acid-modified epoxy acrylate compound of the present invention 3 is separation by distillation. The molecule of the inventive acid-modified epoxy acrylic acid fluorene compound may contain epoxy groups In other words, as described above, when the amount of propylamino acetic acid or its mixture relative to the amount of epoxy compound is adjusted to a predetermined amount in the range A, the unreacted epoxy group remains in the obtained epoxy = compound of month 1. The thus-obtained epoxy acrylate compound is further acid-modified to obtain an acid-modified epoxy propylene diacrylate compound having an epoxy group. Modification? The acid value of the present epoxy acrylate compound may be appropriately adjusted as required. Text is 20 to 200 mg KOH / g and more preferably 30 to 150 mg KOH / g: Father

«11 C: \ 2D-CODE \ 91-O9 \ 91114155.ptd

591054 V. Description of the invention (28) Then, the third product of the present invention is characterized by its eight hardenable resin composition. The hardenable resin group and / or the acid-modified epoxy resin have an epoxy acrylate compound according to the present invention. The composition may contain a known wide dilute acid ester compound. Chemical conversion of the hardenable resin saturated compound of the present invention 3 = fat-reducing, ethylene oxide resin, having an ethylenic agent, a photosensitizer, and the like. Bamboo rabbit polymerization initiator and / or thermal polymerization initiator or acid-modified propylene oxide acid propylene oxide acid brewing compound and / or compound. The text refers to compounds that can be used for this purpose to produce epoxy resins, which can be selected from the group consisting of bis-rioxy resins, greases. Epoxy resin ㈣ Acrylic varnish-type cyclolipid, biphenyl-type epoxy resin, benzoin lacquer-type ring; 2:,! , Acid varnish-type epoxy resin, dimethyl epoxy resin, dicyclopentane; glycidyl hydrazone, cycloaliphatic ^ ^ monoene phenol. 4 lacquer-type epoxy resin, biphenol novolac ^ ^ Japanese patent application Nos. 2 0 1-3 5 3 1 9 4 and 2002-018508 disclosed ppH shisha > γ ^ 14_ μ s " 3 under the PPPE structure of the mounting oxygen resin and bromide this search milk resin —The flame retardant epoxy resin obtained by the person. These epoxy resins can be used alone or in combination. The ethylene oxide resin may be selected from generally known ethylene oxide resins. Ethylene oxide resins include, for example, alkylene oxides such as ethylene oxide, 2-methylethylene oxide, 2,2-dimethylethylene oxide, 3-methylethylene oxide, And 3,3-dimethyl ethylene oxide, 3-methyl-3-methoxyfluorenyl ethylene oxide, 3, 3, di (difluoromethyl) perfluoroethylene oxide, 2- Chloromethyl ethylene oxide, 3,3- (fluorenyl) ethylene oxide, 0OX-1101 (trade name, supplied by TQAGOSEI) and 0OX-121 (trade name, supplied by tqagOSEI). These epoxy resins

C: \ 2D-CODE \ 91-O9 \ 91114155.ptd Page 34 591054

垸 Resins can be used alone or in combination. When and / or epoxy ethylene resin is used in this hair ^

; Day :: Epoxy hardener and / ㈣ hardener can be used. The bad oxygen resin hardener is selected from generally known hardeners. Epoxy resin hardeners include imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, cyanoethyl-2-phenylimidazole, 1-cyanoethyl ^-' 2-ethyl-4-fluorenylimidazole, 2-phenyl-4,5-dihydroxyfluorenylimidazole, 2-phenyl-4_fluorenyl-5-hydroxyfluorenylimidazole; amine compounds such as dicyanodiamidate , Benzyl " difluorenylamine and 4-fluorenyl-N, N-difluorenylbenzylamine; and phosphine compounds such as scaly a. The ethylene oxide resin hardener may be selected from known cationic polymerization initiators. Commercially available products include, for example, SAN-AID SI-60L, SAN-AID SI-80L, SAN-AID SI-100L (supplied by Sanshin Chemical Industry Co., Ltd.), CI-2 0 64 (supplied by Nippon Soda), IRGACURE261 (Ciba Special chemical company), ADEKA0PTMER SP-170, ADEKA0PTMER SP-150 (supplied by Asahi Denka kogyo Industries), and CYRACURE UVI-6990 (supplied by Union Carbide Corporation). Cationic polymerization initiators can be used as epoxy resin hardeners. These hardeners can be used alone or in combination.

The compound having an ethylenically unsaturated group may be selected from compounds generally known to have an ethylenically unsaturated group. Examples include mono- and polyhydric (meth) acrylic acid esters such as 2-hydroxyethyl (fluorenyl) acrylate, 2-hydroxypropyl (fluorenyl) acrylate, polypropylene glycol di (fluorenyl) acrylate, Trimethylolpropane di (fluorenyl) acrylic acid SI, tris (fluorenyl propane tris (fluorenyl) propionate, isopentaerythritol tetra (meth) acrylate and diisopentaerythritol hexa ( Fluorenyl) acrylate;

C: \ 2D-CODE \ 91-O9 \ 91114155 .ptd page 35 591054 V. Description of the invention (30) Epoxy acrylates such as bisphenol A epoxy acrylate and bisphenol f epoxy propylene acid. These compounds having an ethylenically unsaturated group may be used alone or in combination. The photopolymerization initiator may be selected from generally known photopolymerization initiators. Photopolymerization initiators include, for example, α-diketones such as benzyl and diethylfluorenyl, acyloin ethers such as phenylfluorenylethyl ether and benzoin isopropyl ether, and thiaallionones such as sulfur S onion S, 2,4-diethylthio onion g, and isopropylthio onionone, benzophenones such as benzophenone and 4,4, -fluorene (diamido) diamine Acetophenone, acetophenones such as benzyl ketone, 2, 2, -dimethoxy ~ 2 ~ phenacetophenone and / 3- acetophenone, and aminoacetophenone such as 2-monomethyl -1- [4- (fluorenylthio) phenyl] -2-morpholinylpropionone and 2-benzyl-2 ~ diyl-1- (4-morpholinylphenyl) -butanone—丨. These polymerization initiators are used in combination. The photopolymerization initiator may be used alone or in combination of at least two known photopolymerization initiators. Photosensitizers include, for example, N, N-diamidinoethylbenzene. Agents N-dimethylaminoisoamylbenzoate, triethanolamine, and triethylamine bis, N. The thermal polymerization initiator can be selected from Commonly known thermal polymerization initiators include peroxides such as benzamyl peroxide, para-gas / bake 1 ° inclusions, di-third-butyl peroxide, diisopropyl, perylene— Ethylhexyl peroxycarbonate, and azo compounds such as acetone, etc. In addition, when manufacturing the present invention 3, adding known additives such as non-surface treatment agents, flame retardants, purple hardenable resin compositions, Color pigments, external light absorbers, antioxidants, defoamers, surface, and polymerization inhibitors as needed

C: \ 2D-C0DE \ 91-09 \ 91114155.ptd page 36 591054 V. Description of the invention (3)) or = regulator. Inorganic fillers include, for example, stones such as Celite, fused silica and amorphous silica, white carbon, titanium white, gas soluble, natural mica, synthetic mica, kaolin, clay, hydroxide, barium sulfate , E-broken, a-broken, c_glass, L_broken. The hardenable tree obtained in this way \ broken =-solder f photoresist composition, built-in wiring board branch 4 main layer adhesive, printing ink and coating materials. The hardened product of the present invention 3 can be obtained by hardening the first two gases according to a known method of sub-beam, ultraviolet light, or heat, for example, using an electric hardening resin composition. When the ultraviolet light is obtained, the present invention can be a mercury lamp, a medium mercury lamp, and -2! In the hardened 8 temples, a low-modification lamp can be used as ultraviolet light, and ultra-dust mercury lamps, gas lamps, and metal halides. The epoxy resin composition is a thermosetting resin composition 4 having excellent dielectric properties. Pot, two, wide plasticity and heat resistance = epoxidized phenyl duck compound epoxidation; the main function is: its suitable = used as a laminate epoxy resin composition. At first glance, it is mainly a knife. In other words, the present invention 4 provides a laminate which contains a number-average lipid composition represented by formula (I), has epoxy based on each end of the phenylene oligomer, and is divided into 20 to 3,000. As well as hardeners, chenqi compounds as ch3-ch-ch:

OH -CHj-CHCHj 2 [z] ^ ^ " Y- ° -CH ^ C] ⑼

C: \ 2D-CODE \ 91-O9 \ 91114155.ptd Page 37 591054 V. Description of the invention (32) Μ, where Y-〇_, a々b are defined as Formula ⑴, and Z and qd are defined as Formula (4 ), And n is 0 to] ^ c and d are as defined in the present invention 4 and further integers of 1-6. Containing a cyclohexyl resin composition represented by the formula (9), it has an epoxy based extension at each end: its molecular weight is 700 to 3, ⑽0, and it has an acid brewing resin as a component. Low polymer epoxy compound 'and cyanide resin composition, formula H; Description: At least R ?, D / 1 to negative, in epoxy formula (2,) with epoxy compound and hardener. Structure, wherein at least J of the table π-χ— is m = R9 is a hydrazone, and the random soil arrangement of formula (2,) 或 or formula (6) and formula ⑺ is M + Formula (6) or formula ring: ί!: 4Λ epoxy resin composition contains formula ⑻, which has a polymer epoxy compound at each end, ... a low dielectric constant 翔 2 :: reduce its melt viscosity . When the resin composition has voids, moldability is excellent. Qin Zhi-good in nature, will not give im :, formula (9) represented by the phenyl group with epoxy groups at each end = :; 物 ^ compound (hereinafter referred to as "双 官 自 园 _2Ep ”) Were called“ 2 = 〇〇-ca system through the formula phenylene ether oligomer (hereinafter ϊί) di νΐ \ (oxidative polymerization through divalent and -valent) Λ such as epigasol, in In the presence of the test, dechlorination is performed again. The powder can be separated from the reaction solution or the solution in the reaction solution.

P.38 591054 V. Description of the invention (33) The form is used. An embodiment of the manufacturing method of the dual palace energy PE0-2Ep of the present invention 4 will be shown. The formula (,)) represents ^ the aforementioned compound having a phenolic hydroxyl group at both ends and emulsified glycidol

An oil such as epichlorohydrin undergoes a dehydrogenation reaction in the presence of a base, thereby combining PE0-2Ep. The number average molecular weight of the bifunctional PE0-2Ep obtained in B is limited to the range of 700 to 3,000. When the average molecular weight of the aforementioned number exceeds 3, the viscosity of the tree body of the adult = increases. When it is less than 700, the mechanical strength or resistance is decreased. The aforementioned bifunctional PE0-2Ep has low melt viscosity, so its flow is south. Excellent compatibility with different resins. Because both ends contain epoxy, the resin composition containing the bifunctional PE0-2Ep has good adhesion ^. As a result, the resin composition can swell when exposed to high temperatures such as welding after absorbing water ... Because polyphenylene ether resin is a material with low dielectric, it can provide a laminate with low dielectric properties. Properties η, Ming 4 provides the epoxy resin composition forming agent for laminates, including-commonly used hardeners such as-grade amines and: amine hardeners such as grade amines' bisphenol A and phenol novolac hardening Agent, acid anhydride type ^ ^ and acid ester type hardener. These hardeners can be used alone or in combination. The bifunctional PE0-2E.P composition of the present invention can be determined according to / σ. A variety of resins are used. Specific examples of resins include various epoxy resins, modified epoxy resins, ethylene oxide resins, acrylic acid resins, methyl bis-diene, and tree-based compounds such as dipropylene benzene and dipropyl groups. Poly- = acid compounds such as N-vinyl-2-. Bis-pyridone and divinyl monomers such as unsaturated polyesters; polyfunctional cis-butyl σ + & bis-butene difluorene Amines

C: \ 2D-CODE \ 91-O9 \ 91114155.ptd page 39 591054 5. Description of the invention (34)-f amines; rubbers such as polybutadiene; thermoplastic resins such as polyethylene and polyethylene; Engineering plastics such as ABS resin and polycarbonate; and cyanic acid + grease. However, it is by no means limited to the aforementioned resins. ^ 文 ^ The composition of I and f may contain as many as needed. Addition of zibu such as known ..., osmium or organic additives, dyes, pigments, thickeners, moisturizing, coupling agents, photosensitizers, ultraviolet light absorbers and Flame retardant. The cyanate ester compound used in the present invention 4 includes, for example, benzene, 3 ~% ^ benzene, benzene, 1,3,5-tricyanate, 13- M 8 /, ^ = 1 2 its Γ dicyanonaphthalene, 丨, 3,6-Tricyanaphthalene, 4,4_dicyanobenzine: cyanocyanine) methane, 2, 2-fluorene (4-cyanophenyl) propane, 2, 2-fluorene (3, 1, 2) Benzene, propane, 4- (4-phenyl) ether, 4- (4-cyanophenyl), hydrazone (4-cyanophenyl) ¾, ginseng (4-cyanophenyl) phosphite, ginseng & phosphate Ester, 4, 4, -dicyano-3, 3, 5, 5, tetra-methyl biben, 4 ticks: —9 〇y ο ο > η gas, 4 1,2 milk, Z, 3 , 3,5,5'_Hexafluorenylbiphenyl, and novolacs should be obtained from cyanic acid S. 3 lacquer and cyanide inversion Although the 4 composition of the present invention is self-aggregated under heating, the heat hardening catalyst is The composition is used to increase the curing rate * °°, but can be blended and economically effective. Generally known thermal curing catalysts can be used for the resin's thermal curing catalyst for workability. The bifunctional PE0_2Ep composition layer is particularly suitable for copper cladding which requires low dielectric properties. The present invention 4 Ladle laminate can be separated by general methods, and leather printed wiring board into two brush was in solution in an organic solvent, the alkaline material: two two ..., curable resin to heat treatment to obtain a prepreg Shang

C: \ 2D-CODE \ 9l-09 \ 9lH4i55.ptd Page 40 The material is impregnated with a resin varnish & resin said, it is tested 591054 V. Description of the invention (35) Buried, then prepreg The green body and the copper foil are laminated and molded by heating to obtain a copper-clad laminate. However, the method for producing the copper-clad laminate of the present invention is not limited to this method. Organic solvents include acetone, methyl ethyl ketone, ethylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, toluene, xylene, tetrahydrofuran, and N, dimethyl methylamine. The solvent is not particularly limited and various organic solvents can be used. The solvents may be used alone or in combination. Substrates to be impregnated with resin varnish include substrates that are all used for thermosetting resin laminates. Examples include inorganic substrates such as glass cloths and glass nonwovens; and organic substrates such as polyamide nonwovens and liquid crystal polyester nonwovens. With the low dielectric properties of the present invention, it is possible to more effectively use a substrate having excellent dielectric properties, such as D glass cloth or NE glass cloth. Pre-✓ The heat treatment of the redundant material chain is appropriately selected according to the type and amount of the solvent used, the composition of the month, the added catalyst and other additives, but usually the heat treatment is performed at a temperature of 100 to 25 0 t for 3 to 30 minutes. The prepreg 1 and copper deposition layer and heating method are changed according to the type of prepreg chain and the form of copper foil. These materials are usually preferably hot-molded in a vacuum at a temperature of 70 to 230 ° t and a pressure of 10 to 30 kg / cm2 for 40 to [20 minutes. The tree hairpin Γ is a two-sealed epoxy resin composition containing an epoxy resin hardener, an inorganic filler, and an average molecular weight of 700 to 3,000, represented by formula (9). And at each end, a octopant compound was used as a component. * ,, the phenyl ether with a mother milk base is low driving according to the present invention 5, to provide a seal to obtain a 宓 ^ ^, a coating milk bismuth lipid composition, which can be 7 and 7 in the sealing layer, the The sealing layer will not show ρ when the weather is high, but at the same temperature, such as solder reflow, it has a low dielectric constant. According to this matter 5, provide the < & sealing epoxy resin composition 591054 V. Description of the invention (36) = is a better product, in which each end of the formula (9) has a benzyl group called oligomerization In the compound, -X-2R2, R3, R4, R8; ^ U, and at least one of R5, R6, and R7 of -X-is formazan,-,, or Y-is the formula (6) or The arrangement of formula (7) or the combination of formula (6) and formula (7) and, according to the present invention 5, there is provided a hermetically sealed ring-shaped composition according to the foregoing description, wherein an epoxy resin and a hardener are provided. Inorganic milk fineness: the total weight of the compound itself is the basis. The formula ⑻ is expressed at each end: oligomeric phenylene _ content of oligomeric compound is 1 to 60% by weight per pore. According to the present invention 5, a basis is provided. The tightness of the aforementioned is: Wai. Soil: Among them, epoxy resin, hardener, and diester are widely used. ^ The epoxy resin composition of Fan Yinshi Invention 5 with an inorganic filler content of 15 to 95% by weight contains a dibasic test oligomeric compound, so it has a low dielectric strength: Low melt viscosity.胄 Front 杓: Electricity: Number and excellent mechanical properties. At low time, the resin has good fluidity at the time of sealing molding; and, and the melt viscosity of the product is excellent. Youzi 'does not produce voids, and the bifunctional PEO-2Ep has excellent compatibility with low-glare resin groups. A further version of the cattle ", A, -A fork fluidity, and highly adhesive with epoxy resin composition Xuan! ^ End group has epoxy groups, so the tree results when the sealing layer is exposed to 俨; == 1 layer is heated The strength is excellent. Because the polybenzyl ether has: at the same temperature, cracks can be avoided. In addition, the sealing layer with low dielectric characteristics and materials with low electrical characteristics can be provided in the resin composition with low epoxy resin.

C: \ 2D-C0DE \ 91-09 \ 9lll4155.ptd Page 42 Sealability of the present invention 5 591054 Description of the invention (37) The total amount of functional PE0-2Ep and hardener is based on the bifunctional pE0-2Ep content It is preferably 1 to 60% by weight and more preferably 5 to 50% by weight. When the foregoing content is lower than the U weight ratio, cracks are liable to occur in the sealing layer. When the foregoing content is higher than 60% by weight, the melt viscosity is increased during sealing molding, so that cracks occur and moldability is reduced. The inorganic filler, which is a component of the sealing epoxy resin composition of the present invention, includes, for example, inorganic powders such as silica and alumina. The preferred content of none varies depending on the application. & ^ ^ For example, regarding the sealing material used in the manufacture of pottery for molding, the total amount of f, bifunctional PE0-2EP, hardener and inorganic filler is preferably 15 to 60% by weight and better than 20 to 50% weight two: this kind of towel used as a sealing material for pottery manufacturing molding :: = filler content is less than 15% by weight, the strength of the sealing layer is low, the content is higher than 60% At the weight ratio, the moldability of 'sealed molding' is reduced. Tian is also concerned with the use of close shot buckets for injection molding. ^ ^ Nengqing-2EP, hardener and inorganic filler \ = ^ Amount = Oxygen tree ^, Shuangguan ^ Amount is preferably 6. To kiss ratio and dagger. For this purpose, it is used as an injection molding sealing material: When the content of the filler is less than 70% by weight, the increase in the number of poor fillers is easy to cause cracks. When the aforesaid person / seal / reduction coefficient increases the melt viscosity during hermetic molding, it results in :: at 95% by weight, the aforementioned inorganic filler preferably uses a coupling ^ 家 # =, which is low. Compatibility with epoxy resin. Coupling agent example 2 is a modified glycidyloxypropyltrimethoxyxanthoxylate, including a hexaxylamine triylethoxysilane, and

591054 V. Description of the invention (38) N-phenyl-r-aminopropyltrimethoxysilane firing Keshu sealing epoxy resin composition In addition to epoxy resin, bifunctional PE0-2Ep agent, two release agents, colorants, barrier Fuel and stress reducer. r May: Π, 1 plus mountain speed: J, for example, one includes tertiary amines such as 1,8-diazabicyclo'its 7, diethylenediamine and xylylenediamine; imidazoles such as ^; Ethyl-4-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methyldimeter. Sit; organic phosphines such as tributylphosphine and tribenphosphine. Among them, triphenylphosphine can improve the electrical characteristics of the sealing layer, so triphenylphosphine is preferred. Taking, for example, T includes carnauba palm, stearic acid, brown acid and base water, for example, carbon black. The aforementioned flame retardant includes, for example, antimony trioxide. The force reducing agents include, for example, silicone gel, silicone, and silicone oil. According to this Maoming 6, regarding the printed circuit board material, a thermosetting resin composition is provided, which can meet the more demanding requirements of lower dielectric properties, and the conventional characteristic properties such as excellent moldability and heat resistance will not deteriorate. It also has a laminate capable of generating and using a xuan composition and a printed circuit board using the composition. Denichi The present invention 6 provides a resin composition for a laminate, which contains a formula (丨) Table Z 5 having a number average molecular weight of 70 0 to 3,0 0 and a local ether oligomer having #cyano groups at each end. Cyanate compound as a component, N = c- -Y-

〇—C 三 N (10) Two, where X, [〇-, & and 1) are defined as Formula (1) and 2, 0: and (1 is defined as Formula (4)

591054

The present invention also provides a resin composition for a laminate, which contains a phenylene ether oligomer cyanide having a number average molecular weight of 700 to 3,000 and represented by formula (10) at each terminal ^ An acid compound is used as a component, an ester resin and an epoxy resin. In addition to the neon, the present invention 6 provides a resin composition for a laminate according to the foregoing, wherein R2, R3, R4, and R9 of -X-1 are methyl groups, and -X- At least one of R5, R6, and "is methyl, and Y-0- is a random arrangement of formula (6) or formula (7) or a random expression of formula (6) and formula (7)

The resin composition for laminates provided by f invention 6 contains a phenylene ether low polymer cyanate compound based on cyanic acid. Therefore, the resin composition has low dielectric properties, excellent flexibility, and low melting. Body viscosity. When the melt viscosity of the aforementioned resin composition is low, the embedding property of the resin is good when the laminate is molded, and no gaps occur, so the moldability is good. In this issue, 6 provides a description of a diphenyl ether low-supporting cyanate compound of the formula (10) having a cyano group at each end (hereinafter referred to as "difunctional pE0-2cN") and a description of the bifunctional PEO- 2CN is obtained via a dehydrogenation reaction of a bifunctional pE0 of formula (1) and a cyanogen halide such as gasified nitrogen or desert cyanide in the presence of a test. The base typically includes, for example, tertiary amines such as triammine, triethylamine, tripropylamine, methylaniline and roar, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, calcium hydroxide, sodium carbonate , Potassium carbonate and sodium bicarbonate. Alkali is not limited to this. Dimethylben, aerobic, dichloromethane Typical solvents for the reaction include toluene

C: \ 2D-CODE \ 91-O9 \ 91114155.ptd

591054

^ Tetrakis fluorene, chlorobenzene, succinylbenzene, nitrate ^ methylfluorenone, tetrahydrofuran and dioxane. Solvent oysters, acetone, methyl ethyl. When cyanide is used, the reaction temperature is preferably limited to this. point). When cyanogen bromide is used, it is preferably _3〇t: to + 6C to + 13c (the number of bifunctional PE0-2CN thus obtained by the Buddha is flat f. 0 0 0 ^ ^ m two spoon spoon knife is limited to 700 to 3 〇〇〇。 Consumption. Keshu bifunctional PE0-2CN has a low life-saving self-reporting, as low as one ^ t eight 'low-force valley viscosity, so its fluidity is still good. Its compatibility with different resins is excellent In addition, because the beans have acid groups at each end, the resin composition containing bifunctional PE0_2CN has good and good adhesion. As a result, when the resin composition is exposed to high temperatures such as welding after absorbing water, swelling can be avoided. In addition, Since the polyphenylene ether resin is a material having two dielectric properties, a laminate having low dielectric properties can be provided. In the resin composition for a laminate provided in the present invention 6, the content of the bifunctional PEO-2CN is Based on the total amount of the bifunctional PEO-2CN epoxy resin and different cyanic resins, it is preferably in the range of 1 to 60% by weight and more preferably 5 to 50% by weight. When the foregoing content is less than 1% by weight, Not enough flexibility. When the aforementioned content is higher than 60% by weight, the melt viscosity increases, so the laminate Voids appear during production, resulting in a decrease in moldability. One component of the resin composition of the present invention 6, the cyanate resin includes, for example, 1,3- or 1,4-dicyanobenzene, 1,3,5_tri Benzene cyanate, 1,3-, 1,4 ~, 1,6-, 1,8-, 2,6-, or 2,7-dicyanonaphthalene, 1,3,6-tricyanonaphthalene, 4,4 -Dicyanobiphenyl, pyrene (4-cyanophenyl) methane, 2,2-pyrene (4-cyanophenyl) propane, 2, 2-pyrene (3,5-dibromo-4-cyanophenyl) propane贰 (4-cyanophenyl) ether, 贰 (4-cyanophenyl) sulfide, 贰 (4-cyanophenyl) block, ginseng (4-cyanophenyl) phosphite, ginseng (4-cyanobenzyl) Group) phosphate ester, 4, 4'-dicyano-3, 3 ', 5, 5'-tetramethyl

C: \ 2D-C0DE \ 91-09 \ 91114155.ptd Page 46 591054 V. Description of the invention (41) " ---- 2benzene, 4, 4 '—Dicyanide-2, 2, 2, 3, 3 , 5,5,6-hexamethylbiphenyl, and cyanate esters obtained by the reaction of phenolic varnish with cyanide. As the one component of the resin composition of the present invention 6, the epoxy resin disclosed in the present invention 3 can be used as the epoxy resin. First, the resin composition for a laminate provided by the invention 6 is used in accordance with the purpose or use group. Specific examples of resins include various ethylene oxide resins, propane, and methacrylates; polyallyl compounds such as diallyl and allyl terephthalate; vinyl compounds such as N-vinyl -2-Houkou mouth aldosterone and diethyl, knee deficient • Human winter officials such as monomers of polymerized double bond T · ^ ene 3 such as unsaturated polyesters; γ ·, dilute dimer imines; Polyimide; rubbers such as polybutadiene, resins such as polyethylene, polystyrene, and ABS; engineering plastics, such as polycarbonate and polycarbonate. However, it is by no means limited to the aforementioned resins. In addition, the resin composition phase is rich and may contain various additives, for example, known as Γ | 1 person [additives, dyes, pigments, thickeners, lubricants, lubricants, plastics, plastics, etc. "[Photosensitizer, external light absorber, and flame retardant. Ramie II Invention 6 composition hardens itself under heating, but it can be mixed with, or ^ sensitizer in the composition to improve hardening ^ ^ ^ 7 A commonly known thermosetting catalyst is used as the thermosetting catalyst for the resin used in combination with A M Φ. Group #, ϋι ί Copper coating of the resin composition for laminates provided in January 6 > & Printed circuits requiring low dielectric properties: build-up = copper-clad build-up is based on a conventionally known method, in which the substrate is replaced with resin, raw material, resin, or main. It is a method in organic solvent 2: : Shellfish varnish is a thermosetting resin composition. The night substrate is heated to obtain a prepreg.

C: \ 2D-C0DE \ 9l-09 \ 9Hi4i55 ptd Page 47 591054 V. Description of the Invention (42) _ The method of obtaining the copper laminate by laminating and molding the impregnated blank and copper box is not limited to this method. Layer. But copper cladding As for the organic solvent used in the ladle lamination, this: the base of grease varnish #, heat treatment conditions, etc., can make it impossible to expose materials and conditions. Ming 4 has been provided by the present invention 7-the formula (i) is represented by (fluorenyl) acrylate compound 0-Z1 ~ -〇Ύ- · | 〇Χ〇 | --Υ〇—— R15 (11) Φ, 7 ' , A 2 5 is a hydrogen atom or a fluorenyl group, χ—, Υ—0 a, aAb is defined as formula ”,,; an organic group having no branched hydroxyl group, containing one or m or more carbon atoms, which may contain A,,, and milk atoms, and c and d are defined as in formula (4). ^ According to the present invention 7 ', a (fluorenyl) acrylate according to the foregoing description = a substance' is provided in formula (11) () In the acryl) acrylic acid compounds, 1-by-1 ', Y0 has a formula of formula (6) or formula (7) or a formula of formula (6) and formula (7) randomly arranged. According to the invention 7' According to the aforementioned (fluorenyl) acrylate compound, ΐίννη /, τΒ〇—has a structural formula of formula (7). According to the invention 7 ', there is also provided a hardenable resin containing the aforementioned (fluorenyl) acrylate compound. The (meth) acrylate compound of the present invention can be self-polymerized, or can be copolymerized with different compounds, thereby obtaining heat resistance and The excellent electrical characteristics molecule Q ϊ material and a photosensitive resin composition of the present invention is based via a combination of

591054 V. Description of the invention (43) Used for photoresist resins, composite wiring board resins, and liquid external fluids " " " Panel color filter materials, UV first coating composition, a variety of coating material adhesives Etc. In the preferred formula (11), R2, R3, R4, and R8 are also pQ. 7 1 浯 工 今 β 甘 π Κ8 and ruler 9 contain 3 or less carbon atoms = ^ element group, R5, R6 And R7 is a hydrogen atom or a lesser group containing 3 or less carbon atoms, R10 and R11 are 3 or less #; ^. P1Q ^ ^ ^ ^ 勹 3 〇1U ^ alkyl anti-atoms below, and R12 and R13 are lice atoms or alkyl groups containing 3 or less carbon atoms. More preferably, R2, R3, R4, R8 and R9 are methyl groups' R5, and "is a fluorene atom or a fluorenyl group, and R10 and R11 are methyl groups And R12 and R13 are a hydrogen atom or a methyl group. An organic group having no branched hydroxyl group and one or more carbon atoms (may contain an oxygen atom and may be located at Z ,.-(Z, -〇)-including, for example, _ ((Ch2) "〇) _,-(CH2C deleted And-(CH2-Ar-0)-, but not limited to this. The adding method includes a method of directly adding organic ^ to an intermediate product represented by formula (1); and a method using a functional compound, but not limited to this And other methods. There is no particular limitation on the method for producing the (fluorenyl) acrylate compound of formula (1 1) provided by the present invention. The (fluorenyl) acrylate compound of formula (1 1) can be produced by any method. For example, the formula ( 11) (fluorenyl) acrylate compounds are obtained from (12) compounds reacted with (fluorenyl) acrylic acid or (fluorenyl) acrylic acid derivatives. Specifically, (fluorenyl) acrylate compounds of formula (Π) The obtained g = is obtained through the compound of formula (12) and (fluorenyl) acrylic acid in an esterification catalyst such as p-xylenesulfonic acid, trifluoromethanesulfonic acid or sulfuric acid or an acid thereof in the presence of an organic amine, hydrogen In the presence of sodium oxide or sodium carbonate, in a solvent such as benzene, dibenzobenzene, cyclohexane, n-hexane , N - heptane or a mixture of:

C: \ 2D-CODE \ 91-O9 \ 91114155.ptd Page 49 591054 V. Description of the invention (44) The reaction temperature is preferably 70 ° C to 150 ° C. The compound of formula (1 2) is produced, for example, by the method disclosed in Japanese Patent Application No. 2000-1119 6 5 6 9 and then introduced if necessary-(Z '-0 )-obtain. (12) wherein -X-, Υ-0-, a and b are defined as in formula (1), ζ is an organic group having no branched hydroxyl group, one or more carbon atoms, and one oxygen atom, and c and d is defined as equation (4).

For example,-(CH2) m0- or _ (CH2CHRi4〇) n ~ will be introduced as an example of-(z, -10). -(C Hz) m 0-is introduced via the compound of formula (1) and the alcohol represented by formula (1 3) in an appropriate solvent such as alcohol, ether or ketone in a strong test catalyst such as potassium hydroxide, potassium carbonate, Or introduced in the presence of sodium ethoxide; and-(CI ^ CHRhO),-is introduced via a compound of formula) and an epoxy resin represented by formula (14) in a benzene solvent such as benzene, toluene, or dimethylbenzene X- (CH2) m-OH (13), introduced in the presence of a basic catalyst such as potassium hydroxide, sodium ethoxide or triethylamine by a reaction according to the method disclosed in JP-B-52-4547

Where X is gas or bromine 'and m is an integer of 2 or more, R16 where R16 is a hydrogen atom, methyl or ethyl. Next, the hardenable resin composition of the present invention 7 will be explained. Hardenable resin

C: \ 2D-CX) DE \ 91-09 \ 91114155.ptd Page 50 591054 5. Description of the invention (45) The composition is characterized in that it contains the aforementioned (fluorenyl) acrylic acid g compound of the present invention. The hardenable resin composition of the present invention contains a known epoxy resin, ethylene oxide resin, an ethylenically unsaturated compound, a photopolymerization initiator and / or a thermal polymerization initiator, and a photosensitizer. As for the aforementioned epoxy resin, ethylene oxide resin, and compounds having an ethylenically unsaturated group, those resins and compounds already disclosed in the present invention 3 can be used. When an epoxy resin and / or an ethylene oxide resin is used in the hardenable resin composition of the present invention, an epoxy resin hardener and / or an ethylene oxide resin hardener may be used. As for these hardeners, those hardeners disclosed in the present invention 3 can be used. As for the photopolymerization initiator, photosensitizer, and thermal polymerization initiator, those materials which have been disclosed in the present invention 3 can be used. In addition, when manufacturing the hardenable resin composition of the present invention 7, known additives such as inorganic fillers, color pigments, defoamers, surface treatment agents, flame retardants, ultraviolet light absorbers, antioxidants, A polymerization inhibitor and a flow regulator are disclosed in the production of a hardenable resin composition of the present invention 3. The hardenable resin composition thus obtained is suitable for various applications such as soldering photoresist compositions, composite wiring board materials, insulating coatings, adhesives, printing inks, and coating materials. EFFECT OF THE INVENTION According to the present invention, a difunctional phenylene ether oligomer is provided, which is sufficiently soluble in a ketone solvent and has compatibility with a thermosetting resin. Example 2 A varnish for a laminate and a moldability Excellent laminate. According to this

591054 V. Description of the invention (46) The agent is modified to have a compound and a capacitive property. Laminated materials are low dielectric properties. These are excellent materials for 1¾, photoresist, oxidation, good electrical insulation, or multi-layer reliability. The invention of the circuit provides a low polymer having terminal phenolic hydroxyl groups. The basics of the present invention are easy for you; ketones dissolve as a basic structure, and are electrical and electronic materials that are characteristic of PPE polymers similar to engineering plastics. It is soluble in general solvents, and is different from different thermosetting resins. This is easy to oligomerize by the thermosetting phenylene ether of the present invention. According to this: Ming 'provides an epoxy acrylate resin with a high glass transition temperature of two and? I electrical loss tangent value. From the nature of 6, the epoxy acrylate compound of the present invention is a significantly functional high molecular weight material, I Widely used as thermal and electrical properties for various coating agents, UV coating compositions, adhesives and laminates. According to the present invention, a resin composition containing a phenylene ether oligomer ring is provided. This resin composition has high heat resistance and insulation properties, such as low dielectric constant and low dielectric loss tangent value, good moldability and good balance. The printed wiring board using the laminate of the resin composition of the present invention is used in It can be molded well in multi-layer molding, has high-speed processing that can further obtain high-frequency wave signals, and has a low diminution degree. According to the present invention, it provides a dual-functionality? £; 0-2 £? Epoxy composition, which can obtain a sealing layer, when exposed to solder reflow, etc.

591054 — V. Explanation of the invention (47) There will be no step reliability and temperature transmission at low temperature, and the dielectric constant will be low. In this way, a semiconductor device having a highly reliable chip circuit with excellent speed can be provided. The good balance of materials is phenylene ether low polymer cyanide and low dielectric properties. The resin composition has high heat resistance. Composition ... Material; excellent flexibility and flexibility. ❹The circuit design of the resin molding of the present invention, which has a two-layer or thin-layer printed wiring board that can be handled well in multilayer molding time and has low loss. The high-speed invention of the X-frequency wave ^ provides a conversion temperature of acrylic acid compounds, has a low dielectric constant and; ", 焉 glass is obviously applicable to high-functional high molecular weight materials: 2 tangent value, so the gas properties Materials for various coatings, dual-use as thermal and electrical adhesives, photoresist and combined printed wiring & button light coating composition, examples, materials. The examples and comparative examples will be specifically described in this section. It is limited to these examples. The number average molecular denier is two months, but the present invention is not only ^ ^ ^ ^ ^ ^ W (GPC) ^ ^ GPC curve and molecular weight calibration curve are performed. Eighty-seven, science and technology As shown in the following formula, the relationship between the standard calibration curve and the calibration curve system is obtained.

LogM = A〇ΧΗΑ, χ2 + Α2χ + Α3 + Α4 / χ2 where M ·· Molecular weight, X: Elution time ~ 1Cj Octahydroxy equivalent is based on 2, 6-dihydrophenol as standard reference and coefficient . (Solution cell method) Absorption at 3,600 cm-1: Tea village materials are analyzed by IR ** Difficulty determination for humans.

591054 V. Description of the invention (48) Example 1 A slender reactor with a volume of 2 liters and equipped with a stirrer, a thermometer, an intake pipe and a baffle was fed with 2.7 grams (0.012 mol) CuBr2, 70. 7 grams (0.55 mol) of di-n-butylamine and 600 grams of fluorenylethylfluorenone. Each component was stirred at a reaction temperature of 40 t, and 55.7 g (0.21 mol) of divalent phenol (2, 2 ,, 3, 3 ', 5, 5'-hexafluorenyl- [1, Γ-Biphenylbu 4, 4, diphenol) (a) and 50. 4 g (0.41 mol) of 2, 6-diphenol in a mixed solution of 600 g of ethyl ethyl fluorenone (Mole ratio of divalent phenol: monovalent phenol = 1: 2) was added dropwise to the reactor over 120 minutes while aeration of 2 liters / minute of air was passed. After the addition was completed, the mixture was stirred for 60 minutes while continuously passing in 2 liters / minute of air. An aqueous solution of ethylene diamine tetraacetic acid disodium dihydrogenate was added to the reaction mixture to end the reaction. It was then washed three times with a 1 N aqueous hydrochloric acid solution and then with pure water. The solution thus obtained was concentrated by an evaporator, and then suction-dried to obtain 100 · 3 g of a reaction product. The reaction product has a number average molecular weight of 650, a weight average molecular weight of 81, a hydroxyl equivalent of 3 10, and is soluble in methyl ethyl ketone. The aforementioned resin will hereinafter be referred to as "(c)". ", Example 2 The same slender reactor used in Example 1 was fed with 1.3 g (0.013 mol) of CiiCl, 79.5 g (0.62 mol) of di-n-butylamine and 6 0 0 Grams of ethyl ethyl ketone. Each component is stirred at a reaction temperature of 40 ° C, and by dissolving 4 .8 g (0.16 mol) of divalent europium (2, 2, 3, 3, 5, 5, 5- Hexamyl- [1,1'-biphenyl] -4, 4, -diphenol) U) and 75.6 g (0.62 moles) of 2, 6-dimethylformate to 600 g of methyl ethyl The mixed solution obtained from fluorenone (divalent phenol: monovalent mol ratio = 1: 4) was added dropwise to the reactor at 120 minutes while 2 liters / minute of air was introduced.

C: \ 2D-CODE \ 91-O9 \ 91114155.ptd Page 54 591054

V. Description of the Invention (49) Qi. After the addition is complete, stir for 30 minutes while continuing to introduce 2 liters / minute of air. The termination of the reaction, washing, concentration, and suction drying were then performed in the same manner as in Example 1, whereby 1 1 · 4 g of a reaction product was obtained. The reaction product has a number-average molecular weight of 1,110, a weight-average molecular weight of 1,450, and a group equivalent of 5,80, and is soluble in fluorenyl ethyl ketone. The aforementioned resin will be referred to as " "(d)" hereinafter. Example j Feeding in the same slender reactor used in Example 1 丨 · 1 g (〇. 〇 丨 丨 Mohr) CuCl, 66.3 g (0.51 Molar) di-n-butylamine and 50 g 曱Ethyl ethyl fluorenone. Each component was stirred at a reaction temperature of 40 ° C, and 20.9 g (0.077 mol) of divalent phenol (2, 2, 3, 3, 5, 5, 5-hexamethyl, 1 Biphenyl] -4, 4'-diphenol) (a) and a mixed solution of 75.6 g (0.62 mole) of 2, 6-diphenol in 600 g of fluorenylethylfluorenone (divalent phenol: 1 The mol ratio of valence phenol = 1 · 8) was added dropwise to the reactor over 120 minutes while aeration of 2 liters / minute of air was passed. After the addition is complete, stir for 30 minutes while continuing to introduce 2 liters / minute of air. The termination of the reaction, washing, concentration, and suction drying were then performed in the same manner as in Example 1, whereby 91.4 g of reaction product was obtained. The reaction product has an f-number average molecular weight of 7,000, a weight-average molecular weight of 2,300, and a hydroxyl group of 820, which is soluble in fluorenylethylfluorenone. The aforementioned resin will hereinafter be referred to as "(e)". Example 4 Use = The same elongated reactor used in Example 1. 111-9 grams of reaction product was obtained in the same manner as in Example 2 & The mixed solution used in Example 2 was replaced with a mixed solution (divalent phenol: monovalent phenol mole ratio = 1: 4),

591054

The mixed solution was dissolved in 41.8 g (0.15 mol) (2 2,3 3,5 5'-hexamethyl- [1, Γ-biphenyl] -4,4'-diphenol) (a) , 56.'7 grams (0,46 moles of 2,6-dimethyl alcohol and 2 ^ g (0.16 moles) of 2,3,6-trimethylamine were obtained at 600 grams of methyl ethyl ketone. The reaction product has The number average molecular weight is 1,000, the weight average molecular weight is 1,350, and the hydroxyl equivalent is 52. It is soluble in fluorenyl ethyl ketone. The aforementioned resin will hereinafter be referred to as "(^). Comparative Example 1" Example 1 was used Feeding the same slender reactor 丨 · 3 grams (〇.〇13 莫耳)

CuCl, 79.5 grams (0.62 moles) of di-n-butylamine and 60 () grams of methyl ethyl fluorene. Each composition was stirred at a reaction temperature of 40 ° C, and 37.4 g of < 啰 (0.16 mole) divalent phenol (3,3 ', 5,5'-tetramethyl- [1,1, Monobiphenyl] -4, 4'-diphenol) (b) and a mixed solution of 75.6 g (0.62 mol) of 2, 6-diphenol in 5 2 g of methyl ethyl fluorene (divalent brewing: The univalent mol ratio (1 · 4) was added dropwise to the reactor over 120 minutes while aeration of 2 liters / minute of air was passed. After the addition is complete, stir for 30 minutes while continuing to introduce 2 liters / minute of air. An aqueous solution of ethylene diamine tetraacetic acid disodium dihydrogenate was added to the reaction mixture to end the reaction. The solid was recovered by filtration. The resulting solid was then washed three times with methanol. The obtained solution was concentrated by an evaporator, and then suction-dried to obtain 80 g of a reaction product. The reaction product has a number average molecular weight of 5,300, a weight average molecular weight of 9,000,000, a hydroxyl equivalent of 3,800, and it is insoluble in methyl ethyl melamine. The aforementioned resin will hereinafter be referred to as "(g)". Comparative Example 2 The same slender reactor as used in Example 1 was fed. 3 g (0. 3 Mo) of CuCl '48.7 g (0.62 Mole) of pyridine and 600 g of 曱 ethylethyl 曱ketone

C: \ 2D-CODE \ 91-O9 \ 91114155.ptd Page 56 591054 5. Description of the invention (51). Each component was stirred at a reaction temperature of 40 ° C, and dissolved in 4 丨 .8 grams (〇 ·· 6 mol) of divalent brewing (2, 2, 3, 3 ', 5, 5'-hexamethyl_ [1 ， [,-Biphenyl] -4,4-dihydrazine) (a) and 75.6 g (0.62 mole) of 2, 6-xylenol in a mixed solution of 520 g of methyl ethyl fluorenone (divalent Phenol: Molar ratio of monovalent phenol = 1 ·· 4) was added dropwise to the reactor over 120 minutes while aeration of 2 liters / minute of air was introduced. The termination of the reaction, washing, concentration, and suction drying were then performed in the same manner as in Example 1, whereby 10.2 g of a reaction product was obtained. The reaction product had a number average molecular weight of 1,100, a weight average molecular weight of 1,820, and a hydroxyl equivalent of 600. The aforementioned resin will hereinafter be referred to as "(h)". Table 1 shows the results of the examples and comparative examples. According to Examples 1, 2 and 3, when the molar ratio of monovalent age is increased, the number average molecular weight and weight average molecular weight are increased, and a bifunctional low polymer having a predetermined molecular weight distribution can be obtained by changing the molar ratio. According to the results of Example 2 and Comparative Example 1, when a 2-position (R4 of formula (2)) without a bisphenol (3, 3 ', 5, 5'-tetrafluorenyl- [ΐ, ι (, -Biphenyl] -4,4, -diphenol) as a divalent compound and used as a raw material, a low polymer having an average molecular weight greater than 5,000 is produced. Unable to efficiently synthesize a bifunctional phenylene group soluble in methyl ethyl fluorenone. In other words, the presence of a substituent at the 2-position (R4 of formula (2)) has a substituent for efficient synthesis of soluble in ethyl ethyl Required for difunctional phenylene ethers of fluorenone. According to the results of Example 2 and Comparative Example 2, when di-n-butylamine was used as the amine, a low polymer having a sharper molecular weight distribution than the low polymer obtained using pyridine was obtained. According to the results of Example 2 and Example 4, compared with the case of using 2,6-dioxine alone as the one-value test, using 2,6-dimethylphenone and 2,3,6-

C: \ 2D-CODE \ 9b〇9 \ 91114155.ptd page 57 591054 V. Description of the invention (52) When the trifluorene mixture is monovalent, an oligomer having a lower molecular weight can be obtained. The reason is that the 3-position fluorenyl group of 2, 3, 6-trisphenol can avoid polymerization and prevent the generation of polymers.

Ex.] Ex. 2 Ex. 3 Ex. 4 CEx.] CEx. 2 resin cdefgh divalent phenol aaaaba Mole ratio M 2 4 8 4 4 4 amine · 2 AAAAAB Μη 650]? 1 1 0 1,700], 000 5,300 u 00 M w 8 1 0], 450 2,300 1,350 9,000 1,820 Μ η / M w 1.25 1.3 1]. 35 1.35 1.70]. 65 Hydroxyl equivalent 3 1 0 580 820 520 3,800 600 Solubility μ 〇〇〇〇〇〇〇 1 E X. = Example, CEX · Two Comparative Examples * 1: Molar ratio: 2,6-xylenol / divalent phenol wood 2: A: Di-n-butylamine, B: Rotidine * 3: Yu Yan Solubility of ethyl ethyl fluorenone Example 5 A reactor equipped with a stirrer, a thermometer and a dropping funnel was cooled to -10 ° C. 200 ml of a dichloromethane solution containing vaporized cyanide (0.129 moles) was placed in a reactor. Then, by dissolving 5 0. 0 g (hydroxy 0. 0 8 6 mol) of the obtained phenylene ether oligomer (bifunctional PEO) and 13.1 g (0.129 mol) of triethylamine in 2 5 A solution of 0 g of fluorenylethylfluorenone was dropped in 60 minutes.

A: \ 9ni4155.pld page 58 591054 V. Description of the invention (53) ′ f f: Add dropwise, keep the temperature of the reaction solution at 10. . Or below. Add Ming Wu Yong to stir for 60 minutes. Then wash 3 = with 0.1N hydrochloric acid aqueous solution. j 1 was washed with pure water, and further filtered to remove the salt and heterozygous sulfonium 5 曱 and methyl ethyl fluorenone from the resulting solution by evaporation and removal, and ^ Γ 'was obtained to obtain 5.1 g of a cyanate compound. According to the obtained cyanide compound r, the absorption peak of the dihydrazone-based hydroxyl group °, _cm ') disappeared and the derivative derived from cyanobis: 0 / ^ 2, 250cm M), so it was confirmed that all functional groups were changed ^ Servants 1 5 ratio Adding tin octoate to 100 parts by weight, the resulting hard dimerization, degassing, and molding are carried out at 16 ° C, and are hardened by kinetic energy at 23 ° C. The hardened product has a glass-breaking transformation temperature. The amount is 242 ° c. Its dielectric constant at 1GHZ is 2.73 and; the tangent value of the electrical loss is 〇〇〇〇61. _ Example 6 π 1. 9 grams of bifunctional PE0 system to achieve the energy PEE has Number average molecular weight !, _, weight gate method eight ^ Fu Yue. 1 Lu and hydroxyl equivalent 520. Buy ten equal knife 篁 1,350 50. 8 grams of cyanate compound Example 5 will be the same as Example 5 The second one containing cyanogen chloride (〇129 mol) was removed, and the dichloromethane and chloroform containing methylene chloride (0.144 mol) was mixed with (0 129 mol) of r glue.尨. R alkane cold liquid 'generation' and 13 ;; [gram • mole] diethylamine based on 4.6 grams (0.144 mole) based on the R fraction of the obtained cyanate compound吣 έ ~ # Substituted by ethylamine. M—]) disappeared, and ran out of its own; = Γ The radical absorption peak (3,600% confirms that all functional groups have changed.) It is seen in the text that the obtained cyanate compound is similar to the example 5 way processing to get the hard page 59: C: \ 2D-00DE \ 91-09 \ 93n4J55.ptd V. Description of the invention (54) Ϊ tt ^ ", J * ^ ^ ^ ^ The damage tangent value is 0. 0053 The dielectric constant is 2.70, and the dielectric 3L of Example 7 is equipped with 槚; a stirrer, Wen Tang Ji Nai, and 40. 〇Ϊ in the reactor of the dropping funnel are fed into 40. 〇 = = ί: executive Example 1 The obtained bifunctional PE0 and 36. · gram of surface milk S. The compound was heated to 丨 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 矿 矿 矿 乙 sodium ethoxide in 250 grams of ethanol after 71 ^ by dissolving 10.5 grams (〇丨 55 Add dropwise over time. Add ΐcheng Desi Luo solution from the dropping funnel to 7JC ^ ^ ^ yjL r. U 70 羑 for 60 minutes, stir for 5 hours. Then return the water / valley with ο. 1 N salt Wash the strips 3 times, and then wash them with έΑ to remove the salt and impurities ^; the strips are further washed with v miscellaneous excess epichlorohydrin. The IR of the compound is distilled off from the resulting solution. According to the bile analysis, the obtained epoxy is derived from the Y Ganfeng (3,6GQ cm—disappeared, all functional groups have been transformed into glycerol peaks, so it is confirmed that all 3 parts by weight m_2_methyl odor thus obtained epoxy compound. at 15〇ν 1 ^ main 1⑽ 仞 weight ratio to 18 ... hardening]. obtained in hours = outgassing and molding, elasticity (_ measured with glass 2 7 hard / The dagger product is 2.75 according to the dynamic sticking number and the dielectric loss tangent value is 0. Example 8 US == ΐ ”water washing service, but Example 3 of 50. A gram of methyl ethyl succinic acid was replaced with 600 grams of methyl ethyl fluorenone in Example 3 and replaced with 600 grams of methanol.

591054

Solution powder volume. Part 0 of double V was obtained by concentrating with a hair dryer to obtain 70% of a bifunctional PE 〇Benzene tf solution.-Concentrated, suction-dried to obtain Lu Yue bPEO has a number average molecular weight of 162, weight average Divided into 2,180 and hydroxyl equivalent of 81. Method for producing dilute propyl compound

, = 71.4 g (hydroxyl 0.062 mol) of Luojie, the aforementioned 70% bifunctional pEα, solution and 14.9 g (0.123 mol) allyl bromide in 150 g of dichloride The solution obtained from the oxane and 120 ml of a 1 N aqueous sodium hydroxide solution were placed at room temperature in a reactor equipped with a stirrer and a thermometer. Further, 2.2 g (20062 耳) of trimethyl n-butylammonium bromide was added as a phase transfer catalyst to the reactor. The mixture was stirred for 5 hours. Then, it was washed three times with an aqueous solution of hydrochloric acid HCl: then washed with pure water, and then filtered to remove the produced salts and impurities. Dioxane was distilled off from the obtained solution, and suction-dried to obtain a 5 · 1.5 dilute propyl compound. According to the R analysis of the obtained allyl compound, the absorption peak (3,600 cm-1) of the age-based group disappeared, and the peak derived from the enene peak appeared according to NMR analysis, so it was confirmed that all functional groups were changed. earth

Melting, degassing and molding of allyl compounds are performed at 150 ° C, and hardened at 230 ° C for 3 hours to obtain hardened products. The hardened product has a glass transition temperature of 216t as measured by dynamic viscoelasticity (DMA). Also, its dielectric constant at 1 GHz is 2.67, and its dielectric loss tangent value is 0.005. Wei Comparative Example 3 3 parts by weight of 1-benzyl-2 -fluorenyl flavor. Add to 100 parts by weight of 3,3,5,5-tetramethyl- [1,1'-biphenyl] -4,4'-glycidyl bond, which is a biphenyl ring for semiconductor sealing materials Oxygen resin. The mixture is melted, degassed and

591054

It was molded at 150 ° C and then hardened at 180 ° C for 10 hours to obtain a hardened product. The hardened product has a glass transition temperature of 1 3 3 t as measured by dynamic viscoelasticity (j) M a). The dielectric constant at 1 GHz is 3.06, and its dielectric loss tangent is 0.0 3 0. ", Up to comparative example 4

3 parts by weight of benzyl-2-fluorenimidazole was added to 100 parts by weight of a dicyclopentadiene-type epoxy resin for a semiconductor package. The mixture was melted, degassed, molded at 150 ° C and then hardened at 180 ° C for 10 hours to obtain a hardened product. The hardened product has a glass transition temperature of 18 2 ° C as measured by dynamic viscoelasticity (DM A). Its dielectric constant at 1 GHz is 2.90, and its dielectric loss tangent is 0.020. The dielectric constant and the tangent of the dielectric loss are obtained according to the cavity resonance oscillation method. Table 2 shows the foregoing results. Table 2

E x. 5 E x. 6 Ex · Ί Ελ.8 CE x. 3 CE x. 4 Dielectric constant (] GHz) 2.73 2.70 2.75 2 · 6 7 3.06 2.90 Dielectric loss tangent 値 0.006] 0.0053 • 0.0] 40 0.0035 0.030 0.020 (] GHz) Ding (DM A) / ° C 242 25]] 97 2 1 6] 3 3] 82

Ex. Two Examples, CEx · = Comparative Example Example 9

C: \ 2D-CODE \ 91-O9 \ 91114155.ptd Page 62 591054 V. Description of the invention (57) The slender reaction of the dual-functional PE0 with a volume of 2 liters and equipped with a stirrer, thermometer, intake pipe and baffle The device was fed with 11.3 grams (0012 moles) of CuCl, 70.7 grams (0.55 moles) of n-butylamine, and 400 grams of methyl ethyl ketone. Each composition was stirred at a reaction temperature of 40 ° C, and 432 g (0 16 mol) of divalent phenol (2, 2, 3, 5, 5, 5'-hexamethyl- [1, Γ-biphenyl) was dissolved through dissolution. ] -4, 4, -diphenol) and 58.6 g (0.48 mol =) 2,6 dimethyl formaldehyde was tested at 800 g of methyl ethyl ketone, and the solution was added dropwise over 120 minutes. The reactor was vented with 2 liters / minute of air at the same time. After the addition is complete, it is sucked out for 6_0 minutes while continuously passing in 2 liters / minute of air. Aqueous ethylenediaminetetramethylene disodium hydrogen solution was added to the reaction mixture to end the reaction. Then t one t two t f = liquid wash three times, and then wash the strips with pure water. The solution thus obtained was PEO. The low polymer was ordered to obtain 96_7 grams of difunctional, in, R, and octyl groups with an average molecular weight of 810, a weight average molecular weight of 1,105, and a base equivalent of 475. Synthesis of epoxy compound 4 Γ ^ A0 1 1 ^ VI degree leaf and dropping funnel were fed into the reactor with 50 grams of gal)) Λ as dissolved in 30 grams of ethanol ^ from the solution / solution 8.6 grams (◦ · 13mol) After the addition of sodium ethoxylate is completed, the small Japanese sun drop is mixed; the bucket is added dropwise over a period of 60 minutes. Then, it was performed with pure water; and then 3 salts and impurities were washed out with an aqueous solution of hydrochloric acid. The excess table "ί, 4 steps of filtration to remove the dryness produced to obtain 53.2 grams of epoxy resin solution steam-saturated removal, suction suction dry analysis, coffee base absorption of two substances"; = epoxy compound ㈣ (3, 60 cm) disappeared, according to NMR

C: \ 2D-CODE \ 91-O9 \ 91114155.ptd page 63 591054 V. Description of the invention (58) Thornthorn: The peak of raw glyceryl ether dihydrate appears in 5 ′, so it is confirmed that all functional groups have been transformed. The resin has a number average molecular weight of 965, 1,213 and an epoxy equivalent of 543. Ten spoons of a thousand miles of oxyacrylic acid [synthesis of dagger compound, = blender, thermometer, and reflux reactor were fed with 25 grams of the former compound, 3.3 grams of acrylic acid, 20 grams of carbidol acetate, 013 g of diphenylphosphine and 13 mg of hydroquinone ether. The mixture was heated to 120 t and allowed to react with stirring. The acid value was measured during the reaction, and the reaction continued until the acid value became 2 μg 1 (011 / g. The stirring time at 120 ° was 5 hours. The reaction solution was diluted with 40 g of methyl ethyl ether. Add dropwise to methanol to obtain 1 again. 1 Recover solids by filtration, and then suction dry to obtain 25.2 grams of framed oxyacrylate compounds. Epoxy acrylate compounds have a number average molecular weight of 1,375 and a weight average molecular weight of 1 Example 1010 g of the epoxy acrylate compound obtained in Example 9 was melted, degassed, and molded at 150 C, and then hardened at 200 ° C for 6 hours to obtain a hardened product. Example 1 1

6 g of the epoxy acrylate compound obtained in Example 9 was dissolved in 4 g of carbidol acetate, and 0.6 g of Darocur 1173 (a photopolymerization initiator supplied by Ciba Specialty Chemicals Co., Ltd.) was added to the solution to obtain a resin composition. Resin Composition 1 Do not apply to the surface of the copper clad laminate with a screen printing machine, and then dry it at 30 ° C with a hair dryer. The patterned film was placed on the coating, and the coating was exposed to an ultraviolet light irradiation device (supplied by EYE GRAPHICS: UB0 151, light source: metal halide lamp) at 2,000 millijoules. After exposure, display with fluorenyl ethyl fluorenone

591054 V. Description of Invention (59) Shadow. When only the unexposed part is dissolved, the hardened product develops the pattern. Ethyl ethyl sulphate is used to obtain resin K54 0 0). "The damage strength of the hardened product by mistake (JIS Example 1 2) The acid-modified cyclohydrogen rain is equipped with a stirrer, thermometer, and reflowed epoxy acrylated character obtained in Example 9. ^ 1 should be fed in 10 grams of solid G of tetrahydroxylene,. The mixture was heated to the card =: "Purpose and measured after 2. 5 8 hours, derived from the sharp peak of _ ^ ^ ^ / / should be modified with tartaric acid epoxy acrylate Sand + so the acid value of the end vinegar compound is 81 mg K0 克 / g: the acid-modified diacrylate epoxy acrylate has a number average molecular weight 丨 76 clothes-hole acrylate example 13 U69 and weight I average molecular weight 2 M. 1 g of Darocur 1173 (supplied by Clba Specialty Chemicals, Inc.), two plus / 10 g of the acid-modified epoxy acrylic acid obtained in Example 12 was acetated. Synthesis. Phase The screen printing machine was applied to the surface of the copper laminate, and then dried with a hair dryer at 80 for 30 minutes. The pattern film was placed on the coating, and the coating was irradiated with ultraviolet light (Supplied by ΕΕΕ graphics company: UB〇151, light source : Metal gear lamp) exposed to 20 ㈣mJ. After exposure, 1% hydroxide The aqueous solution was developed. At this time, only the unexposed part> was disintegrated in the sodium hydroxide aqueous solution to obtain a developed pattern of the resin hardened product. The pencil damage strength (J 丨 s K 5 4 0 0) of the resin hardened product was HB. Comparative Example 5 38 Grams of tetramethyl bisphenol diglycidyl ether (YX4000 ...

C: \ 2D-CODE \ 91-O9 \ 91114155.ptd Page 65 591054

Guangxi Qi, Ying · epoxy equivalent 190) and 14 · 4 g of acrylic acid were dissolved at 60 ° C. Then, 19 g of diphenylphosphine and 9 mg of hydroquinone methyl ether were added to the mixture. The resulting mixture was heated to 1000 ° C, and the mixture was stirred for 10 hours. Measured during the reaction, after the value changed to 2 μg κ 〇 Η / g, the mixture was cooled to 60 ° C to obtain a resin. The resin is a viscous liquid at 60 ° C. Comparative Example ft 10 g of the resin obtained in Comparative Example 5 was melted, degassed, and molded at 200 ° C, and then hardened at 20 Gt for 6 hours to obtain a hardened product. Comparative Example 7 10 grams of bisphenol A epoxy acrylate (SP1 509, supplied by Showa Polymer Co., Ltd.) were degassed and molded at 20 ° C, and then hardened at 20 ° C. 6 A hardened product was obtained in hours. Comparative Example 8 10 g of novolac epoxy acrylate (SP4010, supplied by Showa Polymer Co., Ltd.) were degassed and molded at HO ° C, and then hardened at 20 ° C for 6 hours to obtain a hardened product. The hardened products obtained in Example 10 and Comparative Examples 6, 7, and 8 were evaluated for their properties by the following methods. Glass transition temperature (Tg): It should be known from dynamic viscoelasticity measurement (DM A). The measurement was performed at an oscillation frequency of 10 Η z. Dielectric constant and tangent of dielectric loss: obtained by cavity resonance oscillation method. Table 3 shows the results of the foregoing property evaluation. table 3

C: \ 2D-C0DE \ 9l-09 \ 91114155.ptd Page 66 591054 V. Description of the invention (61) Loss tangent 値 () GHz: ----- CE χ. 6 CEx. 7 CEx. 8 --- ---- Η) 8 165 1 40 1 42 ----- 2.74 --- 3. 12 j. J 1 3.10 --- J 0.036 0.052 0.032 dg (° C) Dielectric constant (] GH: Dielectric EX · = Executive example, CEX · = Comparative example t Example 1 4 ♦ JPE0-2Ed of the metallurgical industry, ^ Equipped with a stirrer, thermometer and a >, g (Base 0.077 Molar) Example Liquid The reactor of the funnel was fed with 40.0%. The Japanese and the Japanese made it. 4 The bifunctional PEO and 21 3.5 g of epichlorohydrin 2 ° = to 100 ° C: then dissolved by 6 · 3 G (0 · 09 2 Mosman, 八; · 0 gram of ethanol solution was added dropwise from the dropping funnel in 60 minutes. Add 穸 成 尨 士, 丄 人 *…, silly to pure Washed with water, further processed; to: remove raw salt and impurities. ㉟ gauge gas alcohol was distilled from the resulting solution = 仃 仃 dried by suction to obtain 43.1 grams of bifunctional 1 ^ 0-25 ^ (number Average, =. 丨 '15〇). According to 1R analysis, the bifunctional PEO-2Ep [A], the absorption peak of phenol ^ (3,6 00 cm-disappeared, according to nmr analysis, derived from = Gan, the peak appears, so it is confirmed that all the functional groups have been converted. The aforementioned bifunctional PE0 — 2EP, 20 parts by weight of four = n oxygen resin (large Supply from Japan Ink & Chemicals Co., Ltd. product: ο. F will: 153), 10 parts by weight of 4,4, _diamine diphenyl methane and 0. heart weight! 2_ methyl hydrazone is dissolved in forma Methyl ethyl ketone to make

591054 V. Description of the invention (62) A varnish with a resin content of 60% by weight is prepared. Glass cloth (NE glass product: trade name WEX983, supplied by Nitto Boseki) was impregnated with the aforementioned varnish, and then treated with a hot air blower to obtain a B-stage prepreg. Eight sheets of prepreg and copper foil (thickness: 18 microns, M itsui Mining & Smelting Company, trade name: 3EC-3) were combined, and these materials were hot-pressed at 2000 ° C for 2 hours to A 0.8 mm thick copper clad layer was obtained. Table 5 shows the physical properties of the copper clad layer. ^ Example 15 and Comparative Examples 9 to 1 1

Chemical Industrial Company supplies a general-purpose PPE polymer: Mitsubishi (jas, application, number average molecular weight: 24,000).

C: \ 2D-CODE \ 91-O9 \ 91114155.ptd Page 68 591054 V. Description of the invention (63) Bis-cyanic acid prepolymer: 2, 2- (4-phenylphenyl) cyanate . Four > Stinky two-stage A epoxy resin: EPICL0N-1 53, supplied by Dainippon Ink Chemical Company. Shuangwen A epoxy resin: DER-331L, supplied by Dow Chemical Japan. Ageing acid varnish type epoxy resin: EPPN-201, supplied by Nippon Kayaku Co. table 5

Ex. 1 4 Ex. 15 CEx. 9 CEx.] 0 CEx.]] Glass transition temperature (DMA method)] 9] ° C 2nt 156 ° C 202〇C] 90 ° C Frost constant (] G Η z) 3 · 4 3.5 4.2 3.5 4.0 Mess loss tangent] (] GHz) 0.0078 0 · 00] 8 0.021 0.0046 0.014 Copper foil peeling strength (kN / m) 1. 1] .2] .4] .2 0.9 Wedge plasticity 〇〇〇X 〇 Heat resistance to welding after absorbing water (swelling times / testing 3 times @)] hour treatment 0/3 0/3 0/3 2/3 0/3 2 hours treatment 0/3 0 / 3 0/3 3/3 0/3 3 hours processing 0/3 0/3 2/3 3/3] / 3

E X · = Example, c E X. = Comparative Example In the examples and comparative examples, the measurement was performed by the following apparatus and method. • Glass transition temperature (T g): Known from the peak of loss tangent (1 0 5) measured by dynamic viscoelasticity.

C: \ 2D-C0DH \ 91-09 \ 91114155.ptd Page 69 591054 V. Description of the invention (64) ~-:-b Dielectric constant and dielectric loss tangent value: measured by cavity resonance oscillation method jo " ο Copper copper peeling strength: 1G mm wide copper box measured at 9 () degrees according to JIS C648 1. ^ Heat resistance to soldering after water absorption: Test samples were made by removing intact copper foil, and the samples were 121 under PCT conditions. (: Accept absorption treatment at 0.2MPa) to 3 = 'then the sample was immersed in a 26th generation solder bath for 30 seconds. Visually observe whether the sample appeared delamination (swelling). • Moldability: Based on 70 micron thick copper pig Determine whether the inner layer pattern can be embedded without voids. [Reference Example 1] Manufacturing method of bifunctional PE0-2Ep (l) (manufacturing method of bifunctional PE0) The phenylene ether low polymer solution is based on the examples. Obtained in the same manner as 3, but 500 g of methyl ethyl fluorenone was replaced with 500 g of toluene, and g of meridine was replaced with 600 g of methanol. The resulting solution was concentrated by an evaporator to obtain 70% difunctionality. PE0 toluene solution. Part of the solution is further concentrated to obtain a powder. The powder has a number of g measured by Gpc method kijun y knife ϊ 1,6 2 0, and a hydroxyl equivalent of 8 J 〇 (Manufacturing method of bifunctional PE0-2Ep ) 41.5 grams of bifunctional! ^ 0_2 £ 15 (number average molecular weight: 1780 is called "difunctional PE0-2Ep [B]") 俜 膏 膏 」M" 'obtained, but using gram (Essence; 0; Mo V = phase PE0 toluene solution, 228.5 g epichlorohydrin, bifunctional (0.059 mole) ethoxylate Satisfied. Depending on the yeast and 4.0 g of acetic g

Like the IR of the bifunctional PEO-2Eρ [Β]

C: \ 2D-C0DE \ 91-09 \ 91114155.ptd Η Page 70. 591054 V. Description of the invention (65) · ~ " --- Knife analysis shows a peak derived from glycidyl ether, so it confirms all functional groups All have changed. [Reference Example 2] Manufacturing method of bifunctional pE0 —2Ep (2) (manufacturing method of bifunctional PE0) 7 〇 / 〇 Shuanglu PPE0 methylbenzyl solution was obtained in the same manner as in Reference Example j, but was used by dissolving 11 · 9 grams (〇.044 mol) of mountain methyl-u, r-biphenyl) _4,4, _ 2 and 79.9 grams (() / 66 Mo ^ bis == cresol in 600 grams The mixed solution obtained from methanol (divalent phenol: monovalent phenol mole ratio 1 · 1 5). ° 卩 minutes> Cereal solution was further concentrated and suction-dried to obtain an average molecular weight of 3,34G in powder number and a base number of 166. The number of thousands of knives / knife is measured in the same way as in Reference Example 丨 (Manufacturing method of bifunctional PEO-2Ep) 49 · 8 grams of bifunctional PE0-2Ep (number average molecular weight: 3 5⑽, called "bifunctional PEO -2Ep [C] ") (Pay in the same way as Lost 7 丨, '") Spike Mai Case 1, but use 71.4 grams (hydroxyl: 0024 苴: ϋ, y / + Mohr) as above Bifunctional PEO transcript> Valley fluid, 155.7 g epigastrol, β ^ mol) sodium ethoxylate. According to the reference example! The phase acetic acid and 2.0 g 029 have changed. Phase ^ method, confirmed that all functional [Reference Example 3] Preparation of epoxy-modified polyphenylene ether, peel method 4 7 · 7 grams of epoxy-modified polyphenylene ether (obtained by the ppEj formula) but used 50 g of commercially available polyphenylene bond Erzheng Examination Example 1

GasC-i Industrial Co., Ltd .; ΐ ;; lipid base: 0.03 mole), 200 grams of methylbenzyl, molecular weight: 1 6,000, ^ · 9 grams of epichlorohydrin, 2.2 grams of ethyl alcohol

C: \ 2D-C0DE \ 91-09 \ 91114155.ptd Page 71 591054

Alcohol and 0.6 g (0.09 mol) of sodium ethoxide. According to the same method as in Reference Example 1, it was confirmed that 95% of the functional groups had been changed. Example 1 6 32. 40 parts by weight (7.02% by weight) γχ4〇Η (supplied by Japan Epoxy Resin Co., Ltd., epoxy equivalent 195) was used as the biphenyl type epoxy resin, and 108 q parts by weight (2.34% by weight) 195XL (supplied by Sumitomo Chemical Co., Ltd., epoxy equivalent: 195) as a cresol novolac epoxy resin, 3.8 parts by weight (0.82% by weight) EBS400T (Sumitomo Chemical The company supplies, epoxy equivalent of 40 0) as a flame retardant bivariate epoxy resin, η · 5 parts by weight (2 49% ratio) bifunctional PEE_2_2EP [B], 15.93 parts by weight (3 45% by weight) KAYAHARD ΝΗΝ (supplied by Nippon Kayaku Co., Ltd. with a hydroxyl equivalent of 140) as a naphthalene-type phenol resin composition, 15.93 parts by weight (3.45% by weight) ΜΙΕΕ225- 3L (Myotsu Chemical Co., Ltd. supplies' hydroxyl equivalent 173 ) As a para-diphenol copolymer, a powder was obtained. The powder was processed by combining 3605 parts by weight (78. 8% by weight) with a fused silica powder and 2.13 parts by weight (0.46 ° / o). Weight ratio) 7 ^ -glycidyloxypropyltrimethoxysilane, weight ratio of 0 95 parts (0.21% by weight) Phenylphosphine, 1.36 parts by weight (0.30% by weight) Natural Brazilian brown wax, 0.99 parts by weight (0.21% by weight) carbon black, and 5.40 damage Gadolin ratio (1.17% by weight) was obtained with antimony trioxide. First, a bifunctional PEO-2Ep [B] and an epoxy resin were dissolved in benzene to obtain a homogeneous benzene solution with a concentration-to-weight ratio. The amidine solution was removed from the amidine solution to obtain a mixture of epoxy resin and bifunctional PEO-2EP. The aforementioned substances were added to the mixture, and the resulting mixture was mixed with a heating roller at 85 t for about 5 minutes. Then the kneaded mixture was pulverized to have a diameter of about 5 mm, thus obtaining

591054 V. Description of the invention (67) Examples of sealed epoxy resin compositions 7 to 19 and comparative examples 2 1 4 The male epoxy resin composition was obtained in the same manner as in Example 丨 6, but the materials were based on The quantities shown in Table 6 are mixed. The obtained sealed epoxy resin compositions of Examples 16 to 19 and Comparative Examples 12 to 14 were subjected to a soldering heat resistance test, and the dielectric constants of these resin compositions were evaluated. Further, the J viscosity of the resin composition is measured, the flexural strength of the hardened product is measured, and the moldability of the resin composition when used for sealing is measured. One of the moldability test and welding heat resistance test is performed under the following conditions. 7.6mm X 7.6mm X 〇 · 4mm (thickness) semi-conductor mounted on the alloy lead frame, the lead frame has a die pad size of 8 2 true fj m 1 with silver paste 'use outer diameter 19 mm x 15 mm " mm (thickness) 60-pin flat package molded compression mold to prepare test pieces. The ultrasonic detection device was used to check whether the sealing layer was present in the presence of voids and had good moldability (indicated by 0). Go to the gap. s 不 ^ r. (. X ^ ^) 〇 ^ # 5 Each test piece at 85 t: and 85% relative humidity absorbs water for 72 naps. Let 260. . 10 seconds in solder. Absorption and immersion process], and then immersed, then check the sealing layer twice with an ultrasonic probe. A cracked seal is considered defective. There are cracks, and the dielectric constant is measured based on JIS-K-6911. The measurement is based on the bending strength of the hardened product as follows. Sealed to prepare a test piece with a size of 10 mm x 4 mm X 100 mm, a hard resin composition, and a test piece

591054 V. Description of the invention (68) Measure three-point bending strength at room temperature and at 240 ° C, under the conditions of fulcrum distance = 64 mm and crosshead speed = 2 mm / min. The melt viscosity of the aforementioned resin composition was measured at 175 ° C using an elevated flow tester. Table 7 shows the foregoing results. It was confirmed that when a bifunctional PE0-2 Ep having a number average molecular weight of 70 to 3,000 was used, moldability was good, no voids appeared, low dielectric constant, high bending strength, and low melt viscosity. Table 6 (Unit:% weight ratio)

E X. = Example, C E X. = Comparative Example Note: As for the bifunctional PEO-2Ep [A], the bifunctional PEO-2Ep [A] obtained in Example 14 was used.

A: \ 91114155.ptd Page 74 591054 V. Description of Invention (69) Table 7

Ex. 16 Ex. 17 Ex. 18 Ex. 19 CEx. 12 CEx.] 3 CEx.] 4 Number of cracks after welding Number of defects / number of test pieces 0/5 0/5 0/5 0/5 2/5 5 / 5 '5/5 Dielectric constant 4.6 4.1 4.6 4.6 4.6 4.4 5.] Moldability 〇〇〇〇〇. × 〇 Bending strength room temperature 156 160 157 156 147 148] 44 (MPa) 24 0〇C 12.7 13.7 12.7 Π.7 7.8 8.8 5.9 Melt viscosity (Pa · s) 30 34 22 25 37 94 20 EX · = Example, CE X. = Comparative Example Example 2 0 The bifunctional PE0 manufactured in Example 2 was used. Bifunctional PE0 was treated in the same manner as in Example 5 to obtain 50.1 g of a cyanate compound (difunctional PEQ — 2CN). According to IR analysis of the cyanate compound, the age-based absorption peak (360 cm-1) disappeared, and the absorption peak (2,250 cm-1) derived from the cyanate group appeared, so all the functions were confirmed The bases have changed. 30 parts by weight of the aforementioned bifunctional PEO-2CN, 30 parts by weight of the two-stage A-type cyanic acid prepolymer, and 20 parts by weight of tetrabromobisphenol A epoxy resin (supplied by Dainippon Ink Chemical Co., Ltd., commodity Name: EPICL 〇 N-1 5 3), 20 parts by weight of bisphenol A epoxy resin (D ow C hemica 1 J apa η company, trade name · DER-331 L) and 0.04 parts by weight铁 Iron pyruvate dissolved in methyl ethyl nail

591054 V. Description of the invention (70) Ketones to prepare varnishes with a resin content of 60% by weight. The glass cloth (NE glass product: trade name: WEX9 83, supplied by Nito Boseki Co.) was impregnated with Lishu varnish, and then treated with a hot air blower to obtain a B-stage prepreg. Eight pieces of prepreg and copper foil (thickness: 18 micron, supplied by Mitsui Mining & Smelting, trade name: 3EC-3) were laminated, and the material was hot-pressed under vacuum in 2000 for 2 hours in thickness Copper clad layer. Table 9 shows the copper-clad laminates & f · 耄 ratios Example 15 and 16 Milky The copper-clad laminates were mixed in the same manner as in Example 20, and the lipids were mixed at the ratios shown in Table 8. Comparative Example 5 was also used as a 'but thermosetting tree ethyl ethyl fluorenone, and therefore was used as a solvent. Because the ingredients are insoluble in Table 8 "

A: \ 91114155.ptd R48 page 76 591054 V. Description of the invention (71) Table 9 Εν.20 CEn.] 5 CEx.] 6 Glass transition temperature (DMA method) 2] OcC 2 ore 1 9〇ΐ Dielectric constant (] GHz) 3.5 3.5 4.0 Dielectric loss tangent (I GHz) 0.0048 0.0046 0.014 Copper foil tear strength (kN / m)]. 2 1.2 .2 0.9 wedge plastic 〇X 〇 heat resistance to welding after water absorption (Number of swellings / number of trials 4)] Hour treatment 0/3 2/3 0/3 2 Gum treatment 0/3 3/3 0/3 3 hours treatment 0/3 3/3] / 3 Curvature intensity ( MPa) 4 85 368 498 Buckling elastic constant (M P a) 1 7S00 17 200 1 92 00 Bending flexibility coefficient (%) 2.9 2.4 2.8 Example, CE X. = Comparative example • Mechanical properties Head speed: 1.0 Millimeters per minute. Example 2 1 [Synthesis of bifunctional PE0] Volume 5 liters, equipped with a stirrer

Ex fulcrum distance: 20 mm, 13.3 g (0.0 3 0 mol) CuCl, 176.8 g (1.34 mol) di-n-butyl, fed into the slender reactor measured at room temperature and the inlet pipe and baffle thermometer. Amine and 1,000 g of fluorenylethylfluorenone. Each composition was stirred at a reaction temperature of 40 ° C, by dissolving 108.0 g (0.40 mol) of divalent phenol, 2, 2 ', 3, 3', 5, 5'-hexafluorenyl-biphenyl] -4, 4'-diphenol and 14 6. 5 g (1.20 mol) of 2, 6-dihydroxyphenol in 2,000 g of methyl ethyl ketone

C: \ 2D-mDE \ 91-09 \ 91114155. Ptd page 77 591054 V. Description of the invention (72) The Yu / Valley solution was added dropwise to the anti-warehouse in 120 minutes, and the air was ventilated in minutes. After the addition was completed, the mixture was stirred for 60 minutes while H was raised / minute and air was introduced. Ethylenediaminetetraacetic acid dihydronaphthalene was dissolved in water to react the mixture to end the reaction. Then wash with N hydrochloric acid aqueous solution = add to reverse water for washing. The solution thus obtained was concentrated by means of an evaporator to obtain 241.8 g of bifunctional PE0 resin as pure bran. The resin has, number == sub-set 810, weight average molecular weight ^ "and hydroxyl equivalent 475. (Z-position introduction) 50 grams of t gauge base is fed into a reactor equipped with a stirrer, thermometer and reflux tube. 11 mole) of the aforementioned bifunctional PEO resin, 14.5 g of potassium carbonate and 400 * l of acetone, and the mixture was refluxed under nitrogen for 3 hours. Then 21.0 g of 6-bromo-i-hexanol was used for 1 hour. Add dropwise to the mixture. After the addition is complete, mix for 30 hours. After neutralizing with i N hydrochloric acid aqueous solution, add a large amount of pure J ": to obtain-precipitate, add toluene for extraction. The obtained solvent was concentrated, and the concentrated solution was added dropwise to methanol to obtain again. The solid was recovered by filtration. It was then suction-dried to obtain the bifunctional PEO resin introduced into it. The resin has a number average ^ 7 9. k 1, 〇 2 4, weight average particle diameter 1, 3 8 5 and hydroxyl equivalent (synthesis of acrylic compounds), f, f, agitator, thermometer, and reflux tube were fed into the reactor with 30 grams.吝 S 驮 and 0.3 g of hydroquinone. Allow the mixture to reflux and heat. Raw water is quantified and collected using a water dosing receiver. Collect 0.8 g

591054 V. Description of the invention (73) When water is generated, the reaction mixture is cooled. . The mixture should be dissolved in 20% sodium hydroxide in water, and then to 120 C. Inverse m 2,,,, ^, combined, and neutralized at night, and then with 20% sodium chloride water acid to win rid of the water; two: minus Pressed the hair to remove the solvent 'to obtain 29.5 grams of propylene = polyacrylic acid resin having a number average molecular weight !, and a weight average molecular weight of 1,5 6 2. fExample 2 2 (Z-position introduction)

Internal time and density = 50 g of the bifunctional pE0 obtained in the foregoing Example 21 was fed into the reactor, and 1 g of potassium hydroxide was added to the reaction as additives. The atmosphere inside the reaction chamber was replaced with nitrogen. The mixture was then heated with stirring, and the inside temperature reached 70 ° C. At 0 o'clock, 5.1 g of ethylene oxide was injected into the mixture under pressure to heat it to 1000 c, and the addition reaction was performed. The reaction mixture was aged for 4 hours for 1 hour. The reaction product was washed with 1N aqueous hydrochloric acid and washed with pure water. The solvent was removed by evaporation under reduced pressure to obtain 49.2 g of resin. The bifunctional PEO resin with a Z-position introduced therein has a number average particle diameter of 901, a weight average particle diameter of 丨, 2 丨 3, and a hydroxyl equivalent of 524 ° (synthesis of acrylic compounds)

A reactor equipped with a stirrer, a thermometer, and a reflux tube was fed with 30 g of the aforementioned bifunctional PEO resin having a zeta-position, 4.9 g of acrylic acid, 30 g of toluene, and 0.1 g of p-xylene. Acid and 0. 03 grams of hydrogen. The mixture was heated under reflux. The water produced is quantified and collected using a water dosing receiver. When 0.9 g was collected, the reaction mixture was cooled when water was generated. The reaction temperature is Π 0 to 120 ° C. The reaction mixture was neutralized with 20% aqueous sodium hydroxide solution, and then with 20% sodium chloride water.

591054

(74) Acid ί 2; t. Evaporate under reduced pressure to remove the solvent to obtain 29.7 power: two. The acrylic resin has a number average molecular weight of 1.042, propylene, and a molecular weight of 1,773. U42 and weight (introduced at z-position) 50.5 grams with z-position introduced its average particle \ milk 'ethane is replaced by 6-7 grams of propylene oxide. The resin has the number 541. Diameter 941, weight-average particle diameter 丨, 25 5, hydroxyl equivalent (synthesis of acrylic compounds), the resin was treated in the same manner as in Example 22 to obtain 2 9 · 3 g of acrylic resin. The acrylic resin has a number average molecular weight of 1.084 and a weight average molecular weight of 1,422. f Example 24 Degassing 10 grams of Example 2 1 The acrylic resin obtained in Example 1 was melted and molded, and then hardened at 200 ° C for 6 hours to obtain a hardened product. G of the acrylic resin obtained in Example 2 2 was melted and molded at 150 ° C, and then hardened at 200 ° C for 6 hours to obtain a hardened product. f. Example 10 Degassing 10 grams of the acrylic resin obtained in Example 23 was melted and molded at 150 ° C, and then hardened at 200 ° C for 6 hours to obtain a hardened product. fExample 2 7

C: \ 2D-C0DE \ 91-09 \ 911I4155.ptcl Page 80 591054 V. Description of the Invention (75) " ----- 6 grams of Example 2 1 The epoxy acrylate compound obtained in 1 was dissolved in 4 grams of card Bichan Yi, ester, 0.6 g Darocur 1173 (Clba Specialty Chemicals Co., Ltd. photopolymerization initiator) was added to the solution to obtain a resin composition. The resin composition was applied to the surface of the copper-clad laminate with a screen printing machine, and then dried at 80 C for 60 minutes with a hair dryer. The patterned film was placed on the coating, and the coating was exposed to an ultraviolet light irradiation device (supplied by EYE GRAPHICS: UB01 51, light source: metal halide lamp) at 1,500 millijoules. After exposure, shadowing was performed with methyl ethyl fluorene. At this time, only the unexposed portion was dissolved in methyl ethyl fluorenone to obtain a resin hardened product developing pattern. The pencil damage of the resin hardened product (JIS K5400) is B. & Example 2 8 6 g of the acrylic resin obtained in Example 2 2 was treated in the same manner as in Example 27 to obtain a developing pattern of a resin hardened product, in which only unexposed portions were dissolved in fluorenyl ethyl ketone. The pencil damage strength (JIS K5400) of the resin hardened product is B. Example 2 9 6 g of the acrylic resin obtained in Example 2 3 was treated in the same manner as in Example 27 to obtain a developing pattern of the resin hardened product, in which only the unexposed portion was dissolved in fluorenyl ethyl ketone. The streak damage strength (JIS KK5400) of the resin hardened product is B. & Comparative Example 1 10 g of Shuangfan A ethylene oxide fired adduct dipropionic acid g (LIGHT-ACRYLATE BP-4EA, supplied by KYOE I SHA Chemical Co., Ltd.) was degassed and molded at 100 ° C , And then hardened at 200 ° C for 6 hours to obtain a hardened product.

C: \ 2D-CODE \ 91-O9 \ 91114155.ptd Page 81 591054 V. Description of the invention (76) The hardened products obtained in Examples 2 4, 2 5 and 26 and Comparative Example 17 were evaluated for their properties. Table 1 0 shows the results of physical property evaluation. Table 10 EX. 2 4 Ex · 25 Ε χ. 2 6 CEx. 1 7 Ding g ('c)] 8 5] 83] 8 6] 05 Dielectric constant (] GH2) 2.7] 2.72 2.7 2 3.2] Loss IE cut (] GHz) 0.0096 0.0]] 0 0.0] 02 0.0302 EX · = Example, CE X. = Comparative Example

A: \ 91114155.ptd Page 82 591054 Brief description of the diagrams Figure 1 shows the GPC spectrum of the product of Comparative Example 1; Figure 2 shows the GPC spectrum of the product of Example 2; and Figure 3 shows the passage of reaction time in Example 2 And the changed GPC map. 〇

C: \ 2D-CODE \ 91-O9 \ 91114155.ptd Page 83

Claims (1)

591054 93 · 4. -5 Replaces this case No. 91114155 6. Scope of patent application— ~ ^^ ^ 1 · A difunctional oligophenyl ether oligomer of formula (1), via a divalent phenol of formula (2) and Obtained by oxidative polymerization of a monovalent phenol of formula (3), Η — {— 〇—Υ — ^ ~~ (—0 —X —〇 — ^ {— Y —〇—Η (1) Η0—X · —OH ( 2) Y -OH (3) (where -X- is represented by formula (2 '), (2,) where R2, R3, R4, R8, and R9 are the same or different and are _ atom, a sulphur group or a radical containing 1 to 6 slave atoms, R5, R6, and R7 may be the same or different and are Hydrogen atom, halogen atom, alkyl group or phenyl group having 1 to 6 carbon atoms; Y-0- is represented by formula (3,), 〇— (3,) where R10 and R11 may be the same or different and are halogen atoms or alkyl or phenyl groups containing 1 to 6 carbon atoms, R12 and R13 may be the same or different and are hydrogen atoms, tooth atoms, An alkyl or phenyl group containing 1 to 6 carbon atoms, but Y-0- is a structural arrangement defined by formula (3 '), or a random arrangement of structural formula defined by (3,)' and a & b 〇 ～ 3〇〇 ^ C: \ Total file \ 91 \ 91114155 \ 91114155 (replacement) -1. Ptc page 84 591054 --- 911H1RR __ ^ Month day amendment 6. Integer scope of patent application 'but a and b are different 0), R2, R3, R4, R8, R9, R10, and R11 of formula (2 ') and formula (3') are required to be non-hydrogen atoms. 2 · If the oligomer of item i in the scope of the patent application, wherein "" of formula (丨), R3, R4, R8, R9, R10 and R11 are methyl groups. 3 · If the low polymer of the scope of patent application 1 It has a number average molecular weight of 500 to 5,000. 4 · As for the low polymer in the first item of the patent application scope, wherein the molecular weight distribution variable (Mw / Mn) is 1.1 to 2.5. 5 · If the patent application scope The oligomer of item 1, wherein the divalent expectation of the formula (2) is 2, 2 ', 3, 3', 5, 5'-hexafluorenyl ~ [1, Γ —biphenyl] -4, 4, -Diphenol. 6. The oligomer according to item 1 of the patent application, wherein one of the formula (3) is expected to be 2, 6-xylenol alone, or 2, 6-xylenol and 2, 3, 6 -A mixture of tricresol 'and when it is a mixture, the proportion of 2, 3, 6-trisphenol in the monovalent phenol of formula (3) is 10 to 70% mole ratio. For example, the method for preparing an oligomeric polymer according to item 1 of the scope of patent application, which comprises adding a mixture of a copper catalyst, an amine and a ketone solvent to the reactor, adding a divalent phenol of formula (2) and a monovalent phenol of formula (3). With divalent phenols: Molar ratio of valent phenol is added in the range of 1: 1 to 1: 1, and the oxidative polymerization reaction of divalent phenol of formula (2) and monovalent phenol of formula (3) is carried out. At a temperature of 25 to 50 ° C, the original The phenol concentration of the material is 8 to 70% by weight, and the pressure in the reactor is from one atmosphere to 20,000 kg / cm2G. 8 · As in the method of applying for the scope of patent application item 7, the solvent is g-soluble C: \ master file \ 91 \ 91114155 \ 91114155 (replace) -1.ptc page 85 591054 591054 fix Where R13 is a hydrogen atom or a methyl group; _χ_, γ_〇_); ζ, C, and d are defined as A 彳, y 丨, a, and b are as defined in the formula, as defined in formula (4), and n is 0 to 10 Integer number ^ or 911141.RR 6. The scope of patent application (1) Y-0- has the formula ⑴ expressed as ^ around the item 10, and u +, as shown in the formula (β) as the item 10 in the patent range Judges & Scoring Scope 10th Quotation, Ten, 々Ή n 忒 α) or the arrangement structural formula of formula (7), or the formula (fn 好 々 (7) Randomly arrange the structural formula. The formula (6) and the formula ^ ^ 61 'b ^ ^ ^ # ^ ^ ^ t If ^ should be obtained. The epoxy acrylate compound and the carboxylic acid or carboxylic anhydride are inversely hardened according to 14.g. The product is obtained by hardening the epoxy acrylate compound as described in the scope of the patent application, and / or the acid-modified epoxy acrylate compound, as described in the scope of the patent application. An epoxy resin composition containing a weight fraction of f. F., An average molecular weight of 700 to 3,000, and an epoxy-based oligomer i | g) said 0-01 5.0 part by weight hardening accelerator, and 5-5 billion parts by weight of a flame retardant to 1 part by weight of hard 1〇〇 agent 'to, OH ： H2-CH-CI 丨 Private ~ ° ~ Y ~ ~ ^ chx—〇》 -Υ—0——zJ ~ -ch2 * ch \: h2 ⑼ Among them -X-, Y-0-, a and b Defined as in formula (1), z, C and d are defined as in formula C: \ Overall \ 91 \ 91114155 \ 91114155 (replace) -1.ptc Page 87 591054 Case No. 91114155 6. The scope of patent application (4) and η is an integer from 0 to 10. 16. The epoxy resin composition for a laminate according to item 5 of the patent application scope, which further comprises 10 to 200 parts by weight based on 100 parts by weight of an oligomeric test oligomeric compound represented by formula (9). Cyanate resin. 17 · As for the epoxy resin composition for laminates according to item 5 of the patent application scope, in the phenylene ether oligomer compound of formula (9), R2, R3, R4, R8, and R9 of _χ-1 are Methyl, in addition, at least one of X1, R6 and r? Is a fluorenyl group, and Y- has a structural formula or formula arranged by formula (6) or formula (7) as cited in item 10 of the patent application range (6) and the random arrangement structural formula of formula (7). 1 8 · The epoxy resin composition for laminates according to item 5 of the patent application scope, which is used for prepregs, laminates or printed wiring boards. 1 9 · A sealing epoxy resin composition containing the epoxy resin composition as cited in item 15 of the scope of patent application, and a phenylene scale oligomeric compound represented by formula (9) per 100 parts by weight It further contains, as components, 1 to 500,000 parts by weight of different epoxy resins and 10,000 to 4,000 parts by weight of inorganic filler. 2 0. The sealing epoxy resin composition according to item 9 of the scope of the application for a patent, wherein -X- in the phenylene ether oligomer compound having an epoxy group at each terminal group represented by formula (9) R2, R3, R4, R8, and R9 are fluorenyl groups, and in addition, at least one of R5, R6, and R7 of X- is fluorenyl group, and γ-10- has the formula as cited in item 10 of the scope of patent application ( 6) or the formula (7) array structure formula or the random array structure formula of formula (6) and formula (7). 2 1 · If the sealing epoxy resin composition of item 丨 9 of the patent application scope, C: \ master file \ 91 \ 91114155 \ 91114155 (replace) -i.ptc Page 88 Wherein the formula (9) 矣; 4 test oligomeric compounds Λ in each, Λ has an epoxy-based phenylene agent, and low-medium / 3 miles, with a range of% oxygen resin, hardener, inorganic filler . -The total amount of Α5 compound itself is based on 1 to 60% by weight of 2 in the pot 2 and 2 inferior to the machine. Application of the sealing epoxy resin composition of item 19 in the right section, agent, I oligomerization Content, with epoxy resin, hardener, inorganic filler range.总量 The total amount of fluorene is based on a combination of 15 to 95% by weight: cyanide :: layer: with a resin composition, containing a kind of phenylene ether oligomer,, 〇, and cyanic acid based on each At the end, it is expressed by the formula (10) where -X-formula (4) 〇Y 0-, a and b are defined as formula ⑴ and 2, c and 4 are defined as 24 · as the scope of patent application No. 23 is based on 100 parts The weight (by formula) shows 50 to 200 parts by weight of different cyano epoxy resins, and 40 to 100 parts by weight of hardening accelerator. Resin composition for laminates, the cyanate compound shown further contains an ester resin, 30 to 150 parts by weight of a flame retardant, and 0.01 to 5.0 parts by weight The resin composition for laminates according to item 23, which is among the cyanic compounds of formula (10), a χ-one of R2, R3, R4, ruler 8 and ^ methyl 'and one of [R5, R6, and R7 At least one of them is methyl, with 591054 --ti 虎 91114155__ 年月 日 倐 正 _ VI. Scope of patent application and γ_0—It has the structural formula or formula (6) and formula (6) or formula (7) as cited in item 10 of the scope of patent application. (7) The random arrangement structure. 2 6. The resin composition for laminates according to item 23 of the scope of patent application, which is used for prepregs or printed wiring boards. 27 · — (meth) acrylate compound represented by formula (11), 0-2- (η) wherein -X-, Υ-0-, a, and 13 are defined as formula (d, Z, is an organic group, which does not have a hydroxyl group in a branch chain and has 1 to 10 carbon atoms, and contains an oxygen atom, c and d are defined as in formula (4), and R15 is a hydrogen atom or a methyl group. 28. As in the (27) (fluorenyl) acrylate compound of the scope of patent application, wherein -X- is represented by formula (5), and γ —〇- has an array structural formula of formula (6) or (7), or a random array structural formula of formula (6) and formula (7). 2 9 · Hardened products, which are hardened as described in the patent application (7) Obtaining the (fluorenyl) acrylate compound of item 7.