TW200915932A - Copper foil with dielectric layer - Google Patents

Abstract

A copper foil with a dielectric layer for use in improving the adhesion between the surface of an inner-layer circuit of an inner-layer core member and the dielectric layer and in forming a capacitor circuit layer having a low dielectric loss tangent. The copper foil with a dielectric layer is used for forming a capacitor circuit layer by joining the copper foil to the surface of a printed circuit board with an embedded circuit produced by so embedding a circuit in a resin base that the top surface of the circuit is generally in flush with the surface of the base. The copper foil with a dielectric layer (1) has a dielectric layer (4) formed of a semicured resin containing a dielectric powder (3) on one side of the copper foil (2).; The copper foil with a dielectric layer (1) is characterized in that the dielectric layer is a dielectric powder-containing resin layer formed in such a way that a dielectric powder is dispersedly contained in a resin composition including an epoxy resin, an active ester resin, a polyvinyl acetar resin, and a curing promoter and the resin composition is semicured. The copper foil with a dielectric layer is used for manufacturing a printed circuit board.

Description

200915932 * IX. Description of the Invention: [Technical Field] The present invention relates to a copper foil having a dielectric layer used in forming a capacitor circuit of a printed circuit board. [Prior Art] In recent years, electronic communication devices have been required to have high-speed signal transmission characteristics of the GHz to THz level. A printed circuit board having a communication circuit for a communication device that is required to transmit such a high-speed signal at such a high frequency is also required to be compact and high-density. A communication circuit that requires such a high-frequency signal to be transmitted, "the high-frequency current flows only in the vicinity of the surface layer of the wiring circuit, and the (skin effect), if there is unevenness in the vicinity of the surface layer, causes a signal noise. Therefore, the surface state of the wiring circuit is preferably in a smooth and flat state. In order to prevent electrical interference caused by interference of high-frequency signals generated between adjacent circuits when a high-frequency current flows through the wiring circuit, the wiring circuit is buried in the insulating resin substrate, and the circuit gap is buried with insulating resin. A printed circuit board having a buried circuit in which the upper surface of the wiring circuit and the surface of the substrate are located in slightly the same plane. Then, in the inner layer circuit of the buried printed circuit board, the operation circle of the electronic device is realized to achieve power saving to form the capacitor circuit layer. Then, from the viewpoint of electronic component mounting, it is also required to prevent the signal delay and signal attenuation by using a printed circuit board with a built-in circuit for speeding up the transmission speed of the signal of the electronic communication device. of

2213-9834-PF 200915932 by using capacitors that have been mounted on the surface of printed circuit boards. . The so-called passive element of the coil, the edge resistor can be formed to reduce the wiring distance, and the second is: the layer printed circuit pole, the dispute + η can reduce the electrical noise to the Xiong Guang, in the proximity of the mobile phone Wait for more than Ding. In the device of operation, I seek to reduce the signal transmission loss from the frequency-frequency signal produced in the high-frequency field. Therefore, in: the circuit of the circuit board capacitor circuit, when the 曰ρ brush circuit board is built in

, t ..., requires a small loss of transport. This is the case that the dielectric loss and the conductor loss are low, and the dielectric loss is required. Therefore, in order to make this pass, the conductor loss is small. [Transfer Known Loss] = "Jie Lei Tu · 1 Shi Ren ^ ^ 电知失] + [Conductor Loss] W Electric ^ Loss, calculated by the formula 2 rate and the dielectric positive g Μ formula, The lower the value of the Thai baht is, the lower the value is. Because, when the package is used, the dielectric connection is also small, and the right dielectric loss is small [Equation 2] The value of the square is also linked. [Dielectric loss] two Κχ [周波However, the person "L" "electro-leather" X [dielectric positive connection] However, the coefficient of variation of the material of the multilayer printed 1 electric material is determined by the formula 3: the capacitance of the capacitance circuit built in the road board, the polar area And the distance between the electrodes can be understood as follows. If the electric capacitance is made smaller, and the second two is purely lowering the dielectric constant, the capacitor circuit is only positively connected to the cold circuit. Therefore, if you consider together. A spare capacitor is as small as possible. One [Formula 3]

2213-9834-PF 200915932

[Capacity] = [Specific Dielectric Rate] X [Vacuum Dielectric Rate] χ ([electrode / [electrode distance]) Product J Therefore, 'the material is formed on the inner layer of the printed circuit board for the frequency, and the dielectric is positively connected and The dielectric loss is small, and it is preferable to have a moderate insulating material to form a dielectric layer. Then, when a built-in capacitor circuit is formed on the sound inside the printed circuit board, a copper foil having a dielectric layer is generally used. 3, t, as a dielectric layer suitable for the copper foil having such a dielectric layer, for example, in Patent Document 1 (Japanese Patent Application No. 2, 4, 21, G941), the disclosure includes The curable mixture formed of the active vinegar compound and the resin is blended with the curable mixture:: = "Electrical pottery powder, and resin mixture with polyarylate. In addition, Patent Document 2 (曰 National Patent Application: Special Kaiping = ::) [Opening the book is a copper box used for the formation of small high-frequency circuits: thermosetting resin, hot plastic resin, and Tao Yusuke The electric body = as an essential component, and by adjusting the ratio of the content of the ceramic powder to the adhesive of the adhesive agent, the high-frequency circuit is inferior to the Tao Yun soil plate in the high-frequency circuit. The dielectric foil of the copper foil is an adhesive. However, in order to cope with the miniaturization and high density of the high-frequency circuit, ▲ I:::' is only the second one of the above-mentioned Patent Document 1 and Patent Document 2: the performance of the document 1 and the suede. The following is a description of the problem in the case where the invention disclosed in Patent Document 1 and Patent Document 2 is applied to the formation of a dielectric layer having a copper box.羯 using the copper enamel of the resin composite layer disclosed in Patent Document 1, the steel layer having the dielectric layer is provided on the inner core material.

2213-9834-PF 200915932 « Try to manufacture a printed circuit board with a capacitor circuit. As a result, it is known that the formed dielectric layer is fragile and lacks flexibility, and it is necessary to pay attention to the lack of adhesion stability between the dielectric layer and the wiring circuit of the inner core material during operation, and the dielectric valley circuit The electrical characteristics are not stable. In addition, the adhesive for the steel box used in the formation of the small-sized high-frequency circuit disclosed in Patent Document 2 is adjusted by adjusting the content ratio of the dielectric ceramic dielectric powder to the adhesive for the adhesive. A copper box with a dielectric constant similar to that of the ceramic substrate is coated on the surface of the copper box to obtain a copper crucible having a dielectric layer. However, as a dielectric material, the more the dielectric ratio is similar to that of ceramics, the more the dielectric powder content is increased, the more significant the lack of the dielectric layer in the Jielei & The adhesion between the wiring circuits of the materials 'and the formation of people'; the electrical layer is weak and lacking, and care should be taken during operation. Therefore, in the present invention, the post-printing with the buried circuit in which the inner layer circuit is disposed is embedded in the smuggling resin substrate, and the slab is used as the inner core material. The surface is bonded with a dielectric 々κ® gentleman a 』, white & 丨 electrical layer 'will be located in the outer layer of the dielectric layer of the copper foil of the steel, the white layer is etched to form a capacitor snow road to obtain In the manufacture of high-frequency signal transmission wind power, the thickness of the inner layer circuit surface and the dielectric layer of the copper foil with the dielectric layer used for the printed circuit board used in the manufacture of the high-frequency signal is 0±.., a.. #: After the core of the D Hai inner layer is made into a capacitor with a low dielectric positive connection, the '(10) is provided as a shape. A copper box with a dielectric layer on the road layer

2213-9834-PF 200915932 [Problems to be Solved by the Invention] In order to solve the above problems, the inventors of the present invention have made intensive studies and have found that the above problems can be solved by using a copper foil having a dielectric layer as described below. The copper with a dielectric layer for the manufacture of printed circuit boards for the sake of the poor is placed in the base resin, and the I4, Tian box, which is the same plane as the substrate and the surface of the substrate, is used. The surface of the printed circuit board having the buried circuit on the surface of the circuit board having the buried circuit is a copper foil having a dielectric layer forming a capacitor circuit layer, and the copper substrate of the electric layer is attached to the surface of the substrate. A dielectric layer formed of a + hardened resin containing a dielectric powder on one side of a copper box, which is characterized by: an epoxy resin, an active weave, an ethylene glycol shrinkage resin, and a hardening grease combination. The dielectric powder in which the dielectric powder state is dispersed is contained in the resin layer. To further improve the weight of the resin composition formed by the epoxy resin, the active vinegar resin, and the ethylene resin (4) having the dielectric layer according to the present invention, to make the dioxygen The resin is preferably 25 parts by weight to 60 parts by weight of the tree. The formation of the first wood is the 介 硐 硐 > > > > > > > > > > > > > > > > > > > > > > 〇重"The saplings of the composition of the saplings are then formed and then have a dielectric J <

2213-9834-PF 200915932 The layer is a total amount of the weight of the resin composition containing the epoxy resin, the active ester resin, and the hardening accelerator, and the weight of the dienol resin, the epoxy resin, and the active ester resin. It is preferred to use a resin composition containing a portion to form a composition.重量份〜95重量的铜层的铜膜 The copper resin having a dielectric layer is made of epoxy resin, active vinegar resin, poly- mer: ==, hardening promotes the vinyl acetal resin i parts by weight to 2 〇 8 to use the poly-containing material. A resin composition having a dielectric layer formed in accordance with the present invention to form a copper sheet having a dielectric layer in the present invention, wherein the electric layer is a sputum, a tongue ester resin, The polypyrazole inhibits the β π acetal resin, and the hardening promotes the formation of the jin. The weight of the composition is 0.01 parts by weight of the chemical accelerator, and the weight of the chemical is 0.01% by weight. 4 2 The resin composition of the knives to form a resin composition having a dielectric layer of copper according to the present invention, wherein the weight of the resin composition is two parts by weight; The total amount of each component of the active vinegar resin and the polyvinyl acetal oxime* is preferably 70 or more. In the copper case for manufacturing a printed circuit board relating to the present invention, the s of the singularity of the singularity of the singularity is in the semi-hardened tree raft with the dielectric powder ', '(10) In other words, it is preferred to contain a dielectric powder in the range of 65 wt% to 85 wt%. In the copper slab having a dielectric layer for the manufacture of a printed circuit board relating to the present invention, the aforementioned dielectric layer is in accordance with MIL_p_13 in the MiL specification.

2213-9834-PF 10 200915932 The resin fluidity at the time of measurement is preferably less than 1%. In the printed circuit relating to the present invention, it is included in the dielectric layer: the particle diameter of the dielectric layer is 〇.〇2em~2, and it is preferably used once. Powder composed of dry dielectric particles In the manufacture of a printed circuit board according to the present invention, the dielectric layer has a thickness of 05 electrocardiograph layer. [Effect of the invention] From M Majia. A dielectric layer having a dielectric acoustic circuit board according to the present invention is printed by S / , and is formed by a capacitive circuit having a low dielectric constant between the compound and the dielectric particles. The dielectric layer of the electric layer is processed by hot pressing, and the lower the resin flowability, the uniformity of the thickness of the dielectric layer can be improved, and the stability can be obtained. Dielectric properties. In particular, the copper flute having a dielectric layer associated with the present invention is used to form a path 'even if the capacitance is relatively low, since the dielectric positive connection is low, and the electric power loss is low. As a result, as a printed circuit board for transmitting a high-frequency signal, it is possible to manufacture a printed circuit board product having a low transmission loss. A copper foil having a dielectric layer related to the present month, a product in which the dielectric layer and the copper foil are laminated, and a manufacturing method and a manufacturing apparatus similar to the conventional copper enamel having the resin can be used for the production. No new equipment investment is required. [Embodiment] Hereinafter, the best mode for carrying out the invention will be described.

2213-9834-PF 11 200915932 Incoming dielectric layer (4), for printed circuit board: There are: 1 electric layer of copper box 1, which is the single sheet of copper flute 2 shown in Figure 1 The dielectric layer 4 of the electric particle 3 is used for the formation of a built-in circuit layer of the circuit board. The copper flute 2, , = used here is limited. But by then 'about its thickness is not particularly thick with 0 / due to the formation of the conductor layer of the capacitor circuit, and 0.5 / ^ ~ 70" range is better. Less than 05 copper flute, due to industrial production difficulties and lack of volume Productivity. If the thickness of the other side exceeds 70", the micro 'cold is not good. X, if you use the problem of not, ^ (4) ^, use the "copper flute of thickness", use "By the bath, join the interface layer pig copper box is better. This is easy to change the operation of the layer of θ. The holder has a thin copper drop and a thin copper box. The dielectric layer 3 is made of a semi-hardened resin containing an epoxy resin, an active ester resin, a bulk powder, and a hardening accelerator to make a dielectric material. . The following 'will be separately described to contain epoxy resin, "on the moon, polyvinyl alcohol shrink resin, hardening accelerator and dielectric powder. 丨之树月日,, and combined ring said: about resin composition. This The resin composition contains this resin, polyethyl alcohol, (4) resin, and hardening promotion. Therefore, the necessary components are explained. For the epoxy resin, the epoxy weight is 100 weights... The resin composition is preferred. ::: 5 parts by weight to 6 ° parts by weight, 11 ‘right & milk resin content is not (five) 25 parts by weight

2213-9834-PF 12 200915932 Condition. In the adhesion between the copper foil constituting the copper foil having the dielectric layer and the dielectric layer, and the adhesion between the dielectric layer and the inner layer circuit of the inner core material, sufficient strength cannot be obtained. On the other hand, if the content of the epoxy resin exceeds the value of =, it is not balanced with other resin components, and it is difficult to simultaneously achieve the dielectric properties as a dielectric layer and the sound of the inner layer of the dielectric layer and the inner core material. Adhesiveness. Here, "the weight of the resin composition is 1 〇〇 来 来 2 2 ' 系 系 系 意味着 意味着 意味着 意味着 意味着 意味着 意味着 意味着 意味着 意味着 意味着 意味着 意味着 意味着 意味着 意味着 意味着 意味着 意味着 意味着 意味着 意味着 意味着 意味着 意味着 意味着 意味着 意味着 意味着 意味着 意味着 意味着 意味着The substances contained in the components (by-products, residues, and residual solvents) are hereby incorporated herein by reference. Then, the epoxy resin is used as long as it can be used for electrical or electronic materials, and there is no particular problem in use. Therefore, various epoxy resins can be used. For example, double-anti-F epoxy resin, double: enamel resin, novolac epoxy resin, o-cresol novolac resin, double = (tetra) epoxy resin, bisphenol novolac epoxy resin, trihydroxy stupid: Wenyu The use of a type of epoxy resin, a tetraphenylethane type ring-on-charge or a halogenated body, etc., is used for the hydrogen addition of ', 曰' '. In particular, those having two or more epoxy groups in the molecule are bisphenol A type epoxy resin, bisphenol F class> earth epoxy resin, phenolic type epoxy #33 lotion, cerium, bisphenol S-type oxygen tree m / ortho-(4) type resin, alicyclic ring # ^ ^ ^ 2 ^ + The group of makeup dust nucleating resin is selected to be used in two or more types. For the active vinegar resin, the function of the jg, the electrical resin, and the ~f 7 ester resin, the low dielectric - the above-mentioned % oxygen resin reaction hardens, and as a ring

2213-9834-PF 13 200915932 Oxygen Tree Moon Hardener comes to you. Here, if the content of the active ester resin is not full, the curing reaction of the epoxy resin is insufficient, and the epoxy resin or the resin is filled. On the other hand, even if the content of the active ester resin exceeds 60 weights, the hardened state of the epoxy resin does not change. As the reaction amount, the amount of the active vinegar resin is considered to be the weight of the epoxy resin. The base is preferably in the range of 75 equivalents to 25 equivalents in terms of hydroxyl groups. The living limulus compound is known to have a linear structure and a ring structure. However, π people you 2 = mid-month, to use an aromatic active ester with a cyclic structure: These active vinegar compounds are obtained by reacting a compound having a phenolic hydroxyl group with a compound having two or more compounds which react with the phenolic hydroxyl group to form a second compound. The oxyhydrogen violent reaction forms the gg. The ggs of the gg. The nucleus of the gg. The nucleus and the iS-methyl thiol group (the chloroform described in Patent Document 1, such as the special fair 4-8444, 2, the aromatic "with 1" The price of the hope class or the Cai categorization of the genius:: the price of the fragrant family and the aromatic (four) compound § the compound specific apt to some active ester compounds human R ϋ + the mouth of the method, can use anhydrous acetic acid Well-known synthesis method such as method, '/, connection method. Implantation: The epoxy resin and the active resin mentioned in the Ϊ Γ , 系 二十 二十 二十 二十 二十 二十 二十 二十 二十 二十 二十 ' The total content of the active resin is 78 parts by weight to 95% Cao 8%/+ _斟π ·> The heavy knife is 佺, the total amount of epoxy resin and active 酉曰 含有 含有 ^ ^ ^ ή, ^ φ , when the time is not divided, the total content of the active vinegar formed exceeds the weight of the other eight-square 'If in the case of the epoxy resin with the knife, then into the other

2213-9834-PF 14 200915932 The content of the polyvinyl acetal resin or the like is small, and the adjustment of the fluidity of the resin is difficult. The unbalanced 'after s piece is more and 'the combination of the oxygen resin and the active s resin is strictly matched with the active ester resin of the oxime resin, η 2 , for 1 equivalent of the epoxy group, into the ^: : To the weight of the epoxy resin, the range of equivalent weight is good. Relatively calculated as 〇·75 equivalents~I, if it is less than 0 75 旦 之 卜 轧 轧 曰 曰 曰 曰 曰 ' ' 舌 舌 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂In the case of a hardening reaction, a dielectric layer having a dielectric positive connection is obtained by a second method. Further, "the amount of the active S resin for the February 若 is super W, and the (IV) hardened dielectric layer. In the middle, the active electricity is not reacted and J is deteriorated due to the heat resistance of the layer. This dielectric is described for the I vinyl alcohol shrink resin. In the present enol acetal resin, τ $ 敫 'polyethylene, '·, and the resin fluidity of the semi-hardened dielectric layer formed by dispersing and mixing the resin composition in the resin composition is used. This polyvinyl acetal resin will be obtained by using vinyl acetate. The vinegar is brewed, and the *J<at JL 5 reactant is obtained by reacting the vinyl acetate obtained by water decomposition with acetaldehyde or butyl. As described herein, polyethylene glycol =:::B: a copolymer of two other ethoxylates: κ port, then, the polyvinyl alcohol used in the present invention is given i±+ In the case of using a degree of polymerization of 15 Å to 25, the degree of shrinkage and the weight of m are preferably. In the case where the resin composition is 1 Torr, the ri 185 water vinyl acetal resin is preferably contained in an amount of 1 part by weight. Polyethyl condensate:

2213-9834-PF 15 200915932

If the weight of the & is less than 1 part by weight in the right side, it is difficult to ensure the flow of the resin in the range described later. On the other hand, if the polyvinyl acetal arsenic RI + day contains s more than 20 weights, it will be made into a tree with an organic solvent. Organic (4) (4) (4) ". For the case of lacquer (-(10)), the hardening accelerator is explained.

Tffi , nt t is a hardening accelerator which has a hardening reaction of a resin at a low temperature and is completed in a short time. As a hardening accelerator mentioned herein, a female imidazole compound such as an aromatic amine or a quaternary ammonium salt compound can be used. Waiting for the ping-pong, ^

Qn σ early temple is better. However, in the case of the present invention, the use of an imidazole compound and the use of an imidazole compound as a hardening accelerator, the semi-hardened energy-hardened resin layer is hardened to form a smooth surface. Therefore, it is preferable that the inner layer of the dielectric layer and the inner core material is electrically improved = and the cured dielectric layer has a good early edge property. The imidazole compound is exemplified as a hardening accelerator, for example, a 21-base taste: sitting, 2-17-seven-salt saliva, 2-ethyl+methyl-salt saliva, 2-phenyl-4-indolyl saliva, 1—Hydrogen B-2 — + — ^ ^ Ethylene Z-decyl imidazole, 1-indolyl-2-ethyl-4-methyl 2 saliva, b-ethyl bromide-4: methyl '5-hydroxyl The imidazoles and the like can be used singly or in combination.

Then, the amount of the hardener added to the epoxy resin is derived from the equivalent, which is strictly speaking, and it is said that it is not necessary to clearly indicate the ratio: the ratio. However, in the case of the resin composition relating to the present invention: in the case where the active vinegar resin also functions as an epoxy resin hardener, the hardening accelerator contains 0. 05 by weight in the weight of the resin, the weight of the compound. ~2 weight is divided into good. If the content of the hardening accelerator is not 2231-9834-PF 16 200915932 at 0. 05 parts by weight, the curing of the epoxy resin and the active ester resin is insufficient due to the content of the epoxy resin. The toughness of the dielectric layer will not increase. On the other hand, if the hardening accelerator exceeds 2 parts by weight, the curing reaction of the epoxy resin and the active ester resin becomes faster, and the hardened dielectric layer is weak, causing a decrease in the strength of the dielectric layer, and the dielectric layer and copper. The continuity of the box is low. The resin composition described above is described on the premise that it is composed of an epoxy resin, an active ester resin, a polyvinyl acetal resin, and a curing accelerator. The resin composition is a substance such as an imidazole compound which can achieve a catalytic action. If a mixture of an epoxy resin and an active ester resin is heated, the arylcarbonyl ion is detached from the vine group of the active vinegar resin towel, and the aryl group is regenerated. The aryloxy group of the ion is from the phenyl group containing a substituent or the naphthyl group. The oxygen ion is added to the epoxy group of the epoxy resin. If aryloxy ions are added to the nucleus of % I, a new oxy ion (-0) is formed, which combines with the arylcarbonyl ion detached from the active ester resin. The reaction of the base ends. From the course of this reaction, it can be understood that in the reaction of the oxygen resin with the active material, there is a hydroxy group which does not have a high polarity, and the dielectric layer of the epoxy resin is used in the hardening reaction. It should be suitable for the formation of a dielectric positive connection. In this case, the weight of the resin composition is 1 〇〇 heavy fat, and the hardening promotion: the resin, the active vinegar resin 1 vinyl alcohol shrinkage tree ^ )' is preferably 70 parts by weight or more. This combination

2213-9834-PF 17 200915932 If the amount is less than 70 parts by weight, the deterioration of the dielectric properties of the cured dielectric layer formed using the resin composition becomes remarkably poor. It is useful for adding it to its ingredients, and it has a rubber component. By adding a rubber component, the toughness of the dielectric layer after hardening can be used to improve the rubber composition. The concept of natural rubber and synthetic rubber is described as the latter. Among the synthetic rubbers of the latter, there are styrene-butadiene , butadiene rubber, butyl rubber, ethylene-propylene rubber, etc. Further, in order to secure the heat resistance of the formed dielectric layer, it is also useful to use a heat-resistant synthetic rubber such as nitrile rubber, chloroprene rubber, Shixia rubber or amine vinegar rubber. About this peptide 腴 腴 八 &#, ά' iL ^ Ai. ^, Knife" his resin component reacts to open) The can is good, and the various functional groups at both ends are 疋 (end "Ding Er Dilute nitrile is useful. In the manufacture of printed circuit boards related to the present invention, there is a dielectric layer: the dielectric layer described above, which contains the dielectric powder: hardened tree moon weight It is 1 〇〇w1;%# ^ ^ ^ contains the second in the range of 65wU~85wt%: If the content of the dielectric powder is not full, Π: The capacitor circuit cannot obtain sufficient capacitance. On the one hand, if the capacitance of the body becomes high: in the case of =: 'Although as a dielectric, the amount of resin in the dielectric layer is changed: the whiteness of the electrode layer and the adhesion of the surface of the road After the hardening, the electric layer (four) is significantly cracked and becomes brittle, and the heart is not good. Then, the dielectric powder used in the range of 'm~2/zm' is used for dielectric dielectric. It is preferable that the powder constituting the aggregate of the particles. “ ^ can meet the design capacitance required by the capacitor circuit

2213-9834-PF 18 200915932 Yes, you can use any material. For example, a metal oxide powder containing at least one metal selected from the group consisting of m, chin, rhodium, cadmium, yttrium, tin, yttrium, yttrium, yttrium, yttrium, yttrium, yttrium, yttrium, yttrium, yttrium, yttrium. Specific examples thereof include titanium oxide strontium, lithium titanium oxide strontium, pTZ (pb(Zr - Ti) ruthenium, PLZT (PbLaTi〇3 · PbLaZrO), SBT (SrBi2Ta2〇9), and the like. When the particle diameter of the particle is less than 〇2 V m, the resin composition is used as a resin lacquer, and it is difficult to uniformly disperse it in the mixture. Therefore, it is not preferable. When the particle diameter of the particles exceeds 2 #m, if the thickness of the dielectric layer of ~4 is too large, the surface of the dielectric layer becomes rough in the semi-hardened state. The tendency is to become higher. Further, 'on the surface of the granules constituting the dielectric particles of the dielectric powder described above, a surface treatment layer for improving particle dispersibility in the resin lacquer is formed as a surface treatment layer. It is also preferable to use the electric particles. At this time, the surface treatment layer on the surface of the particles of the electric particles can be formed by treatment with a decane coupling agent, oleic acid treatment, stearic acid treatment, or the like. k k 偶 ^ ^ treatment 'stable to improve the resin lacquer and the wettability of the surface of the dielectric particles. The copper composition is manufactured by using the resin composition described above and the dielectric powder. Here, the method for preparing the copper layer having the dielectric layer will be described. Make this resin paint

’. Τ 'Epoxy resin, active ester resin, polyvinyl acetal resin, hardening your Buddha, m ^ Jinzhou, other arbitrary rubber into powder, etc., 2213-9834-PF 19 200915932 in the above combination range In the case of internal mixing, the redness of the resin composition is a resin composition. The weight of the epoxy resin is: 25 parts by weight, the weight of the epoxy resin is: the most basic resin composition, the weight of the active vinegar resin is ~20;:: 28 parts by weight to 6 ° parts by weight of 0. 01 parts by weight ~ 2 The combination of the polyvinyl acetal resin of the heavy-duty Ba Li knife and the hardening accelerator of 30 weights and eight knives. Then, the better amount of the active epoxy! grease, 34 parts by weight - heavy duty, 〇 05~1 重 〇 〇 为 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 。 。 。 。 。 。 。 。 。 。 。 。 。 。 # σ (1) The weight of the resin composition is 78, the weight-separable ester resin is added to the total amount of the epoxy resin and the active ester resin, and the active ester resin is blended with the active ester resin. (111) In the case where the components of the basic combination of the rubber component such as the rubber component are added to the upper and second combinations (epoxy week), the upper aldehyde tree 浐... eucalyptus eucalyptus, active ester resin, polyvinyl alcohol The total content of the shrinkage and hardening accelerators is 7. The above three conditions are preferred as materials for satisfaction. ',, 丄, and a lower dielectric dielectric layer. Next, the resin composition is dissolved in an organic solvent to form a solid shape. 0wt% ~ surgery t% resin paint. For the purpose of dissolving the resin for the purpose of preparing the resin for the resin lacquer, for example, Ding Gang,

Cyclohexanone, Ν'N-dimethylformamide, N,N-dimethylacetamide, dioxin, ratio (IV), ethanol, etc., or a mixture of two or more solvents, 2123-9834- PF 20 200915932 is used as possible. However, in the case of the resin composition used in the present invention, the purpose of the next step is to electrically connect the low dielectric layer, and the organic solvent should be selected as in the case of the use of the organic solvent. The resin composition used in the present invention promotes the reaction of the tongue Lt resin with the active vinegar resin. Therefore, it is possible to avoid the use of an alcohol solvent such as ethanol or methanol which has the possibility of fat precipitation. "This point dissolves all the resin composition of the resin composition used in the present invention, and the rate of dissolution of the constituent resin is NN-methyl-polyethylene glycol. The polycondensation resin, .. tI, -methylformamide, n, n-dimethylacetamide, etc. are preferably used. Then, better, if the top is tied into the ^ An aromatic carbonized chlorine-based solvent. This is because the resin composition of all of the resin compositions which can be used in two quickly can be used to heat the heat during the dust processing of the copper bead laminate. / Volatile removal of the ground and the purification of the volatile gas is also easy. The viscosity of the resin lacquer can also be used for the viscosity of the surface of the innocence and the island. The m week is suitable for coating on the copper enamel table. The solvent added herein is added to the resin composition, in the range of the solid resin of the resin, which is divided into 10 resin cracking: in the range of the resin solid content, when coating the surface of the copper box, in the J dimer powder State, and can form a resin film with the best film thickness precision. In the case of 'the viscosity is too low, after the surface is applied, the resin lacquer flows and it is difficult to break the thickness of the film. The uniformity of the film is relative to this. If the resin solidity exceeds the gamma, the viscosity will become old. The formation of a uniform thickness of the resin film becomes difficult. The door is mixed with a dielectric powder for the resin lacquer obtained as above.

22J3-9834-PF 21 200915932 Stirring as a resin lacquer containing dielectric particles. The method of stirring this σ at this time is not particularly limited. However, in the dielectric powder, when the resin emulsion containing the dielectric particles is semi-hardened, when the weight of the semi-hardened resin is 10% by weight, the dielectric is contained in the range of 65 wt% to 85 wt%. The amount of the bulk powder is added to the resin lacquer. Then, the resin varnish containing the dielectric particles is applied on the early surface of the copper foil to form a 3"m~300 "m thickness, and more preferably a "m thickness resin film. For the formation of the resin film, a continuous coating of a co-coater (co_a coater), an edge coater (a knife edge (3) ater), a gravure coater, or the like can be used: the use of the device is It is possible. Then, the shape of the resin film, the tree is dried, and the semi-hardened dielectric layer containing the dielectric powder is formed on the surface of the copper foil to obtain a copper ruthenium having a dielectric layer. The drying conditions at this time are not particularly limited. When the resin flow is obtained, the surface can be obtained, and when it is bonded, the reflow layer of the composite and the degree of control after curing can be reduced to reduce the manufacturing power. The copper electric layer having a dielectric layer according to the present invention preferably has a mobility of less than 1% in accordance with MIL-P-1 3949G in the MIL standard, and the following effects are obtained by making the resin fluidity less than full. In the inner core material table having the inner layer circuit and the dielectric layer of the copper foil having the dielectric layer according to the present invention, the resin composition of the semi-hardened state in which the dielectric powder is dispersed and mixed is also small in fluidity of the resin. Semi-hardened dielectric dielectric The thickness does not change too much. Therefore, as long as the dielectric layer thickness of the semi-hardened state of the stage of the copper foil of the electric layer is known to be the same as the designed thickness of the hardened dielectric layer, it can be 2123-9834- Ρρ 22 200915932 The management focus of the circuit is to reduce the management cost. The resin fluidity referred to here is the value measured according to the MIL specification MU P 1 3949G. That is, from the "Electrical layer of copper-4 sample 4 pieces of 1 〇cm square sample, the four samples in the overlapping state with a pressing temperature of 17rc, pressing the pressure i4kgf / cm2, the time ίο points of the condition For the bonding, the fluidity of the resin at this time is calculated by the formula of Equation 4. However, in the fluidity of the resin in the present invention, 疋 & In the layer of copper berth m &), the sensitivity of the measurement accuracy could not be obtained, and a copper layer having a dielectric layer of $4 thick was intended to be used as a sample. For reference, f uses the usual prepreg and the usual copper box with resin (4) A m thick tree layer). [Formula 4] Resin fluidity = flow 屮 ^tt) xioo tree.../(layered body weight Η copper for the manufacture of printed circuit boards related to the present invention

5# m〜25// m is preferred in the copper foil, the medium Thunder, another " electric slip I θ, thickness is 0. 5# m~25// m is better. Thick; #0.5" The dielectric layer is not fully filled, and it is desired to form a dielectric layer containing a dielectric powder to hold a film thickness of -1 wide and a large area of uniform thickness of dielectric If the layer is also difficult to maintain a thickness of m, it cannot be obtained: if the thickness of the dielectric layer is made to be more than the required Rayleigh, the present invention is shown in the following examples. in. For a clearer understanding [Examples] The dielectric layer of the tongue is made of reed & varnish, coating resin (ingredient A, component A,), active ester

2213-9834-PF 23 200915932 Resin (component B), polyvinyl acetal resin (component c), and hardening accelerator (component D) are basic components, and include other additive components (component E) added as necessary to prepare Three types of resin compositions were used. The constituent components of the resin composition are as follows. Ingredient A: o-cresol novolac type epoxy resin [epoxy equivalent 22 〇] (YDCN-704, manufactured by Tohto Kasei Co., Ltd.) Ingredient A': bisphenol A type epoxy resin [epoxy equivalent 475] (Dongdu Chemical Co., Ltd.) YD-011) Ingredient B: Active ester resin [65 wt% toluene solution, 〇H-based conversion of solid fraction 220] (Tony Oil, INK Chemical Co., Ltd., 9451) Component C: Polyvinyl acetal resin (electrical Chemical Industry Co., Ltd. 6000C) Ingredient D: 2-phenyl-4-indolyl-5-hydroxymethylimidazole (4四4ΜΗΖ from Shikoku Chemical Co., Ltd.) Ingredients: Bridging rubber composition [1 5wt% butanone solution] (JSR) XER-90 manufactured by the company, the resin components described above are blended as shown in the following Table 1, and three kinds of resin compositions (resin composition 1, resin composition 2, resin composition 3) are prepared. 'Use N, N - Dimercaptocarboxamide: a mixed solvent of methyl ethyl ketone = 1 : 4 to prepare a resin emulsion of a resin solid content of 4 〇 wt% (resin lacquer 1, tree lacquer 2, resin lacquer 3). Then, 'the barium titanate powder of the dielectric powder having the powder characteristics shown below in the above resin lacquer (average primary particle diameter = 〇·25 A m, volume cumulative average particle diameter (Dm) = 〇· 5 # m) Mixed dispersion, as a formable

2213-9834-PF 24 200915932 8〇wt% half of the acid bismuth resin paint. The dielectric particle is a resin varnish coating machine containing dielectric particles as obtained above. 2 " m thick copper foil roughening surface, the shape = degree: the resin film with dielectric particles to apply, for 5 minutes: c after 3 minutes in a heating atmosphere of 140 C:; A dielectric layer of a semi-hardened state is obtained, and a copper crucible having a dielectric layer (a copper box having a dielectric layer (4), a copper flute having a dielectric layer 3) is obtained. 1Electrical layer Then, four sheets of 10 〇cm square 枓 were taken from each of the copper layers having the dielectric layer as a sample for resin fluidity, and the fluidity of the resin was measured. As a result, the fluidity of each of the core resins was 0.4%. $6 and 'will each of the copper boxes with dielectric layers' on the surface of the inner core material on the surface, apply 21k / day h 60 minutes of heating to perform the second 180: outside ... 2" thick copper (a) It is processed into a linear circuit for peel strength test obtained by performing a test circuit for a two-dimensional linear circuit and a test electrode circuit having a dielectric characteristic of the upper electrode, and is used for the test. The capacitor circuit evaluates the dielectric properties. This summary is shown in Table 2. The second inner layer is also referred to as the inner core material as follows. The purple layer is formed by the easy-peeling type of copper having a carrier box as shown in Fig. 2 (4).

2213-9834-PF 25 200915932 (The surface of the pig layer 7 with the carrier 5/joining interface layer 6/copper layer 7 is provided as a roughening place: in the copper t舜 is the main 1 fine copper grain 8) The surface is silly ceramic to form the photoresist layer 9 of the surname shown in Fig. 2 (7). However, as shown in Figure 2(c), 'exposure and development on the photoresist layer 9 to form the etch resist pattern 9 for the copper-clad circuit, in order to open the image (shown, the surface of _5 is full:: : The second film forms the _ photoresist layer 9. The "thin dry thin surface" is also formed by the (four) engraving 'from the copper slab layer 7 to form the fine copper particles 8 and the surface is formed to form a picture as shown in Fig. 3 (4). Circuit... :8 Using a commercially available 砮葙r* stand, the batch electric quotation U opens and then becomes ', and j is used to make the hardened dry film swell and remove, 4 into the circuit diagram of the carrier (Fig. 4) 20. Dip material == = :: sample 2 " pre-formed resin substrate shown in Figure 4 (1), so that the formation is formed; laminated plate I at this time, as the first surface is in contact with the prepreg 12 _" 2G As shown in the first diagram of the circuit 11, the chip has a circuit pattern 2 of the carrier. The material 12' is disposed on the outer side of each of the two layers. The copper-clad laminate laminate is 3° apart. As above, in the case After the varnish, the substrate 5 on the outer layer is peeled off from the surface of the substrate in a state shown in FIG. 5(g) to obtain a buried circuit in which the resin on the circuit is embedded, and the circuit is buried in the substrate. To two The printed circuit board 40 between the n-sides of the circuit is then formed to provide a means for ensuring the formation of a via hole. [Comparative Example] This is used as an inner core material.

2213-9834-PF 26 200915932 This comparative example was constructed using a resin which does not use the component c (polyvinyl acetal resin) which is an essential component of the above embodiment. Others, in the same manner as in the examples, copper slabs having a dielectric layer were fabricated, and various performance evaluations were performed. The details are as shown in Tables and Table 2 for comparison with the examples. Table 1 Component Unit Examples |-- Resin Composition 1 Resin Composition 2 Resin Composition 3 Comparative Example Component A ------ 31.9 32. 9 30. 9 35. 3 Intercalation Component A' —- 17.6 19. 6 16.9 19. 7 Electrolytic component B Part by weight 40. 0 42.0 | 38.7 44. 5 Composition of component C 10.0 5.0 10. 0 Component D 0.5 0.5 0. 5 〇. 5 Composition E - 3.0 Resin Solid content * wt% 40 —* . Dielectric powder content wt% 80 *Resin solid content as resin varnish 2 Evaluation item Steel foil with dielectric layer 1 Steel foil 2 with dielectric layer Copper foil of the electric layer 3 Comparative resin Flowability 0.4% 19 9% Peel strength 〇·7kN/m 〇6kN/m Dielectric positive connection (1GHz) 0.006 0. 005 0. 008 0 008 Dielectric ratio (1GHz) 8.8 8.5 8.9 7.7 <Comparison of Examples and Comparative Examples> Refer to Table 2 for comparison of the above-described examples and comparative examples. Looking at the resin fluidity of Table 2, there are very between the examples (copper foil with dielectric layer, copper foil with dielectric layer 2, copper foil 3 with dielectric layer) and the comparative example.

2213-9834-PF 27 200915932 = Different. In the semi-hardened dielectric layer of the comparative example, if it is heated and the 々IL is mobilized, it will show that the Pit is shaken, and the resin flowing in the same degree as the hanging tree is the same. The phase resin is hardly precipitated. Underheated and re-fluidized' The thickness of the dielectric layer of the copper box is different: Example 1 'The dielectric m pellet of the copper foil with the electric layer: 'but the dielectric layer of the embodiment is considered to be comparable The thickness is evenly measured in comparison with t彳丨-5. Therefore, the peel strength of the embodiment is high. .UN/m. Comparing with the dielectric positive embodiment of the comparative example having the dielectric reed H H of the embodiment, the dielectric positive connection of the comparative example can be obtained, and the 4 is equivalent or can be stable and high in value compared with the comparative example. For example, in the examples, the peel strength and the implied value of the examples are better than those of the good ones. 丨, both show an overall balance. [Industrial Applicability] A dielectric layer related to the present invention. The circuit is embedded in the inner layer circuit surface of the inner core material (inner board) disposed in the insulating substrate, and the printed circuit of the inner layer core layer is used to 'make the surface of the inner layer core material' The electrical layer bonding will improve the copper/silicon properties of the dielectric layer on the outer layer, and the resulting capacitor circuit will have a lower dielectric loss even if the capacitance is compared to the copper box layer. As a result, it is possible to &lt; - because the dielectric positive connection is low, the brush circuit board has low transmission loss, and (4) the printing of the frequency signal is possible. [Circular Simple Description]

2213-9834-PF 28 200915932 Fig. 1 is a schematic cross-sectional view showing a copper foil having a dielectric layer for use in manufacturing a printed circuit board according to the present invention. Fig. 2 (a) to Fig. 5 (g) are schematic views for explaining the manufacturing process of the inner core material. [Description of main component symbols] 1 Copper foil with dielectric layer for printed circuit board manufacturing 2 Copper pig 3 dielectric particles 4 Dielectric layer 5 Carrier foil 6 Bonding interface layer 7 Copper foil layer 8 Fine copper grain 9 Etching light Resistive layer 9, etched resist pattern 10 copper foil with carrier foil 11 circuit 12 prepreg 20 circuit pattern with carrier 30 copper foil laminate 40 printed circuit board with buried circuit 2213-9834-PF 29

Claims (1)

200915932 ^ X. Patent application scope: 1. A copper pig with a dielectric layer for the manufacture of printed circuit boards, which is provided with a circuit in which the upper surface of the circuit and the surface of the substrate are slightly in the same plane. A copper foil having a dielectric layer for forming a capacitor circuit layer is attached to a surface of the printed circuit board on which the circuit is embedded, wherein: the copper beryllium copper box having the dielectric layer is provided on one surface thereof to contain a dielectric body a dielectric layer formed by a semi-hardened resin of powder, the dielectric layer being dispersed in a resin composition containing a net shame + (4) dip, an active ester resin, and a vinyl alcohol: rutting accelerator The dielectric powder", the dielectric powder in the hardened state contains a resin layer. 2. If the patent application is patented; the siren, = ^ „ the printed circuit board of the younger brother f is made of Xiu ancient, the copper foil' The above-mentioned medium: ', a vinegar resin, a polyvinyl acetal material, and a resin composition which is a component of the resin composition of the ancient hardening accelerator when the weight is (10) by weight. :.% milk resin 25 weight Parts ~ 60 weight 3 · Such as Shen Qing patent range of the dielectric layer of the copper box, its contention, meaning,., corpse brush circuit board manufacturing with vinegar resin, polyethylene glycol shrinkage: ^ electrical layer is contained The epoxy resin and the resin composition having a weight of 100 parts by weight of the resin composition of the 's hardening accelerator are shaped as follows: 28 parts by weight of the active ester resin, 4. If the patent application range is 1 = object- The steel layer of the dielectric layer, wherein the printed circuit board for the manufacture of enamel, and the like has a vinegar resin and a polyvinyl alcohol:: the electric layer is a resin containing an epoxy resin, a living M, and a hardening accelerator. Composition 2231-9834-PF 30 200915932 When the weight is 100 parts by weight, the total content is - weight =::: = active ~. 0, the composition of the moon 来 composition is formed as follows. Copper foil of the layer, 苴中, t, 1 - Manufacture of the vinegar resin and the polyacetate acyl acid tree for the manufacture of the road board, the resin for each oxygen tree, and the living weight of (10) by weight, the resin of the accelerator The composition is especially formed by using a resin composition having 3 polyvinyl alcohol oxime fractions. For example, the copper foil of the dielectric layer of the patent scope is applied, wherein the epoxy resin used in the manufacture of the circuit board, the polyvinyl alcohol/...1 electrical layer is contained in the epoxy resin, and the living denier (4) The material of the 'hardening accelerator B weight: 100 parts by weight' contains a hardening accelerator. A substance is formed by weighting the resin composition. &quot;_ 里份~2 八申明 Patent 祀 第 第 第 第 第 第 第 第 第 第 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷The resin composition of the layer, the weight of the composition is 5 〇〇 in the epoxy resin, the active ester 杓t into the components of the resin composition, "A 7n ethylene glycol shrinkage resin, hardening promotion The agent kneading knife σ 6 is set to 7 〇 or more. 8' As in the copper layer of the printed dielectric layer of the i-th patent of the patent application, in the middle, the first, the tenth and the eightth, the U-shaped semi-hardened resin has a weight of two: the layer 'is in the medium containing the dielectric powder. Electric powder. /... Contains 6 - Fine 9 · If you apply for a patented ribs, the dielectric layer of the copper box, where: J's printed circuit board is manufactured with 4'1) 1 electrical layer 'in the mil specification according to 2213-9834 -PF 31 200915932 MIL-P-1 3 949G The resin fluidity at the time of measurement was less than 1%. The copper foil having a dielectric layer for manufacturing a printed circuit board according to the first aspect of the invention, wherein the dielectric powder has a primary particle diameter of 0.02//πι 2 //π] A powder composed of a range of dielectric particles. 11. A copper foil having a dielectric layer for use in the manufacture of a printed circuit board according to the first aspect of the invention, wherein the dielectric layer has a thickness of 〇.5//m~25. 2213-9834-PF 32