JPS583299A - Method of producing flash circuit - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a novel flash circuit with excellent yield, and more specifically, a method for forming a desired wiring pattern on a long single-sided metal 1141 laminate or sheet by a continuous method. A 1 ml wiring board is used, and after stacking two continuous wiring boards fat on their backs, a tree layer is formed on both surfaces of the wiring board with uncured or B-stage thermosetting resin layers. Continuously layer 1M fat-adhesive soda film (BL) and heat and pressurize it to fill the non-wiring S of the wiring box with semi-cured or half-cured filling, and cut to form wiring of desired dimensions. After making the board tel, cut the wiring board tel to the desired size using scissors.
Either as is or on the back of the wiring (if lc) with the desired dimensions, prepreg, Jlll film or adhesive sheet, and a laminate or metal cover are laminated and molded, and after curing the resin, the wiring 1 is polished and the wiring metal is This is a method for manufacturing flash circuits characterized by exposing and smoothing the surface.

Conventionally, when manufacturing flash circuits, first the edges are press-molded together with prepreg to obtain a semi-hardened steel laminate with semi-hardened prepreg, then wiring is formed on the laminate and then heated again.・Manufactured using methods such as filling the plated wiring conductor into the resin by lamination molding under pressure, and applying gold plating as necessary, but this method does not allow forging when manufacturing flash circuits in large quantities. The control conditions are small and time consuming, which is very disadvantageous in terms of processability, workability, and mass production.

As a result of intensive research into a method for continuously manufacturing flash circuits that is more productive than conventional methods, the inventors of the present invention have developed a method for continuously manufacturing flash circuits that is more productive than conventional methods.
By introducing a process of transferring the resin of the l film to the non-wiring area, we discovered that it was possible to use a continuous process with spring ink for the process tube layer, and we were able to use two long sheets in the production of single-sided flash circuits. This work was completed after discovering that the resin could be transferred and hardened at the same time on the printed wiring board.

The present invention will be explained in detail below.

The elongated single-sided metal foil-clad laminate or sheet of the present invention may be any ordinary laminate or metal foil-clad laminate that can be used in a long length of 41 mm. Examples of metals include steel, nickel, and steel alloys and nickel alloys. Further, as the substrate or sheet, for example, phenol resin, melamine 1III11, epoxy 8M1 unsaturated polyester resin, isocyanate resin, diallyl phthalate resin, silicone resin, acrylic resin, alkyd resin, 1,2-polybutadiene resin 1, cyanate ester resin layer, polyimide resin or various modified resins thereof 1
Curable resins such as lil11 and reinforcing substrates, such as roving cloth, cloth, Chobut mat, surfacing cloak, etc., can be used with lath cloth and other synthetic or natural inorganic fiber cloth, fully aromatic nylon cloth, glass fiber and fully aromatic nylon cloth. Aromatic nylon blend fabric, vinylon, tetron,
Synthetic fiber cloth such as acrylic, Ia cloth, linen cloth, felt,
Kraft paper, cotton paper, paper-glass blend paper, semi-carbon fiber laminates and sheets, super heat-resistant engineering resins such as polyimide, polyamideimide, polyhydantoin, polyparabanic acid, polyphenylene sulfide, polycarbonate, polyphenylene ether,
There are general-purpose engineering plastics such as polysulfone, polyester, and nylon, as well as heat-resistant general-purpose resins, and modified thermoplastics such as crosslinked network polyethylene, nylon, rjtl), phenylene ether, polycarbonate, and polysulfone. Examples include films or sheets of materials exemplified by resins, and composite substrates or sheets of these and the above-mentioned reinforcing base materials.

The release film of the resin layer--film in which the uncured or B-stage thermosetting 111W layer of the present invention is formed is polyethylenetetrafluoride-ethy5-lene, tetrafluoroethylene-hexafluoropropylene. Fluorine resin films such as copolymers, tetrafluoroethylene-ethylene copolymers, polytrifluorochloroethylene, polyvinylidene fluoride, polypropylene, poly(4-methylpentene)
1. Polyolefin films such as polybutene-1, cellulose-conductor films such as triacetyl cellulose, diacetyl cellulose, and aceto-butyrate cellulose, paper with delamination properties for traps, and plastic films other than those listed above are also used. It can be selected depending on the type II of the thermosetting resin. In addition, as the thermosetting resin composition to be applied to these films to form a single layer, any one can be used as long as it can be used for the substrate or holding sheet of the elongated single-sided metal foil-clad laminate or sheet. However, from the viewpoint of workability, processability, and physical properties of the resulting flash circuit, a thermosetting resin composition is preferable. Also, the thickness of the 111M layer depends on the length of the long continuous wiring board (ml) used. 6- to make it suitable for mass sales, which is necessary for filling non-wiring areas.Among these thermosetting resins, in the present invention, processability, workability, and thickness are determined based on the characteristics of the obtained flash circuit. Of these, cyanate ester resin compositions are particularly preferred.

Now, the cyanate ester resin composition suitably used in the present invention has a cyanate group (-
0-CEN'), or a prepolymer thereof alone, or a resin composition containing these components as essential components. The polyfunctional cyanate ester which is a preferred essential component is an organic compound having two or more cyanogen ester groups, and the preferred cyanate ester is a compound represented by the following general formula. Specific examples include 1.5- or 1.4-diallylbenzene, 1,3.5-)lycyanatobenzene, 1°3-11.4-11.6-11.8-12.6-
or 2,7-dicyanatonaphthalene, 1°5.6-
) ricyanatonaphthalene, 4.4-dicyanatobiphenyl, bis(4-cyanatophenyl)methane, 2.
2-bis(4-cyanatophenyl)propane, 2.2
-bis(3゜s-diyrollo4-sia+-)phenyl)
Furopane, 2,2-bis(3,5-dibromo-4-cyanatophenyl)propane, bis(4-cyanatophenyl)ether, bis(4-cyanatophenyl)thioether, bis(4-cyanatophenyl) sulfone,
tris(4-cyanatophenyl) phosphite, tris(4-cyanatophenyl) phosphate, and/or
These include cyanate esters obtained by the reaction of borac and cyanogen halides. In addition to these, special public
19251.41 meeting @45-18468, l1lI project
@44-4791.411 Kinki 45-11712, Tokuko Sho 44-41112, Jikai 1147-2!1155Ji
Cyanic acid esters described in 2004 and 4151-, 63149 and the like can also be used.

In addition, as a prepolymer obtained by subjecting the improved polyfunctional cyanate ester to heavy metals in the presence of mineral acids, Lewis acids, salts such as sodium carbonate or lithium chloride, and catalysts such as phosphate esters such as tributylphosphine. It can be used.

These prepolymers generally have a my-ugly-triazine ring in the molecule, which is formed by trimerization of cyanide 1 in the cyanate ester. In this experiment, it is preferable to use the above-mentioned prepolymer having an average molecular weight of 40-1a to 600.

As a component for obtaining the cyanate ester resin composition of the present invention by combining with the polyfunctional cyanate ester, maleimides having one or more maleimide groups, preferably two or more maleimide groups are used. Functional or multi-blind hydroxylated (meth)acrylic acid ester, (meth)acrylic-〇epoxy ester, (meth)acrylic acid! - Esters of (meth)acrylic acid such as alkenyl esters and prepolymers thereof; diallyl phthalate,
Polyalkenyl compounds such as divinylbenzene, diallylbenzene, trialkenyl isocyanate and their prepolymers; dicyclopentadiene and their prepolymers; epoxy ms, phenol tll:bo9 vinyl formal, polyvinyl acetal, dtl) hinyl butyral, etc. Polyvinyl acetal resin; acrylic resin, silicone resin, alkyd resin with OH group or C0OH group; polybutadiene, butadiene-acrylonitrile copolymer, polychlorobrene, butadiene-styrene copolymer, polyisoprene, butyl rubber, natural rubber, etc. Liquid elastic rubbers can also be used as appropriate.The cyanate ester resin composition described above itself has the property of becoming a heat-resistant resin by being assembled into a network by applying an electric current. However, for the purpose of promoting crosslinking and reticulation, a catalyst is usually used. Such catalysts include 2-methylimidazo-
V, 2-undecylimidazole, 2-heptadecyl imidazole, 2-phenylimidazole, 2-ethyl-
4-methylimidazole, 1-benzyl-2-methylimidazole, 1-propyl-2-methylimidazole,
1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-
Imidazoles exemplified by cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-guanamineethyl-2-methylimidazole, as well as trimelide forging adducts of these imidazoles; N, N -dimethylbenzylamine, N
, N-dimethylaniline, N,N-dimethyltoluidine, N,N-dimethyl-p-anisidine, p-halogeno-
N,N-dimethylaniline, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, N,N,N',N'-tetramethylbutane Diamine% tertiary amines such as N-methylpiperidine; 7-enol compounds such as phenol, cresol, xylenol, resorcin, catechol, phloroglucin;

Lead stearate, zinc naphthene, zinc octyl,
Organic metal salts such as tin oleate, dibutyltin maleate, mankane naphthenate, cobalt naphthenate, iron 7cetylacetonate; 8nCJJa, ZnC, 142, AJ
(Inorganic metal salts such as Js; peroxides such as far benzoyl oxide, lauroyl peroxide, capri + full peroxide, 7 cetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl sea perphthalate; maleic anhydride, Acid anhydrides such as 7-talic anhydride, lauric anhydride, pyromellitic anhydride, trimellitic anhydride, hexahydro 7-talic anhydride, hexahydro trimellitic anhydride, hexahydropyromellitic anhydride,
Further examples include azo compounds such as azobisnitrile.

The amount of the catalyst to be added is sufficient within the general range of the catalyst amount, for example, it may be used in an amount of 10 weight or less based on the total weight of the catalyst.

KPJ
The method for forming the desired wiring pattern may be the usual manufacturing method for scale continuous wiring boards (AT). This is a method in which a desired wiring pattern is formed on a long laminate or a sheet by continuously carrying out plating, gold plating, etc. processes.

The long continuous wiring board (al) thus obtained is stacked with the wiring pattern portion aligned on the lI& plane and used in the next process. #! A thermosetting resin layer is formed on a film, and the thermosetting resin composition is coated with a solution or solvent-free using a conventional method such as a roll coater method, knife coater method, dipping method, or spray method. This is a method 13- in which a liquid is applied and heated or dried.

On the wiring surface of the above-mentioned continuous one-sided wiring 4 [-], the resin-attached release film (b> 11 skin layer adhering surface) is continuously laid on the wiring surface and heated and pressurized to apply resin to the wiring surface. It is transferred and filled into non-wiring areas and semi-cured, or it is cured manually after being filled and cut to form a wiring board (CL) of desired dimensions.

In the case of the present invention, since the #4j first layer transfer surface always has a surface other than the top surface, the resin layer of the release layer film (BL) has a melting point within the heat curing temperature condition and has a high melt viscosity. is preferable. This is because, for example, if the melting point is 60°C and the general heat curing temperature is 100°C or higher, resin sag may occur under semi-curing conditions, causing defects. Therefore, in this case, When the melting point is low, it is preferable to use a material with a high melt viscosity 1 or a fast curing speed, and usually the melting point is 100 to 150°C and the semi-curing condition is a few degrees Celsius to a few degrees Celsius.
It is preferable that a curing reaction rate of normal curing reaction rate be obtained at 20° C. higher am.

The conditions for transfer filling are as follows: 111 ml of film with 1 l of wood (bl 14-) is carried out at a temperature several degrees Celsius to 20 degrees C higher than the melting point of the wood**, and the pressure is 13 mm when sequentially pressurized with a roll or the like.
It is preferable that the upper surface is 0.1 to 20 to 4, and the upper surface is 0.1 to 20 to 4.

Semi-curing is performed as it is under transfer filling conditions, or after transfer filling, a heating zone is provided and semi-curing is performed, followed by cutting into a desired size to obtain a circuit board (c) of desired size. Here, the semi-curing conditions may be the same as the transfer conditions, or it is preferable to use a higher temperature, for example, 120 to 180°C.

This 1 road board (CL) is laminated with prepreg or prepreg and a laminate plate or metal plate on the back side as necessary, and after laminating the 1st layer and curing the resin, the side surface of the wiring is polished to expose the wiring metal and the surface The flash circuit of the present invention is obtained by performing a smoothing process.

Here, lamination molding is a wiring board of the desired size (CL) to be laminated between smooth plates, such as ordinary stainless steel drawing boards, through a film, or other prepreg, prepreg and laminate as necessary. When integrated with a metal plate or a metal plate, the structure is formed by laminating and molding them.The laminating molding conditions may be the curing conditions of the thermosetting resin composition used for the resin layer-attached release film (BL), which is particularly preferable. In the case of a cyanate ester tree *m which is an embodiment, the temperature is 100 to 500°C in a range of 10 to 100°C.

Further, a conventional method is sufficient for polishing.

The present invention will be explained in more detail with reference to Examples below. Parts indicate parts by weight.

Example 1 2.2-bis(4-cyanatophenyl)propane 10
After preliminarily reacting 00t at 150°C for 150 minutes, it was dissolved in methyl ethyl ketone, and 200t of novolac epoxy resin It (It crystal name: gCN-1275, manufactured by Ciba Geigy) was further dissolved in this to form a homogeneous happy liquid. A varnish was prepared by adding 0.5 F of zinc octylate and 0.32 F of lyethylenediamine as catalysts.

Apply this varnish to a 47 fluoride ethylene film with a thickness of 25 cm and a width of 550 cm and dry it to a resin layer thickness of 56 cm.
B − with ~42 μ and gel time at 170 °C of 40 seconds
A stage thermosetting single layer snow coating device film (4) was obtained.

On the other hand, the thickness of the copper foil is 35 mm with a thickness of 1.50 mm and a width of 5 mm.
11 long pieces of iris steel-clad glass fiber epoxy tree laminate were continuously processed using a conventional method to form a 50◎■×500-standard wiring board, which was then plated with a thickness of 2μ. ,
After further applying MuU plating with a thickness of 1 μm, the wiring patterns were shifted and overlapped on the back side to form a long continuous tied piece I [Circuit 4].

The resin layer surface of the resin layered lug film (4) is placed on the wiring surfaces on both sides of this long interrupted circuit board (8).
After heating and pressurizing with a heating roll at 0°C under a pressure of 10 rl and an average heating time of 50 minutes, the transfer filling resin was heated for 50 minutes to form a transfer filling resin 1 Softening Machine II! 120
The temperature was adjusted to ~135°C, and the ethylene film was peeled off after 4 hours of heating, and then cut to a size of 50G17-Kasumi x 500-.

Put polypropylene films on the top and bottom of this tied wiring board, then put stainless steel plates on top and bottom, and press the polypropylene films at 40% and 170°C for 100 minutes, then press the polypropylene films @j, +
Polished with 1500 sandpaper and alumina polishing liquid,
A flash circuit was obtained by removing the cured resin on the metal wiring.

The test results of this flash circuit are shown in No. 111N.

Example 2 2.2-bis(4-cyanatophenyl)propane 40
00t and bis(4-maleimidophenyl)nietn,
Pre-react for 120 minutes at 6ooor and elsot,
This was dissolved in a warm solvent mixture of N,N-dimethylformamide and methyl ethyl ketone.Novolac-epoxy resin (product name: gcN-1
273, Ciba Geigy Co., Ltd. $1) 1000-1-= After adding f and making it uniformly 111%, zinc octylate 52
%N,N-dimethylbenzylamine 20t was added to make a uniform 4c mixed finish varnish.

Apply this varnish to a long piece of tetrafluoroethylene film with a width of 550 mm and a thickness of 25 mm and dry it for 17 g.
B-sta with resin layer thickness SO ~ 40μ in 55 seconds at 0℃
On the other hand, a long fully aromatic polyamide fiber with a width of 500 mm and a thickness of 0.25 cm (product name Ninomekkusu, dwpon) was prepared with a ge resin layer.
After impregnating and drying the above varnish on T company II), a long steel foil with a thickness of 3511 mm was continuously layered on one side and heated and pressurized to form a long continuous steel clad laminate. After a predetermined wiring pattern was continuously formed by an etching method, the wiring patterns were aligned on the back side and overlapped to form a long continuous wiring board.

This long tying one-piece continuous arrangement - slope (wiring side of Bl 4CB
-s! The resin adhesion surface of the aged resin layer (released resin layer with aged resin layer) was rubbed continuously with a pressure of 15K using a hot roll at a temperature of 1.5G and 10G℃.
g/m and pressurize to reduce the thermal softening temperature of the wiring surface transfer resin [1
A firefly polytetrafluoroethylene film heated to 55 to 154° C. was cut into pieces of 14 cm x 500 m x 500 cm to obtain wiring boards (C) of desired dimensions.

On the other hand, a glass woven fabric was impregnated with the above varnish and dried to obtain B-
Make the stage prepreg (D), put it on the back side of the wiring board (C), then apply a polyimide laminate with a thickness of 1.41111, put aluminum with a thickness of 30 mm above and below it, and attach the outermost MY stainless steel plate. 40kg/ with board
cm”, 120 minutes at 180°C, then 50#/cm
A flash circuit board was obtained by beating and bures molding at 240°C for 200 minutes. After removing the aluminum foil on the surface, it was polished with $1500 sandpaper and alumina polishing solution to remove the resin on the wiring and obtain a flash circuit with a smooth surface. The test results of this flash circuit are shown in Table 1.

Comparative example 1 2.2-bis(4-cyanatophenyl)propane 9D
Df and bis(4-maleimidophenyl)methane 100
After preliminarily reacting with g at 150'℃ for 150 minutes, it was dissolved in methyl ethyl ketone and novolak type epoxy resin (
Product name 2ECN-1273, Ciba Geigy #2
40t was dissolved to make a homogeneous solution, and a varnish was prepared by mixing zinc octylate 0.59, A B-stage outer layer prepreg with an IN-layer thickness of 42 seconds was made.

'On the other hand, as epoxy resins, Epicort 1001 (Shell Chemical @) 8DDf and Epiclon 155 (manufactured by Dainippon Ink & Chemicals) 200f were dissolved in methyl ethyl ketone, and dicyandiamide 30p, 2-ethyl-
Add and mix 1 g of 4-methylimidazole, impregnate a glass woven cloth with this solution and dry in a colander to form the inner layer 2 of the B-stage.
1- It was made into a prepreg for use.

Two prepregs for the inner layer and two prepregs for the outer layer on both sides.
Layer each piece with 55JI thick copper foil to achieve %2.5
9/12 to 150°C for 12-13 minutes, then 40 to 97
cm2.Laminated at 170℃ for 5-7 minutes to form a semi-hardened single-sided copper-clad laminate, a predetermined wiring pattern was formed on this laminate, and this was plated with NI to a thickness of 5 tones and then Au to a thickness of 1J. was applied. At this time, the thermal softening temperature of the resin of the outer layer prepreg of this semi-cured wiring board was 120 to 143°C. Next, this semi-cured wiring board was heated at 200 kll/cxs2.17.
A flash circuit kit was obtained by pressing at 0°C for 60 minutes.

The test results of this flash circuit are shown in Table 1.

22-1 Percoll hardness (GYZJ 954-1)-2
Ultrasonic abrasion resistance O was the usage time until the base material force S is generated Surface unevenness convexity (Surface roughness needle manufactured by Saka Institute) 0 The height difference between the circuit part and the base material part 0 Patent applicant Mitsubishi CEO of Gas Chemical Co., Ltd.! Ilt'''Kichi 23-

Claims (1)

[Claims] 1. Form a desired wiring pattern on a long single-sided metal foil-clad laminate or sheet by a continuous method to obtain a long continuous wiring board (!I), After overlapping the wires W1 on both sides, the resin-attached surfaces of the resin layer material and the box film (b) on which a thermosetting resin layer formed of uncured or B-stags is formed are continuously overlapped and heated and pressurized. The resin is filled into the non-wiring portion of the distribution IsN, semi-cured or cured in the latter half of the filling, and cut into a wiring board (c) of the desired size. Lay the prepreg, release film or post-installation sheet, and laminate or metal plate on the back side of the desired size wiring board (c), and after laminating and curing the resin, polish the wiring surface to expose the wiring metal. and smoothing the surface.Claim 1. Method for producing a flash circuit using mold.2. The resin layer of the resin layer-attached release film (b) is a cyanide soap ester resin composition.Claim 1 Entry-
manufacturing method