JPS58107312A - Manufacture of non-solvent type laminated plate - Google Patents

Abstract

PURPOSE:To obtain a titled laminated plate adapted for a printed circuit board without voids by supplying a non-solvent melting resin composition which has epoxy resin, novolac type phenol formaldehyde resin and a cure accelerator as a base material, thermally pressing and molding it. CONSTITUTION:Novolac type phenol formaldehyde resin (preferably havng a melting point less than 120 deg.C) is used as a hardener for epoxy resin (preferably diglycidyl ether type of bis-phenol A having more than two epoxy groups per one molecule and a melting point of 40-120 deg.C), a hardening accelerator (e.g., benzylmethylamine or the like) is further added, and the mixture is uniformly heated, mixed and molten. After this molten composition is supplied to the base material such as glass cloth, it is thermally pressure-molded with a pressure molding machine having an enclosure frame 3 of the prescribed height between parallel boards 1 and 2, thereby obtaining desired laminated plate.

Description

[Detailed Description of the Invention] Printing arrangement on Fure@ - A product of 71 k
The purpose of this method is to manufacture laminates containing laminates by dissolving American J11 Hibiki into bath additives. From point 06, we were able to provide an epoxy horizontal m board with excellent % brightness without any voids etc. without using solvents. Dry IIIR layer method KA is not manufactured properly.

Dissolve epoxy resin, curing agent, curing accelerator, etc. in a solvent,
Create a varnish with a uniform 1% sweetness, and apply it to the varnish.
Treat 4 materials such as Then, after cutting to the dimensions of the building, the surface was 1 piece of RC copper foil, sandwiched between 7Jl.
◎ However, according to this method FC, it is necessary to remove multiple solvents contained in the varnish in 1 product to make 1 repreg! However, not only does this drying process require a large amount of energy, but a large amount of energy is wasted due to the difficulty in supinating the solvent. In addition, since OC causes problems such as volatilization of bath additives and environmental contamination, various methods for producing epoxy laminated AT using a non-toxic agent OWMV have been studied. For example, threat M introduction 53-1
11369, JP-A-54-155859, JP-A-55-
L5 epoxy IIR disclosed in 109623 etc.
One of the methods is to mix IJW, dicyandiamide, a saponification accelerator, a filler, etc. with a kneading bond. Dicyandiamide has been largely used as a hardening agent for epoxy laminated boards manufactured by the conventional (L)IIIL double layer method, and has been used as a curing agent for epoxy laminated boards manufactured by the (L)IIIL double layer method, and has been used as a curing agent for epoxy laminated boards manufactured by the (L)IIIL double layer method. One of the few hardening agents that can be used is one.However, dicyandiamide is compatible with α epoxy resin in the absence of bath additives. In addition, dicyanthide has the drawback that it is difficult to uniformly disperse t′L.Toriguchi et al. 0 (Kobunshi Papers, Vo, 1.34, Kanha P537-545, J
Uly, 1977) 8 and an epoxy layer without a bath additive.
1jL [As a curing agent other than dicyandiamide, aromatic ynes such as diaminocinenylmethane and diaminodiyl sulfone, borium trifluoride salts,
Polyazed W Lieu, Iidazole-1w1 Anhydrous 1 or JP-A-53-14769. % [disclosed in 555-38005. These saponifying agents are
Compatibility with fat is good, but each.

Each oT has a camphor point, that is, aromatic amines have a toxicity problem, trifluoride boron wood end tjkwA has poor moisture bone resistance, and polyamide side force transfers to 71 laths. It has a low score, has a skin color due to imidazoles, and has a ridged temperature due to Satoshi Toshimuzu (has short pot life, etc.). Using I# storage agent, laminate t
The method for creating # is disclosed in Japanese Patent Application Laid-open No. 55-38005. Ruru.

Considering these points, the Ministry of Invention and others investigated various methods such as combination of epoxy** and saponifying agent, method of forming horizontal m plate, etc. On average, more than 2 epoxy noodles are added to the epoxy 11 & novolac coffee phenol formaldehyde @Mi11 as a hardening agent.
For tR, curing promoter 1! The mixture was heated and mixed uniformly to create a non-silent agent and composition *i, and then supplied to the solvent-free resin composition T4 material of C. A fence with a height of one foot between the parallel plates 11
1! Using the calopressure relative form τ with - heating and pressurization g form,
Void et al.
This relates to a method for creating wrinkles (64).

The present invention (specifically, the present invention) has an average of two or more epoxy M molecules per molecule, and is limited to bones. Isn't there?
For example, diglycidyl ether of bisphenol, epoxy, butadiene diepoxide, 4.4'-di(1,2-epoxy ether) cyanyl ether 1.4
．． 4'-di(epoxy ether) biphenyl, diglycidyl ether of resorcinol, diglycidyl ether of phloroglycin, triglycidyl ether of p-a()7snorli, 1.45-toben(1,2-
epoxy ether) benzene, cibenzone enone in 2,24.4'-tetraglyside, detoglyside phenol formaldehyde, novolac fat phenol formaldehyde
triglycidyl ether of le 1v1 bread, triglycidyl ether of guryurin, halogenated hisphenol A
Diglycidyl ether dust epoxy resin, halogenated novolak phenol formaldehyde resin polyglycidyl ether, triglycidyl isocyanurate,
OSS formula epoxy wTI1.Vinyl Schift 4-benzosendioquinide, 4-epoxycyclohexylmethyl 4-epoxycyclohexanecarboxylate, etc. Hydantoin epoxy @ etc. 0 About epoxy resin 21
1stIIbli1! Because of its ease of peeling, it can be used in liquid form, or in solid form at temperatures ranging from 40 to 120°C.

During mixing, IIg is kept at a separate temperature t^ (must be done,
The curing reaction of the ajisc material is dangerous.Also, in this book, the epoxy 4M tumor treated with bis-28nol A diglycidyl ether has a high precision and cannot be used due to its erratic kinetics. , reaction a! Bisphenol A, bisphenol S1 brominated bisphenol A1 as modifier
It is also possible to reduce the viscosity by using brominated bisphenol S or the like as an epoxy resin for low molecular weight bisphenol A diglycidyl ether type epoxy.

Novo2 Tsuku Jlil1 used as a curing agent in the present invention
7s nor formaldehyde W contains phenol, cresol, xyleral, ether 7s nor, phthylphenol, p-2enylphenol, nonylphenol, and bisphenol A.

Two enols such as resorcinol, aldehydes such as formaldehyde and paraformaldehyde, and aldehyde anti-α4 to α9 for t% phenol II 1.0 mo kfC
5 mol le f? Phenol formaldehyde 11jI is sweetened by a conventional method.
The melting point of 7I is 120℃ from Enzan, which is the same as that of epoxy shaver.
The following is needle-like. In addition, the residual 2s of the remaining 2s in the phenol-formaldehyde mjllr is more likely to be small. Epoxy'l1ik and 7borak 1jM phenol-formaldehyde Shin'ei's # & 21L1 violet is 1-piece. For epoxy-induced hyperplasia, L6 to 1.2 water acupuncture equivalents of novo 2 m phenol formaldehyde preparations were given.
However, if it is outside this range, the axial properties of the cured laminate will be adversely affected. Preferably α9~LO water 111j[i
The curing accelerator used in the present invention is a tertiary compound such as benzyldimethylamine, 4I
I & ammonium salt li1.4! r6 imidazole,
Amino-triazole-1t8-diazabisic0(5
, 4, 0) Undecene-7 and its salt, Hokuki trifluoride-
There are salts, pyrazole, amino-pyridine, antuquinaldine, aminoquinoline steel, and amino-pyridine.

Addition of saponification accelerator mjiFX epoxy filter 10011i1
1 [LO1~'LO weight part weight L(, 101
If the amount is less than part by weight, the curing accelerating effect will not be exhibited.

X40] [If it exceeds the mold part, it will harden and adversely affect the axial properties of the FC laminate.

As the base material, conventionally known base materials such as glass cloth, glass nonwoven fabric, paper, organic SL fiber, and cloth can be used.In the present invention, the epoxy W side, Novolac fat phenol formaldehyde w side.

Depending on the saponification accelerator IiK and 111, flexibility imparting M, viscosity-lowering diluent, % plow repellent, filler, and additives may be added.

In addition, the solvent-free W embroidery composition technology in the present invention is similar to the conventional method 2.
1 Bath agent removal process (C) does not use heavy solvents, so there is no problem in using image-type solvents.

12 Tsuku II! Methods for uniformly heating and kneading 2-enol formaldehyde IIJ11 and the curing accelerator include a method of stirring at Lv high speed using a stirring motor, a method using a kneading machine using a roll, kneader, etc., and a method using extrusion INK! Appropriate methods include a method using a dispensing device that mixes the amount of grease needles and a method using a dispensing device with a mixed amount of oil needle, and a method using a direct injection molding with a reactor. If the liquid is violet in A degree, it is necessary to heat it, or if the liquid is in violet form, heat it until it becomes soft or liquid. However, it is not unreasonable to use -21111 heat that causes curing to progress during mixing.

Regarding the order of addition of curing accelerators and other thickening agents, please note that if the saponification accelerator is too heavy or too little, the epoxy will go bankrupt if it does not cure properly when heated and mixed. , Novo 2 Tsuku! It is also possible to add a curing accelerator and other masking agents to phenol formaldehyde at the same time.
Dynamics that harden too much during s mixed St is 1r evo medium 1
1. Heat and mix 1J111 and NOBO2 fat phenol formaldehyde*li% and other additives. 1. Then add a curing accelerator and uniformly sweeten in as short a time as possible.
It's disgusting.

11i#! The method of applying and impregnating a 5vrh base material with the agent is to apply the ageless agent on a single base material, and then heat and pressurize it with heat and pressure. tX<S Required number: 1 The bath-free side composition may be applied on the bedded substrate,
Alternatively, it can be applied by sandwiching it between the substrates.Also, if a low molecular weight liquid epoxy medium *mrh is used, the solvent-free resin composition O equipment is presented, but if the RT is low. It is also possible to impregnate the base material by immersing the base material in a solvent-free *fat composition, similar to the case of mellowing. .

The pressure-molded frame used for Honto #4 is preferably a foot-height enclosure frame with a pair of 1,000 rows of carps. Use %E)k where nine castles are lit in one. The reason for installing the enclosure frame mt parallel fiK is that the internal pressure is easy to build up, and it is difficult to remove dust etc.
! To make it easier, the above-mentioned bath-free mercury composition tube is not B-staged, so when using the conventional parallel plate pressure molding method using one plate, the viscosity of ** during pressurization is low. .

The voids cannot be removed because 5 yen pressure is not applied, probably due to the embroidery flowing out from the periphery. Therefore, in the present invention, in order to form a void-free laminate using the low-viscosity, solvent-free 4If filtration process, an enclosure frame tJj, VC= of a constant height of the parallel heating plate plate is used. 9 It is possible to create a void-free laminate by applying internal pressure by preventing the outflow of the fat when pressurized 〇 The first example is the collapse of an enclosure frame of a certain height, but θ Its shape is the length of the tube (h), the width (b) is the angle of the tube (- is the short length of the tube).

When harvesting the island, the thickness of the board used to make butterflies is adjusted to the desired thickness. Regarding the angle, it is better to add 900 to ll in Figure #11, or 90° or more. Width (Do not place the RTB limit on the bJ. If the structure is such that internal pressure is applied to the no-bath agent embroidery assembly when pressurized, it is L. Figure 2 shows a frame type or a lower parallel plate. An example is shown below.

Gradually, the laminate plate hfFj is formed, the effect of the base material, or one piece of copper, etc., 16 pieces of I gold is added and molded under heat and pressure to make a gold lI4 foil laminated pigeon board□ Usually it is 6 times, but
There is no problem with gold 14w1.The metal foils used are steel foil and Arun leaf.

In addition, the base material and steel weight etc. soaked in the bath-free stomach fat composition are heated in parallel with M1.
In addition, some of the base materials are held in a frame shape, and the work required is 1%.◇ The present invention will be explained in detail with Example t below. However, the present invention is limited to the following embodiments. The f'L is 4%.

[Chuo IIIA Example 1] Bisphenol AM liquid Evo medium sea fat 1 manufactured by Yuka Shell Co., Ltd.
Song name: Ebiko) 828 (Ehoxy weight: 19σg/eq
, ) Novo 2 Tsuku Ig made by Hitachi Chemical on 1 o o g! Phenol formaldehyde am.

Part name HP-607N (softening point 85℃, hydroxyl group weight 1
G 6 g/eq, ) 55L8 g (Epoxy @ fat store, oxidizing agent violet to violet ratio of 1:10)
was added and heated at 110°C until the HP-607N became hostile, and after -t, the stirrer was stirred for 2 minutes using a stirring motor. and stirred for 1 minute to obtain a uniform solvent-free composition.
Crow cloth G-9020-BZ of size X310U
-2 (manufactured by Nittobo) zavm, and on top of that 170X2
50 seagull size glass cloth G-9020-BZ -
21r2 & 1Lt2 Te, Sono Shino @lCf1 extended @Furthermore, on top of this, two pieces of small size glass cloth, x
2 pieces of Naiz glass cloth km, Western style 3 on the greedy side of this.
5〃 TAL torture steel foil t moneta, cn1 upper parallel plate or 268 thin x 310 fin 〇 size flat plate and lower S board is outside 1 1901111 x 27Qswi1
A glass cloth of a small size was placed between a parallel mold on which crushed grains with a width of 5 sn were deposited, and an INK charge was placed inside the enclosure eal, followed by heating and pressure molding. The forming strip fF has a temperature of 170"C and a pressure of 80 kg for forming IIjkfI6.
f/(IM when la type) was 60 minutes U.This logging plate A
There is no void and Iso 11! Characteristic.

It also has good electrical bone properties, making it suitable for use as an immediate successor.
Table 1 shows the zero errors that occurred.

[5A Example 2] Implementation tllIK stool t, 71-vinyt 828,10
0gK, HP-607N3A 1g! Nato 2 pmobis 2 enol AC7X&A-White neck 2 as a l-responsive am agent
72 g/eq,) S a2 g (!bo+shi*fatakura and HP607N violet and nato 2 bromo bisphenol kAQ
i weight)jtBmltjt”C1,0: [L 59:
a41 and w: 21IJ, 13G'CrCfL et al! #c
lU1-#/c @ Audience & stirring in a cabinet - Added 4.0g 9f of benzyl dimethyl azene to this ugly thing, stirred for 20 minutes, and left a uniform #I static lubricant composition. Did you implement anything other than changing the molding time to klO minutes?
Similar to 111, VC is applied to glass cloth and then heated and pressure molded to reduce void-free Bt-Samurai 7to characteristics.
niboting.

[Example 3] Bisphenol A type Evo dt manufactured by TM Shell Co., Ltd. @Tj
th m Product name Epicote IQQICIIR point? 0℃x
, gxi"h'lk475 g/eq,) 10 D
gKHP 607N223. (Todoroki Kaif) II-m, t
, 130” Cτ Epicote 1001 and HP60711!
Heat it with a reed and stir with motor for 2 minutes.
Mixed and stirred from c@this mixture*@tic Kikashishindo as 2-ester 4-methylimidazole α2gk, stirred for 1 minute, and made a uniform bath-free composition R Samurai'It, <I
C (2J @ solventff1a'il120gk170
Glass cloth G-902 with size nX250m111
0-BZ-2, 4 On the fallen Kao-zheng & Enku-kon 〇Furthermore, on top of this, the above-mentioned 4 glass cloths 1, the breakdown of this f'L 11 [i 55μ thick TAI treatment This thing with copper foil t outside 19 QsnX 27 Qwa.

^Size 1.4m, width 5m v733 frame addition (ZJ Q
'K ML l' * Set between the upper and lower parallel plates b
a) Hot and pressure molded.

The heat plate strength of the keiki fF is 170″G, and the maximum molding pressure is 8Qk.
gf/cx1. Ift, the annotation of the log board C that was met and obtained in 60 minutes during the formation time is shown in Speech 1〇 ([IIA Example 4
] Manufactured by Nippon Ciba Geigy Co., Ltd., fruit-based bisphenol A type epoxy Shinji, trade name Araldai) 80 eyes (softening point 75°C epoxy Knp 49 D g/eq-) 1oogKnp6o
Add 7sz1.61 (white head @) 1 and add or subtract at 150℃ until 7lardite 8o11 and 607N are reached. The molten MlIJllr composition was made into the same al. as flk and applied to 1, and after being supplied to a glass cloth, it was molded under heat and pressure to obtain 1 layer @Dk. Table 1 shows the zero extensibility.

[Comparative IHFII) Araldite 8011.150gk was stirred at 130℃, dicyandiamide 4.5gk was added, and stirring was continued for 05 minutes.
Add 3 g 1 lj of penzyl dimethalone to 11, which had not included the melt and one white axial crystal had been destroyed, and stir for 1 minute. After supplying it to glass cloth as l11 and IW1, it was molded under heat and pressure at 170°C for 60 minutes.
The skin was not gelled, and when the cold RJ deposit was removed, white dispersion of dicyandiamide #1 remained.

XI M711141's characteristics are better than the characteristics of fc, but according to @Ming, using a non-adhesive Evo medium composition, it has good properties without voids.
l
The I value is S.

The distance between the stations is 41 yen, and in Figure 1 there is a one-height frame and a pair of ten-line blocks are 4 f apart.
A picture of a pressure-molded ball ◎The second one is a pair ^sa V-
This is the second illustration of the lower part of the 1,000-row chest, with 9 pieces of sandals.

Code a light 1 Upper S parallel plate 2 Lower a thousand line plate 3 Frame wave on il

Claims (1)

[Claims] 1. Mix Epo medium resin**, novolac wrinkle phenol formaldehyde 11 fat, hardening accelerator, and Lm Sebata IIs to prepare an M-free embroidery composition, and prepare this non-greasy composition. 11k After supplying the base material, pressurize it with a high frame of constant width [type fJat, and apply heat and pressurize area to form a marrow layer with no mellow agent. Sales management method. 2. The hard frame 1jII of constant strength is pressed with at least one parallel and body Kjll. .