JPH0237714B2 - RYOMENDO BARIZETSU ENHIMAKUNOSEIZOHOHO - Google Patents

Description

[Detailed description of the invention]

[Technical Field of the Invention] The present invention relates to a method for manufacturing a double-sided copper-clad insulating film useful as a copper-clad laminate used in a printed circuit board. [Prior Art] Conventionally, copper-clad insulating coatings are generally produced by coating copper foil with epoxy prepreg or polyimide prepreg containing a glass cloth base material, and then hot pressing. However, the above method has drawbacks such as easy entrainment of air bubbles, poor reliability of withstand voltage, and difficulty in continuous production. [Summary of the Invention] The present invention was made with the aim of improving the above-mentioned drawbacks, and it is possible to apply a thermosetting water-dispersed electrodeposition paint and a thermoplastic water-dispersed electrodeposition paint onto a copper foil polymerized with a fibrous base material if necessary. An electrodeposited layer is formed by electrodeposition using an electrodeposition paint mixed with a paint, and then the deposited layer is treated with an organic solvent, and then the water and organic solvent are volatilized by semi-curing to form a continuous film. We propose an economical, highly reliable, and continuous production method for producing double-sided copper-clad insulation films by overlapping copper foil on this continuous film and hot pressing. [Structure of the Invention] In the present invention, a mixture of a thermosetting water-dispersed electrodeposition paint that can be cured by heating and a thermoplastic water-dispersion electrodeposition paint that does not harden by heating is used as the electrodeposition paint, and After forming an electrodeposited layer by electrodeposition coating and treating this deposited layer with an organic solvent,
By heating and semi-curing, water and organic solvent in the deposited layer are evaporated to form a continuous film. Then, the obtained single-sided copper-clad insulating coating and copper foil are bonded together by hot pressing to produce a double-sided copper-clad insulating coating. In the second aspect of the invention, a similar treatment is applied to the fibrous base material side of a copper foil polymerized with a fibrous base material to produce a double-sided copper-clad insulating film with a fibrous base material interposed therebetween. As the thermosetting water-dispersed electrodeposition paint used in the present invention, acrylic-modified epoxy-based water-dispersion electrodeposition paint, polyesterimide-based water-dispersion electrodeposition paint, etc. can be used without particular limitation, but printed circuit boards, etc. When used for solder heat resistance, paints with excellent heat resistance are preferred because they have high temperature and short-time solder resistance. In addition, as the thermoplastic water-dispersed electrodeposition paint used in the present invention, phenoxy resin, polyphenylene sulfide, polyether sulfone, etc. are used.As for the method of making the electrodeposition paint, for example, the above resin is reduced to 30 μm or less. A method is adopted in which the pulverized material is dispersed in water containing a surfactant. As the surfactant used here, if the above-mentioned thermosetting water-dispersed electrodeposition paint is anionic, an anionic activator is used, and preferred examples include sodium laurylbenzenesulfonate and sodium lauryl sulfate ester. etc. The mixing ratio of thermosetting water-dispersible electrodeposition paint and thermoplastic water-dispersion electrodeposition paint is 100 parts by weight (solid content equivalent) of thermosetting water-dispersion electrodeposition paint to 10 to 10 parts by weight of thermoplastic water-dispersion electrodeposition paint. 100 parts by weight, preferably 20~
It is 80 parts by weight. If the thermoplastic water-dispersed electrodeposition paint is less than 10 parts by weight, it is undesirable because it will cause a decrease in adhesive strength with the copper foil, and if it exceeds 100 parts by weight,
When used for printed circuit boards, etc., it is not preferable because the solder heat resistance (high temperature and short time) decreases. The concentration of resin solids in the mixed solution containing the above electrocoating paint is preferably about 5 to 20%. If it is less than 5%, it will take time to obtain the desired film thickness;
If it exceeds %, steps such as washing the electrodeposited layer with water before heating are required, which is not preferable. In order to further smooth the insulating film when using the above-mentioned electrodeposition paint, it is also possible to add a small amount (0.01 to 0.1%) of a fluorocarbon surfactant that provides a leveling effect to the paint. As the fibrous base material used in the present invention, glass or polyamide fiber is used, and a particularly preferred example is glass cloth (Arisawa Seisakusho,
EPC050, EPC102, EPC160, LPC070,
LPC110) and aromatic polyamide fibers (Karbou Glass Fiber Co., Ltd., Kevlar 49 cloth (K-120, K-220,
K-181, K-281). In electrodeposition coating, an electrodeposition layer is formed on one side of the copper foil by using a mixture of the electrodeposition paints as an electrodeposition paint, or
Alternatively, an electrodeposited layer may be formed on the fibrous base material side of a copper foil on which the fibrous base material is polymerized. The operations and conditions for electrodeposition coating are the same as those for general electrodeposition coating. When the electrodeposited layer formed in this way is immersed in an organic solvent for a short time or brought into contact with organic solvent vapor, the water-dispersed particles in the deposited layer are partially swollen by the organic solvent and pinned by heating. A continuous film without holes can be formed. After the organic solvent treatment, heating is performed to semi-cure the water and organic solvent to volatilize and form a continuous film. When forming a continuous film, it is preferable to bring the film to the so-called B stage state rather than completely curing it, so the heating conditions are 100 to 200
10-30 minutes at ℃ is suitable. When adhering the thus obtained single-sided copper-clad insulating coating or single-sided copper-clad insulating coating containing a fibrous base material to another copper foil by hot pressing, the preferred processing conditions are 200 to 300°C and a pressure of 2 kg/cm ² This will take 10 to 30 minutes. less than 200℃ or less than 2Kg/ ^cm2 ,
Alternatively, if the duration is less than 10 minutes, the adhesion between the insulating film and the copper foil is poor and is not practical. Hereinafter, the present invention will be explained in detail with reference to the drawings.
FIG. 1 and FIG. 2 are system diagrams each showing another embodiment of the present invention. In the manufacturing method shown in Fig. 1, a thin copper foil 3 is fed from a roll 1 into an electrodeposition tank 2 containing electrodeposition paint, and then passed through a roll 4 whose surface is insulated by being covered with an elastic material such as rubber. move it. Then, in the electrodeposition tank 2, a DC voltage is applied between the counter electrode 5 and the copper foil 3 by the DC power supply 12, and electrodeposition coating is performed to form an electrodeposition layer of a desired thickness on one side of the copper foil 3. do. Subsequently, the copper foil 3 is passed through an organic solvent steam bath 6 to be treated with an organic solvent, and further passed through a semi-cure furnace 7 to be heated and semi-cured to remove moisture and organic solvent in the deposited layer and harden the deposited layer. , forming a smooth and uniform continuous film on the copper foil 3. Thereafter, another copper foil 8 is stacked on the coated side of the copper foil 3 and supplied between hot rollers 9, and heat-pressed to heat-seal the foil. The double-sided copper-clad insulating film produced in this way is wound up by a winding machine 10. 11
a and 11b are rolls. In FIG. 2, the copper foil 3 and the fibrous base material 14 are supplied between the rolls 13a and 13b and polymerized, and in the polymerized state, the copper foil 3 and the fibrous base material 14 are supplied from the roll 1 to the electrodeposition bath 2 in the same manner as in FIG. An electrodeposited layer on the 14 side is formed.
Then, it is treated with an organic solvent in a steam bath 6, and after semi-curing in a semi-curing furnace 7, another copper foil 8 is polymerized on the side of the continuous film containing the fibrous base material 14, and is thermally fused with a hot roller 9 to form a double-sided copper-clad insulation film. Manufacture. [Embodiments of the Invention] Examples of the present invention will be described below. Reference Example 1 Put 1,900 g of ion-exchanged water and 2.4 g of lauryl sulfate ester soda into a four-necked flask and pass N ₂ gas through it for about 30 minutes while stirring. Then, the flow of N ₂ gas was stopped, and the temperature was raised to 70°C. Next, a solution of 2.0 g of ammonium persulfate and 0.7 g of sodium bisulfite dissolved in 100 g of ion-exchanged water was added, and then immediately 240 g of acrylonitrile, 60 g of α-methylstyrene, 60 g of styrene, and methacrylic acid were added.
A mixed solution of 20g of glycidyl methacrylate and 20g of glycidyl methacrylate was dropped over about 30 minutes, and after the dropping was completed, the reaction was carried out at 70°C for 3 hours to produce an acrylic-modified epoxy thermosetting water-dispersed electrodeposition paint A with a non-volatile content of 19.5%. . Reference example 2 Diaminodiphenylmethane in a four-necked flask
206g, anhydrous trimelitz 400g, m-cresol
After preparing 600g and reacting at 150℃ for 1 hour,
Polyester terephthalate 400 heated to 200℃
g, 200 g of tris-(β-hydroxyethyl) isocyanurate, and 4 g of tetrabutyl titanate were added and dissolved. Next, after reacting at 220 to 240°C for about 3.5 hours while distilling m-cresol and the produced ethylene glycol out of the system, FC431
(fluorine-based surfactant, manufactured by 3M) 1.2 g was added and stirred for about 15 minutes to obtain a polyesterimide resin. The obtained resin was pulverized with a jet mill to an average particle size of 11 μm. Add 500g of this powder to ion exchange water containing 5g of lauryl sulfate ester soda.
A polyesterimide thermosetting water-dispersed electrodeposition paint B having a non-volatile content of about 10% was produced by dispersing it in 4,500 g. Reference example 3 Phenoxy resin (manufactured by U, C, C company, PHKK)
was ground to an average particle size of 14 μm using a jet mill, and 500 g of this powder was dispersed in 4500 g of ion-exchanged water containing 5 g of sodium laurylbenzenesulfonate.
A phenoxy resin-based thermoplastic water-dispersed electrodeposition paint C having a non-volatile content of about 10% was produced. Reference example 4 Polyether sulfone (Mitsui Toatsusha,
Victrex) was ground to an average particle size of 13 μm using a diet mill, and 500 g of this powder was mixed with ion-exchanged water containing 4.0 g of sodium laurylbenzenesulfonate and 1.0 g of FC431 (fluorosurfactant, 3M).
A polyether sulfone-based thermoplastic water-dispersed electrodeposition paint D having a non-volatile content of about 10% was prepared by dispersing the mixture in g. Examples 1 to 5 Using the electrodeposition paint shown in Table 1, a release sheet was pasted on one side of a copper foil with a thickness of 35 μm, a width of 200 mm, and a length of 200 mm according to the method shown in Figure 1. As an anode,
Apply a DC voltage of 50V between the counter electrode for 10 seconds,
An electrodeposited layer was formed. This electrodeposited layer was immersed in dimethylformamide solution for 30 seconds and heated to 100-150°C.
Heat for 20 minutes to semi-cure, then cut to a thickness of 35μ
Another copper foil having a width of 200 mm and a length of 200 mm was placed on top of the other copper foil, mounted on a press, and heated at 200 to 250° C. for 10 to 30 minutes to produce a double-sided copper-clad insulating film. The properties of the obtained double-sided copper-clad insulating film were measured. Table 1 shows the results.
Shown below.

[Table] Examples 6 to 12 Using the electrodeposition paint and fibrous base material shown in Table 2, and by the method shown in Fig. 2, a film with a width of 500 mm and a thickness of 35 μm was prepared.
A fibrous base material 14 was polymerized on a continuous copper foil 3, the copper foil side was used as an anode, and a DC voltage of 50 V was applied between it and the counter electrode 5 in the electrodeposition tank 2 to form an electrodeposited layer. . Next, after passing through a steam tank 6, it passes through a semi-cure furnace 7 at a temperature of 100 to 200°C, and is further preheated.
Overlaid with another copper foil 8 of 500 mm and 35 μm thickness, and heated to 200
Heat fusion was performed using a hot roller 9 at ~350°C to produce an insulating film containing a double-sided copper-clad base material. Table 2 shows the properties of the obtained double-sided copper-clad insulating film.

【table】

〔Effect of the invention〕

According to the present invention, after forming an electrodeposited layer on one side of copper foil and performing organic solvent treatment and semi-curing,
Since it is overlapped with another copper foil, it is possible to continuously manufacture a double-sided copper-clad insulating film in a cost-effective and highly reliable manner. Furthermore, by polymerizing a fibrous base material onto copper foil and performing the same operation, it is possible to produce a double-sided copper-clad insulating film with high strength and a small amount of electrodeposition paint.

[Brief explanation of drawings]

FIGS. 1 and 2 are system diagrams showing other embodiments of the present invention. In each figure, the same reference numerals indicate the same or corresponding parts, 2 is an electrodeposition tank, 3 and 8 are copper foils, 4 is a roll, 5 is a counter electrode, 6 is an organic solvent vapor tank, 7 is a semi-cure furnace, and 9 is a The hot roller 14 is a fibrous base material.

Claims (1)

[Scope of Claims] 1. Forming an electrodeposited layer on copper foil by electrodeposition using an electrodeposition paint containing a mixture of a thermosetting water-dispersed electrodeposition paint and a thermoplastic water-dispersion electrodeposition paint, A double-sided copper-clad insulating film characterized in that the deposited layer is then treated with an organic solvent and then semi-cured to volatilize the moisture and organic solvent to form a continuous film, and this continuous film is overlaid with copper foil and hot pressed. manufacturing method. 2. The double-sided copper-clad insulating coating according to claim 1, wherein the thermosetting water-dispersed electrodeposition paint is an acrylic-modified epoxy-based water-dispersed electrodeposition paint or a polyesterimide-based water-dispersed electrodeposition paint. Production method. 3. A patent claim characterized in that the thermoplastic water-dispersed electrodeposition paint is a phenoxy resin-based water-dispersed electrodeposition paint, a polyphenylene sulfide-based water-dispersed electrodeposition paint, or a polyethersulfone-based water-dispersed electrodeposition paint. A method for producing a double-sided copper-clad insulating film according to scope 1 or 2. 4. The method for producing a double-sided copper-clad insulating film according to any one of claims 1 to 3, wherein the hot press is a hot roller. 5. Form an electrodeposited layer on the copper foil polymerized with the fibrous base material by electrodeposition using an electrodeposition paint containing a mixture of a thermosetting water-dispersed electrodeposition paint and a thermoplastic water-dispersion electrodeposition paint. Then, after treating the deposited layer with an organic solvent, the moisture and organic solvent are volatilized by semi-curing to form a continuous film, and this continuous film is overlaid with copper foil and hot pressed. Method of manufacturing the film. 6. Claim 5, characterized in that the fibrous base material is glass cloth or polyamide fiber.
A method for producing a double-sided copper-clad insulating film as described in .