JPS59103396A - Circuit board with resistor and method of producing same - 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 circuit board with a resistor and a method for manufacturing the same.

Conventionally, a circuit board with a built-in resistor is generally provided in the form of a laminate consisting of an electrically insulating layer, a layer of a resistor bonded to this layer, and a highly conductive layer bonded to the resistor. In addition, when fabricating the desired resistance circuit pattern, insulating areas (all layers on the insulating layer are removed), resistance areas (only the highly conductive layer is removed), and A conductive region (without removing any of the layers, usually a thin film of a noble metal such as gold is applied on top of this highly conductive material) is formed by a sapractic method (master etching method). Alternatively, it may be formed by a direct forming method in which the resistor portion or the like is printed through a screen printing plate having a predetermined pattern shape.

By the way, resistor materials in this technical field are composed of carbon-based materials, metal oxide materials, metal materials, and mixtures thereof. Methods for forming resistor layers from such materials include printing a paste-like material, such as carbon particles mixed with various resin components, and carbonizing various hydrocarbon compounds under various conditions and vapor deposition. A method of vapor-depositing a metal or an alloy of two or more elements, and a method of sputter-linking are known.

However, in the case of printing paste-like materials, it is difficult to control the resistance value itself, and furthermore, the resistance value varies widely over the entire surface of the circuit board, resulting in poor characteristics. In addition, it is difficult to control the resistance value even with vapor deposition and sputter link methods.
Moreover, the equipment is expensive.

Therefore, in recent years, attention has been paid to a method of producing a low-antibody layer efficiently and stably in a large area at low cost by plating. For example, JP-A-48-73762 discloses a method for manufacturing resistors made of nickel-phosphorus alloys by electroplating, and JP-A-50-7151.3 describes a method for manufacturing resistors made of nickel-phosphorus alloys by electroplating. Various methods have been proposed for forming resistor layers using electroplating. However, it has been found that the above-mentioned alloys have many drawbacks in terms of properties and workability as intended resistor materials.

In short, in a circuit board made of such metal thin film resistors, by reducing the thickness of these metal films, a resistor having a sheet resistance value suitable for the purpose can be obtained. However, as the metal film becomes thinner, it becomes difficult to obtain microscopic uniformity of the metal film itself, and there is a natural limit to the film thickness. For example, the sheet resistance value of the above-mentioned nickel-IJ alloy that can be used industrially is at most 100 Ω/unit,
It is difficult to obtain a material with an even higher sheet resistance value. Moreover - even during the subtractive processing process there are serious defects.

In the subtractive method, photoresist is applied to the entire surface of the copper foil (highly conductive material) of the circuit board. Then,
After exposure through a photomask that leaves resist on the intended resistor and conductor portions, the resist is developed. In order to form an insulating region, unnecessary copper and resistor layers are sequentially etched away using respective dedicated processing solutions. Subsequently, the film is exposed to light through a photomask that leaves only the conductor portion, and then developed. By etching away the exposed copper foil (forming a resistance area), the desired circuit board (
However, some resist remains in the conductor region.

In the above process, when a portion of the copper foil corresponding to one resistor pattern area is removed by etching, it is essential that the material of the resistor is stable to the etching solution and is hardly etched.

However, it was found that the resistor made of the above-mentioned nickel-phosphorus alloy had poor etching selectivity with the copper foil, and the resistor was also partially etched when the copper foil was etched, resulting in a significant increase in resistance value. . In other words, there was a drawback that the intended setting value did not directly correspond to the resistance value after processing.

Furthermore, the various binary alloys shown in the above-mentioned Japanese Patent Application Laid-Open No. 50-7151.3 were proposed as being able to generally obtain higher sheet resistance values than single metal plating films. However, it has not yet been industrially adopted for the following reasons. In other words, there is a problem in that it is difficult to balance the increase in resistance value due to the thinning of the film with other properties such as etching selectivity, and it is also difficult to stably produce an alloy plating film of a constant composition without variation in resistance value from these plating baths. This is because there is a problem that it is extremely difficult to do so.

In view of these circumstances, the present applicant has already devised a tin-nickel alloy as a resistor material different from the above-mentioned proposed alloys. This alloy (accordingly, it is possible to form a film compared to the above-mentioned proposal), and this makes it possible to
It has been found that a sheet resistance value of 0.00 Ω/hole can be obtained, and that the etching selectivity is improved and the uniformity of dropstone properties when formed by electroplating is also excellent.

In subsequent research on resistor materials made from tin-nickel alloys, the inventors discovered that when copper and sulfur were further incorporated into tin-nickel alloys, circuit boards with even higher sheet resistance values could be obtained. −
This led to the completion of this invention.

That is, the present invention provides a circuit board having a structure in which a highly conductive material is bonded to at least one side of an electrically insulating layer via a resistor layer, in which the resistor is made of a quaternary alloy of tin-nickel-copper-sulfur. The present invention relates to a characteristic circuit board with a resistor.

According to the above-mentioned quaternary alloy in this invention, the above-mentioned tin-
In addition to obtaining good etching selectivity and excellent uniform electrodeposition during electroplating similar to those obtained with nickel alloys, circuit boards with extremely high sheet resistance values can be manufactured easily and with good stability.

For example, in the case of the tin-nickel alloy, if the sheet resistance is about 100 Ω/hole, the film thickness must be several 100A or less, and if it is about 300 to 4 ooΩ/hole, the film thickness must be made even thinner than the above. did not become. On the other hand, according to the quaternary alloy of the present invention, by simply setting the contents of copper and sulfur atoms in the alloy appropriately, the film thickness can be made from 200 to 300 Å or more to several thousand amps without reducing the thickness very much. However, it is possible to obtain a sheet resistance value of about 500Ω/day. On the other hand, when the film thickness is reduced, the above-mentioned sheet resistance value becomes even larger, and a sheet resistance value of up to about 104 Ω/'D can be easily and stably obtained.

In addition, the circuit board of the present invention has excellent resistance stability by using the above-mentioned quaternary alloy as the resistor material, and the rate of change in resistance value is small when left in high humidity or high humidity conditions. Also from this point of view, there is an advantage that a highly reliable circuit board can be provided.

At present, it is not necessarily clear why the resistor made of the quaternary alloy of the present invention is able to produce the above-mentioned effects. It is speculated that this is caused by the refinement of the crystal grains of the above-mentioned alloy and the change in the crystal structure due to the incorporation of copper and sulfur atoms as non-metallic components.

Copper foil is most commonly used as a highly conductive material in this case, but other conventionally known materials such as nickel foil, tin-plated steel foil, and zinc foil can be widely used.

Further, the manufacturing method of these highly conductive materials is not particularly limited, and materials manufactured by various methods can be applied.

The layer of the resistor made of the quaternary alloy in this invention is
1. It is generally formed by electroplating on the highly conductive material, and its alloy composition is 30 to 80% by weight of tin, preferably 35% by weight, based on the total amount of tin, nickel, and copper.
~75% by weight nickel, 20-70% by weight, preferably 2
5-65% by weight and 0.1-30% by weight of copper, preferably 0
．． It is desirable that the sulfur content is 5 to 28% by weight, and that the relative strength ratio of sulfur to the nickel contained is 3 to 80%, preferably 4 to 75%, as measured by ESCA. If the content of tin, nickel and copper deviates from the above range, the sheet resistance value of the circuit board will not be high enough.
It is difficult to obtain good results due to circuit characteristics. In particular, since the presence of copper greatly contributes to an increase in the sheet resistance value due to its coexistence with sulfur, it should be set within the above-mentioned optimum range, taking the sulfur concentration into consideration. Furthermore, if the sulfur concentration is too low, the sheet resistance value will not be so high, and if the serial number is too high, good results will not be obtained in terms of circuit characteristics, especially in terms of long-term moisture resistance.

Note that the ESCA measurement described in this specification refers to Electron 5pect'roscopy f
It is an abbreviation that takes the initials of orClemitical Analysis (electron spectroscopy for chemical analysis),
The results were actually measured using an X-ray photoelectron spectrometer ESCA 650 B manufactured by Shimadzu Corporation. This type of ESCA measurement is often employed to express the relative content of a particular metal by its relative intensity ratio.

Formation of the layer of the resistor by electroplating techniques contains an alkali metal salt of polyphosphoric acid, a water-soluble organic sulfur compound or a salt thereof and preferably an α-amino acid or a salt thereof, together with a tin salt, a nickel salt and a copper salt. A plating solution is used, and a layer of a resistor is electrodeposited from the plating solution onto a highly conductive material by electroplating.

The above tin salts include stannous chloride and stannous pyrophosphate.
Examples include tin and stannous sulfate, each of which can be used alone or in a mixture of two or more.

The amount used is 2 to 45 f in terms of metal! /l, preferably 3~
It is 409/l.

Further, examples of the nickel salt include nickel chloride, nickel pyrophosphate, nickel sulfate, and nickel sulfamate, and each can be used alone or in a mixture of two or more. The amount used is 2 to 257/l, more preferably 3 to 20 y/e in terms of metal.

Further, examples of the copper salt include cupric chloride, copper pyrophosphate-copper sulfate, etc., and each can be used alone or in a mixture of two or more. The amount used is 0.1 to 3.59 in terms of metal.
/l, preferably 0.2 to 3.2y/e.

Examples of alkali metal salts of polyphosphoric acid include potassium salts and sodium salts thereof, which can be used alone or in a mixture of two or more. Note that polyphosphoric acid is a general term for compounds having the general formula %, and in this invention, n
It is preferable to use an integer of 1 to 3.

The amount of alkali metal salt of polyphosphoric acid to be added is 100 to 45, considering the total amount of tin, nickel, and copper salt added above.
The range is 0 y/lr.

The water-soluble organic sulfur compound or its salt is used to incorporate sulfur atoms into the single-plated alloy. In order for the organic sulfur compound to be water-soluble, it is preferably one having an amino group, hydroxyl group, carboxyl group, etc. as a functional group, or a potassium salt, a sodium salt thereof, etc. Cystine, homocystine, cystine hydrochloride, Thiol Histidine-Glutathione, Homocystine Thiolaftane Hydrochloride, Cysmethionine, Methionine, Ethionine, Cystine, Homocystine-Cystine Disulfoxide, Cystic Acid, Thioglycolic Acid, Sodium Thioglycolate, Thiolactic Acid, Sodium Thiolactic Acid, Thiolactic Acid Calcium, sodium thiosalicylate, dithiosalicylic acid, thiomalic acid, thioacetic acid-thiobutyric acid, sodium diethyldithiocarbamate-potassium ethylxanthate, sodium ethylxanthate, sodium isopropylxanthate, 1-
Thiosorbitol, thioglycerin-2-mercaptoethanol, 2-aminoethanethiol, thiomorpholine, thiodiglycol, thiodiglycolic acid-3,3'-
Examples include thiopropionic acid, 2-thiophenecarboxylic acid, dithiodiglycolic acid, 3,3-dithiodipyridine, saccharin, thiazole, thiourea, thiosemicarbazide, allylthiourea-ethylenethiourea, and thioformamide, each alone or in combination. Can be used in a mixed system of more than one species. The amount used is 0.0597e or more up to the saturation concentration, preferably 0.1 to 20 y/l.

In addition, as the α-amino acid added as necessary,
Examples include glycine, histidine hydrochloride, phenylalanine, leucine, aspartic acid, and glutamic acid. The amount added is O~50y/1! , preferably 5-301
Within the range of il, each can be used alone or in a mixed system of two or more. In order to improve the plating efficiency and improve the characteristic values, suitable amounts of hydrochloric acid, sulfuric acid, sulfamic acid, pyrophosphoric acid, aqueous ammonia, potassium hydroxide, etc. may be added as a PTL adjuster to the plating bath.

In electroplating using the above plating solution, the plating bath temperature is in the range of 20 to 60°C, the plating current density is 0.0 A,/dm" or more, and 3
It is preferable to carry out plating with a total plating electrical quantity of 1,000 coulombs/drn''. Particularly preferably,
In consideration of plating workability and cost issues, the plating current density is set at 0.05 to 5.0 as shown in FIG. OA
/drn2, the amount of plating electricity is 5 to 600 corons/
dm range is good. If the plating bath temperature is not appropriate or the current density is too low, the stability of the plating bath will be impaired, causing variations in the resistance value of the resulting resistor and deterioration of various characteristic values.

As the material used as the anode, any of insoluble electrodes such as carbon electrodes, platinum-coated titanium electrodes, and stainless steel electrodes, and soluble electrodes such as nickel electrodes and nickel-tin alloy electrodes can be used.

After forming the resistor layer in this manner, an electrical insulation layer is further provided on this layer by a conventional method, thereby obtaining a circuit board with a resistor, which is the object of the present invention. Epoxy resins and other thermosetting resins are preferably used as materials for forming the electrical insulating layer, and prepregs made by impregnating glass cloth or other fiber base materials with these resins are used. By heat-pressing (curing) these materials onto the resistor layer, an insulating layer with excellent electrical properties and heat resistance can be obtained.

As described above, according to the present invention, as a method for manufacturing the industrially useful circuit board, a tin salt of 2 to 45 y/l in terms of metal, 2 to 25! j/l nickel salt-〇, 1-3. ．． 5
100-450 y/e with g/l copper salt
A plating solution containing an alkali metal salt of IJ acid, a water-soluble organic sulfur compound or its salt at a saturation concentration of 0.05 y/i or more, and an α-amino acid or its salt at O~50 y/i is used. It is possible to provide a method for manufacturing a circuit board with a resistor, which is characterized in that a resistor layer is formed on a highly conductive material by electroplating from a plating solution.

FIG. 2 shows a process diagram for manufacturing a circuit board from the circuit board of the present invention obtained as described above, and this manufacturing process is not particularly different from the conventional circuit board.

That is, first, in step (A), a photoresist 4 is formed on the highly conductive material 1, and then in step (13), it is exposed to light through a photomask and developed to form a predetermined pattern. - Thereafter, in step (C), nickel plating 5 and gold plating holes are applied to the resist removed portions to form a plurality of one-to-two electrodes 7. Then, in step (I)) electrode 7.
The photoresist 4 is exposed again through a photomask such that the photoresist 4 remains between 7 and 7, and then developed. Subsequently, in the step (E), the high conductor layer 1 and the resistor layer 2 exposed in the portion where the resist was removed in the step (D) are etched away to expose the electrical insulating layer 3. Furthermore, in step (F), electrode 7.
The photoresist 4 between the photoresists 7 and 7 is removed, and the highly conductive body 1 exposed thereby is etched away in step (G).

This leaves a layer 2 of resistor spanning between the electrodes 7.
A protective film 8 is formed on the resistive element in step (II).
A circuit board is manufactured by forming a circuit board.

As detailed above, the circuit with resistor of this invention □
The major feature of the circuit board is 100Ω/J
:, ], It is possible to freely form a resistor with a high sheet resistance value of up to about OKΩ/mm with any film thickness, but it also has good heat resistance, moisture resistance, etc., and the reliability of the resistor is excellent. Our goal is to be able to provide circuit boards.

EXAMPLES Below, examples of the present invention will be described in more detail. Note that this invention is not limited only to the following examples.

Example 1 0-L shaped electrolytic copper foil (35μ thickness) of a predetermined size (20σ angle)
After cutting this copper foil, an adhesive protective sheet for masking the entire surface of the drum on one side during production is crimped, and this is mixed with a cleaning solution (a ratio of 1 volume of Nutra Clean 68 manufactured by Silapray Co., Ltd. to 1 volume of water). (a diluted aqueous solution) for 3 minutes at room temperature.

After that, rinse with running water, and then add it to deionized water.
I washed it with water. Next, ammonium persulfate 200y/I!
and an aqueous solution consisting of 15+++ e/l of concentrated sulfuric acid (hereinafter referred to as
(simply referred to as ammonium persulfate treatment solution) for 2 minutes at room temperature, and after washing with water, the current density was 0.5 A / d ~ 2.
A layer of a resistor was formed by plating a tin-nickel-copper-sulfur alloy for a predetermined period of time at a bath temperature of 25°C. In addition, the following bath composition was applied to the plating bath.

Stannous chloride 30y/z (SnC
12・2F120) Nickel chloride 30y/I! (Ni
c, 2-611゜0) Copper pyrophosphate 1.5y/1
(cu2P2o7.3I■2o) Potassium pyrophosphate 175'l/1(K
41) 207) Chrysin 20y/i (Nl-
12CI-12COO I) Cystine
2. Oy/l(+100CCI-1(
N1-12) Cl-1°S+2 After forming a resistor layer as described in 1, it was thoroughly washed with water and dried. Then,
After peeling off the protective sheet on one side of the copper foil, remove the resistor layer.
- and an epoxy resin-impregnated glass cloth (commonly known as prepreg) were combined and heat-pressed using a lamination press to obtain a circuit board with a resistor.

In Example 1 above, the plating time for forming the resistor is 1
．． Using a circuit board set at 50 seconds, the composition of the quaternary alloy that spans the resistor was investigated using the following method. The results were as shown in Table 1.

<Measurement of alloy composition> The entire surface of the copper foil of the test board was etched with Nutra-etch (copper etching solution manufactured by Silapray; 50°C 11) H-7,
6 to 7.8).

After thoroughly rinsing with water, a 2 cm square piece was cut from the center, thoroughly rinsed again with water, and dried to obtain an ESCASC phase sample.The sulfur concentration contained in the alloy was measured by the relative intensity ratio to the nickel atoms contained. On the other hand, the remaining part of the sample in 1. was thoroughly dissolved in water δL again, and then completely dissolved using a solution consisting of 30 me of nitric acid and 70 me of deionized water, and the concentrations of tin, nickel, and copper were determined by atomic absorption spectrophotometry. IIIJ was determined by

According to the first table, in the above Example 11, the plating time f 4
Using various substrates obtained by setting the heating time to 0 to 250 seconds, circuit boards were produced in the following manner. The results of examining the heat resistance and moisture resistance of this circuit board (which had a predetermined resistance value by setting the plating time) were as shown in Table 2 below. Note that heat resistance indicates the rate of change in resistance (%) when left at 100°C for 100 hours, and humidity resistance indicates the change in resistance when left at 40°C for 100 hours under 190% RI-1. It shows the percentage (%).

In addition, the results of investigating the correlation between the average resistance value of the entire board surface of the circuit board described in 1., the surface distribution (range of variation) of the resistance value, and the plating time are as shown in Figure 3. .

Preparation of circuit board with resistor> The circuit board with resistor was immersed in the above-mentioned cleaning solution at room temperature for 3 minutes, then washed with water and dried. After that, AZ-119 (positive photoresist manufactured by Silapray) was applied using a roll coater.
The photoresist film was formed on the surface of the copper foil by coating the copper foil with water, naturally drying it in a horizontal state for 5 to 10 minutes, and then drying it at 70°C for 15 minutes.

Next, a 3KW ultra-high pressure mercury lamp (1-IMW-N 6-3 manufactured by Oak Seisakusho Co., Ltd., irradiation distance 65 cm) was applied to the photoresist film to give an integrated light amount of 300 ml 7a.
A predetermined pattern for applying nickel plating and gold plating to each electrode and polarity of a large number of resistive elements was printed using AZ-303 (an alkaline developer manufactured by Silapray). The photoresist film on each electrode portion was removed and washed with running water and deionized water for 30 to 60 seconds.Then, the photoresist film was developed at room temperature for 3 minutes with the above ammonium persulfate treatment solution. After processing for seconds,
Washed with water. 2 A/dm2.50 in this removed part
``Nickel plating is applied under the conditions of ``C-5 minutes (7)'',
Furthermore, this plating layer is 0.5 A/dm2.4
Gold plating was performed at 0° C. for 115 minutes, followed by washing with water and drying to form a plurality of one-to-two electrodes.

Next, each resistor element is exposed to light using the exposure device under the same conditions as described above through a photomask that leaves the photoresist film on each resistor element portion. The photoresist film other than the portion was removed. After that, the aforementioned Neutra Ecchi V
The electrolytic copper foil exposed in the removed portion was etched away using an Li trowel. After washing with water, add concentrated sulfuric acid 335 me, concentrated nitric acid 15
The layer of the resistor exposed in the area where the copper foil was removed was removed by etching using an etching solution consisting of 50 ml of concentrated hydrochloric acid, 10 ml of hydrogen peroxide solution, and 590 ml of deionized water.

Subsequently, after removing the photoresist film remaining on each resistor element portion with acetone for 10 to 20 seconds at room temperature,
The copper foil exposed in this removed area was removed by etching using the same etching solution as described above using Nutra Etch v1), thoroughly washed with water, and then dried. In this way, the layer of each resistor that connects one pair of two electrodes is exposed, and this exposed resistor is used as a resistor element, and solder resist ink is screen printed on this element and a part of the electrode part near this element. It was applied by. By heating and curing this under predetermined conditions, the desired circuit board with a resistor was produced.

Table 2 Comparative Example 1.2 No cystine added as a plating solution for resistor plating,
The amount of copper pyrophosphate added is 7. Oy/I! (Comparative example 1
) and copper sulfate (pentahydrate') instead of copper pyrophosphate
5. A circuit board with a resistor was produced in exactly the same manner as in Example 1 except that a plating solution containing Oy/e (Comparative Example 2) was used. The alloy composition of this substrate is also listed in Table 1 above. Also, a circuit board was obtained from this board in the same manner as described above,
The results of determining the relationship between the plating time (12 to 150 seconds) and the resistance value of the obtained circuit board are as shown in FIGS. 4 and 5. Judging from the shapes of these curves, it can be seen that the maximum resistance value is about 100 to 300 Ω/port. For reference, the resistance value is 25-170Ω/
The results of examining the heat resistance and moisture resistance of two ml each in the mouth area are also listed in Table 2 above.

Example 2 A circuit board with a resistor was produced in the same manner as in Example 1 except that glycine was not added to the plating solution for resistor alloy plating. The alloy composition of the resistor of this board was investigated in the same manner as in Example 1, and the results were 68.9% by weight of tin, 28.4% by weight of nickel, and 2.7% by weight of copper.The sulfur content was determined by ESCA measurement. The relative strength ratio to nickel was 27.5%.

A circuit board was prepared from the above substrate in the same manner as in Example 1, and the relationship between the resistance value of this circuit board and the plating time was investigated, and the results were as shown in FIG. In addition, the results of examining heat resistance and drastic humidity in the same manner as above were
It was as shown in the table.

Table 3 Examples 3 to 6 A circuit board with a resistor was obtained in the same manner as in Example 1, except that the plating solution shown in Table 4 below was used as the plating solution for resistor alloy plating. The results of investigating the alloy composition of this substrate and the characteristics tests performed on a circuit board made from this substrate and having a resistance value of about 900 Ω/hole are shown in Table 4.

Reference Example Example 6 as a plating solution for resistor alloy plating
In addition to the plating solution composition, 3.5y/I of copper pyrophosphate is added!
A circuit board with a resistor was produced in the same manner as in Example 1 except that additional addition was made. The alloy composition of this substrate is also listed in Table 4.

Further, a circuit board was obtained from this substrate in the same manner as described above, and the relationship between the plating time (10 to 250 seconds) and the resistance value of the obtained circuit board was determined, and the results were as shown in FIG. It was found that the resistance value was at most 150Ω/mouth. For reference, the results of a characteristic test conducted on products with a resistance value of about 100 Ω/mouth are also listed in Table 4.

Examples 7 to 12 Circuit boards with resistors were obtained in the same manner as in Example 1, except that the composition shown in Table 5 below was used as the plating solution for resistor alloy plating. The results of investigating the alloy composition of this substrate and the characteristics tests performed on a circuit board made from this substrate and having a resistance value of about 6000/unit are shown in Table 5.

Examples 13 to 16 As a plating solution for resistor alloy plating, the amount of glycine added was changed to 10y/i - the amount of cystine added was changed to Q, 5 to 1
0y/1! A circuit board with a resistor was produced in exactly the same manner as in Example 1, except that the additive was used and the plating time was fixed at 100 seconds. The results of examining the alloy composition of this substrate and the heat resistance and moisture resistance of a circuit board made from this substrate are as shown in Table 6 below. Further, FIG. 8 illustrates the relationship between the amount of cystine added and the sheet resistance value.

To Table 6 Example 17 22 The plating conditions were <0.1 to 2.5 as shown in Table 7.
A circuit board with a resistor was produced in the same manner as in Example 5 except that the A/dm was 2.35 to 55°C. The results of investigating the alloy composition of this board and the resistance of a circuit board produced from this board with a resistance value of approximately 1200 Ω/mouth, heat resistance and moisture resistance are listed in Table 7. Met.

[Brief explanation of drawings]

Figure 1 is an explanatory diagram showing the range of suitable plating conditions for forming the resistor layer on the circuit board with resistor of the present invention. Process diagram for forming a predetermined circuit board from a circuit board, 3rd
6 and 8 are characteristic diagrams showing the performance of the circuit board with a resistor of the present invention, and FIGS. 4 and 5 are characteristic diagrams showing the performance of the circuit board with a resistor shown for comparison, FIG. 7 is a characteristic diagram showing the performance of a circuit board with a resistor shown for reference. 1. High conductor, 2. Resistor layer, 3. Electrical insulation layer. Figure 1: Plating electric cable (Fig. 2, Figure 3, Figure 4), yA curve gate (so), dark area (kai), figure 6, mark jp,, Q (#), Figure 7, plating. Summary (edited) Figure 8 '41JU'g (LfI/l) Procedural amendment dated July 8, 1980 To the Commissioner of the Japan Patent Office 1, Indication of the case Patent application No. 1982-212948 2, Title of the invention: Resistor element Relationship between the circuit board and its manufacturing method 3, and the case of the person making the amendment. Shoji Numaguchi (1) The scope of the patent claims is corrected as shown in the attached sheet. (2) Page 9, lines 13 to 15; 25～
65 Heavy Duty 96” is replaced with “30 to 79.9% by weight of tin,
Preferably 35-74.5% double volume, 20-69% nickel.
9 weight%, preferably 25 to 64.5% by weight.'' (3) 5th line from the bottom of page 10; This is an actual measurement. '' was actually measured.In addition, during this actual measurement, the four electric elements of the circuit board were removed by etching to expose the resistor layer τ, and the above photoelectron spectra were determined from this exposed surface side by 1iJl. It is something.”
I would like to correct this. ) Page 12, line 1 from the bottom; In addition, as a sub-machine, it is generally in the range of 45 to 550, preferably 65 to 45.
The sulfur content is preferably in the range of 0, and the sulfur content is usually 5.
~80% by weight, preferably 8-70% by weight. A specific example of such an organic sulfur compound is,'' I am correcting. (5) Page 17, 3rd line from the bottom; ``It is in particular'' is in 1. In particular, it has a sheet resistance value of 400 Ω/hole, which was difficult to obtain with the resistor layer made of a tin-nickel alloy previously proposed by the present applicant, and preferably 500 to 3,000 Ω/hole. It also has the advantage that circuit boards with excellent resistance stability can be manufactured with stable quality. ” I will correct it. Attachment Amended Claim r A circuit board with a resistor, characterized in that it is made of an alloy.(2) The quaternary alloy is 30 to 79.9% by weight of tin, 20 to 69.9% by weight of nickel, and 0 copper in the total amount of tin, nickel, and copper. .1 to 30% by weight, and the relative strength ratio to this contained nickel is 3 to 8 according to ESCA measurement.
Claim No. 1 comprising 0% sulfur
) A circuit board with a resistor as described in item 2. (3) When manufacturing a circuit board having a structure in which a highly conductive material is bonded to at least one side of an electrically insulating layer via a resistor layer, the metal equivalent is 2 to 45? /L tin salt, 2-25y
Alkali metal salt of polyphosphoric acid of 100 to 450 'j/l with nickel salt of /'L and copper salt of 0.1 to 3.5 fl/l, not less than 0.05 fl/l'
A plating solution containing a water-soluble organic sulfur compound or its salt up to a saturation concentration and an amino acid or its salt ranging from 0 to 50 fi'/4 is used, and a highly conductive material "2" is produced by electroplating from this plating solution. A method for manufacturing a circuit board with a resistor, characterized by forming a body layer. ” Patent applicant: Nitto Electric Industry Co., Ltd.

Claims (3)

[Claims] (1) A circuit board having a structure in which a highly conductive material is bonded to at least one side of an electrically insulating layer via a resistor layer, wherein the resistor is made of a quaternary alloy of tin-nickel-copper-sulfur. Circuit board with resistor. (2) The quaternary alloy contains 30-80% by weight of tin, 20-70% by weight of nickel and 01-30% by weight of copper in the total amount of tin, nickel and copper - relative to the nickel content in parentheses by ESCA measurement A circuit board with a resistor according to claim 1, which contains sulfur in an intensity ratio of 3 to 80%. (3) When manufacturing a circuit board having a structure in which a highly conductive material is bonded to at least one side of an electrically insulating layer via a resistor layer, the ratio is 2 to 45 R/1 in terms of metal! of tin salt, 2-25y
100-450 with a nickel salt of /p and a copper salt of 0,1-3.577/! /e alkali metal salt of polyphosphoric acid -0,05y/1! Water-soluble organic sulfur compound or its salt up to saturation concentration and O~50 y/e
A method for manufacturing a circuit board with a resistor, which comprises using a plating solution containing an α-amino acid or a salt thereof, and forming a resistor layer on a highly conductive material by electroplating the plating solution.