JPS61288483A - Molding having printed circuit board - 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 molded product having a printed circuit board. More specifically, it is a molded product having a printed circuit board, (A
) an ethylene copolymer having at least an ethylene unit and at least one unit selected from the group consisting of a carboxylic acid unit, a dicarboxylic acid unit, an anhydride unit thereof and a halfester unit; An electric/electronic device comprising a thermoplastic resin or a composition thereof laminated with a thin material having at least a crosslinked product of a mixture of an ethylene copolymer having at least one unit selected from the group consisting of glycidyl units and glycidyl units. The object is to provide a molded product in which a printed circuit board is integrated by a simple method.

Modern electrical and electronic devices are rapidly becoming smaller, lighter, and more dense. In particular, printed wiring boards have been commercialized for use in home appliances such as radios and video cameras. Nowadays, its use in industrial equipment such as telephones, computers, and printers is expanding due to its mass productivity and high reliability.

Conventionally, in order to achieve high-density three-dimensional packaging in a narrow space for miniaturization, it has been common practice to attach a printed circuit board to the inside of a molded casing with screws or with an adhesive. However, with this method, it is difficult to downsize the casing, and furthermore, the casing may peel off due to vibration or come into contact with nearby wiring, causing failure.

Furthermore, when a conventional thermosetting substrate is adhered to a housing, it often peels off due to the difference in thermal expansion from the housing. In addition, with miniaturization, problems such as poor workability have arisen because components are mounted in a narrow area.

From the above, the present invention does not have these drawbacks (problems), and not only has good heat resistance using a simple method, but also has a printed circuit board, which makes it compact and lightweight. It's about getting things.

. Fortune telling
According to the present invention, these problems can be solved by (A)
r Consists of at least ethylene and at least one type of unit selected from the group consisting of carboxylic acid units, dicarboxylic acid units, anhydride units thereof, and halfester units thereof, and the content of ethylene units is 30 to 99.5% by weight. 1 to 99% by weight and CB)
"Ethylene copolymer consisting of at least ethylene units and at least one unit selected from the group consisting of hydroxyl units, amine units and glycidyl units, and containing 30 to 99.5% by weight of ethylene units." [hereinafter referred to as "ethylene copolymer (B)"]9
Solved by a molded article having a printed circuit board formed by laminating a thermoplastic resin or a composition thereof and a thin article having a thickness of 3 microns to 51 mm and having at least 9 to 1% by weight of a crosslinked mixture. be able to. The present invention will be specifically explained below.

(A) Ethylene copolymer (A) The ethylene copolymer (A) used in the present invention contains at least ethylene units and a group consisting of carboxylic acid units, dicarboxylic acid units, anhydride units thereof, and halfester units thereof. It is an ethylene copolymer containing 30 to 99.5% by weight of the ethylene units.

This ethylene copolymer (A) contains at least the second component (
Copolymers that can be obtained by copolymerizing the following seven monomers to form A), multi-component copolymers of these and other monomers, and acid anhydrides in these copolymers. Examples include those obtained by hydrolyzing and/or alcohol modification of the group.

Typical examples include acrylic acid, methacrylic acid, and ethacrylic acid, which contain at most 25 carbon atoms.
unsaturated monocarboxylic acids as well as maleic anhydride, tetrahydrophthalic anhydride, maleopimaric anhydride, 4-methylcyclohexan-4-ene-1,2-carboxylic anhydride and bicyclo(2,2,1)-hebutyric anhydride. -5-en-
4-50 carbon atoms such as 2,3-dicarboxylic anhydride
unsaturated dicarboxylic acid anhydrides.

Also, other materials having at most 30 carbon atoms (preferably 10 or less) such as methyl (meth)acrylate, ethyl (meth)acrylate, hydroxymethyl (meth)acrylate, and diethyl fumarate.
and vinyl esters having at most 30 carbon atoms such as vinyl acetate and vinyl propionate.

Among the above ethylene copolymers (A), copolymers of ethylene and unsaturated dicarboxylic anhydrides or multicomponent copolymers of these and unsaturated dicarboxylic esters and/or vinyl esters are hydrolyzed and The dicarboxylic acid anhydride units of these copolymers can be converted to dicarboxylic acid units or Hafester units by modification with alcohol. Ethylene copolymers (A) obtained by replacing part or all of the acid anhydride units with dicarboxylic acid units or halfester units can also be preferably used.

To carry out the hydrolysis, the ethylene copolymer (A
) in the presence of a catalyst (e.g. tertiary amine) in an organic solvent (e.g. toluene) that dissolves the copolymer.
It can be obtained by reacting with water at a temperature of ~100°C for 0.5 to 10 hours (preferably 2 to 6 hours, preferably 3 to 6 hours), followed by neutralization with an acid.

To perform alcohol modification, the ethylene copolymer (A) can be obtained by the solution method or kneading method described later.

The solution method is similar to the case of hydrolysis, in which the reaction is carried out in an organic solvent in the presence or absence of the above-mentioned catalyst (the reaction is slow in its absence).
2 minutes to 5 hours at the reflux temperature of the alcohol used in
Preferably from 2 minutes to 2 hours, preferably from 15 minutes to 1 hour.
time).

On the other hand, in the cross-wire method, the tertiary copolymer is usually 0.01 to 1.0 parts by weight (preferably 0.05 to 0.5 parts by weight) per 100 parts by weight of the ethylene copolymer (A). Generally from 0.1 to the dicarboxylic acid unit in the amine and the copolymer.
3.0 times mole (preferably 1.0 to 2.0 times mole)
of saturated alcohol at a temperature above the melting point of the ethylene copolymer (A) but below the boiling point of the alcohol used, using a kneading machine such as the Banbury Mixer 1 extruder commonly used in the fields of rubber and synthetic resins. This is a method in which the reaction is carried out while kneading for several minutes to several tens of minutes (preferably 10 to 30 minutes).

The saturated alcohol used in the above modification with alcohol is a linear or branched saturated alcohol having 1 to 12 carbon atoms, and includes methyl alcohol, ethyl alcohol, and -butyl alcohol.

In the case of the above hydrolysis and in the case of modification with alcohol, the conversion rate to dicarboxylic acid and the halfesterization rate are both 0.5 to 100%, and 10.0 to 100%.
100% is desirable.

The ethylene units in this ethylene copolymer (A) are 30
-99.5% by weight, preferably 30-99.0% by weight, particularly preferably 35-9θ, 0% by weight. Also,
The proportion of carboxylic acid units, their anhydride units and halfester units in the copolymer is 0.1 to 70% by weight in total, preferably 0.5 to 70% by weight, particularly 0.5% by weight. ~80% by weight is preferred.

If an ethylene polymer in which the proportion of carboxylic acid units, anhydride units and halfester units in this ethylene copolymer (A) is less than 0.1% by weight is used, the ethylene copolymer described below When crosslinking with (B) by heating, not only is the crosslinking incomplete, but also the adhesion with the metal layer is poor. Heavy! There is no need for %*m,
Unfavorable from manufacturing and economical standpoints.

In addition, when using a multicomponent copolymer containing the unsaturated carboxylic acid ester and/or vinyl ester, the total amount thereof is usually at most 70% by weight, and 6% by weight.
When using an ethylene copolymer in which the copolymerization ratio of unsaturated dicarboxylic acid ester and/or vinyl ester exceeds 70% by weight, which is preferably 0% by weight or less, the softening point of the copolymer becomes high, and the softening point is 150°C. The temperature below is not only undesirable because fluidity is impaired, but also economically unfavorable.

(B) Ethylene copolymer CB) In addition, the ethylene copolymer (CB) used in the present invention (
B) contains at least ethylene units and hydroxyl units,
At least one unit selected from the group consisting of amino units and glycidyl units" [hereinafter referred to as "second component (B)"]
], and its ethylene units are 30 to 98.
It is an ethylene copolymer containing 5% by weight.

This ethylene copolymer (B) is a copolymer obtained by copolymerizing at least ethylene with the following seven monomers to constitute the second component (B), and a copolymer of these and other monomers. Examples include saponified products obtained by saponifying multicomponent copolymers and copolymers of ethylene and vinyl ester (especially vinyl acetate).

These seven polymers include glycidyl alkyl (meth)acrylates and human mixyalkyl (meth)acrylates represented by the following general formula (the number of carbon atoms in the alkyl group is usually 1).
~25 bias), α-fulkenyl alcohol having 3 to 25 carbon atoms, α-amine having 2 to 25 carbon atoms, and primary or secondary 7-minoalkyl (meth)acrylate (the number of carbon atoms in the alkyl group is usually 1 to 25).

(Here, R1 is H or methyl group R2 has 1-1 carbon atoms.
Typical examples of this heptamer (which is two linear or branched alkyl groups) include butene tricarboxylic acid monoglycidyl ester, glycidyl methacrylate, glycidyl acrylate, glycidyl ethacrylate, itaconate glycidyl ester, hydroxymethyl ( meth)acrylate, hydroxymethyl(meth)acrylate,
Hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyhexyl (meth)acrylate, allyl alcohol, allyl amine and aminoethyl (
Meta)acrylates are mentioned.

Moreover, examples of other monomers include the unsaturated carboxylic acid esters and vinyl esters.

The ethylene unit in this ethylene copolymer (B) is 3O
N is 99.5% by weight, and 30 to θ8.0% by weight is desirable, particularly 35 to 99.0% by weight.

Further, the proportion of hydroxyl units, amino units and glycidyl units in the copolymer is 0.1 to 70% by weight for the same reason as in the case of the ethylene copolymer (A), and is 0.5 to 0.5% by weight. 70% by weight is preferred, especially 0.5-6
0% by weight is preferred. Furthermore, when using a multicomponent copolymer containing the unsaturated carboxylic acid ester and/or vinyl ester, the total amount thereof is generally at most 70 It is preferably 60% by weight or less.

Melt index (JIS K-721) of the ethylene copolymer (A) and ethylene copolymer (B)
0, measured under condition 4, hereinafter referred to as "Ni, .1 to 500 g710 minutes is preferred6. M, 1.
When these ethylene copolymers having a weight of less than 0.01 g 710 min are used, it is not only difficult to mix these copolymers uniformly, but also the moldability is poor.

Among these ethylene-based copolymers, when produced by a copolymerization method, the amount is usually 500 to 2500 Kg/cm.
ethylene and the second component (A) or the second component (B) or these and other components in the presence of a fast chain transfer agent (e.g. organic peroxide) at a temperature of 120 to 280° C. under high pressure of It can be obtained by copolymerizing and the method for producing them is well known.In addition, among the above ethylene copolymers (^), by hydrolysis and/or modification with alcohol, The manufacturing method and the saponification method of the ethylene copolymer (B) are also well known.

(C) Production of mixture (1) Mixing ratio In producing the mixture of the present invention, ethylene copolymer (A) and ethylene copolymer (B
) Ethylene copolymer (A) in the total amount (total)
The mixing ratio of the ethylene copolymer (B) is 1 to 99% by weight [that is, the mixing ratio of the ethylene copolymer (B) is 99 to 1% by weight], and 5 to 99% by weight.
95% by weight is desirable, particularly 10-80% by weight. Ethylene copolymer (A) in the total amount of ethylene copolymer (A) and ethylene copolymer (8)
) is less than 1% by weight or more than 99% by weight, the crosslinking of the mixture by the method described later will be insufficient, and for example, the adhesion with the conductive metal layer described later will be poor.

(2) Mixing method To produce this mixture, it is sufficient to uniformly mix the ethylene copolymer (A) and the ethylene copolymer (B). Triblending may be carried out using a commonly used mixer such as a Henschel mixer, or melt kneading may be carried out using a mixer such as a Banbury, extruder, or roll mill. At this time, a more uniform mixture can be obtained by triblending in advance and melt-kneading the resulting mixture. When melt-mixing, it is necessary that the ethylene copolymer (A) and the ethylene copolymer (B) do not substantially undergo crosslinking reaction (
If the resulting mixture is crosslinked, it will not only deteriorate the moldability when molding the resulting mixture as described below, but also cause a decrease in the shape of the intended molded product and the heat resistance when crosslinking the molded product. Therefore, the melt-kneading temperature is preferably room temperature (20°C) to 150°C, and preferably 140°C or lower, although it depends on the type and viscosity of the ethylene polymer used.

As a guideline for this "substantially no crosslinking", [residual aroma with a diameter of 0.1 micron or more after extraction treatment in boiling toluene for 3 hours] (hereinafter referred to as "extraction residual aroma") is generally 15% by weight. It is preferably at most 10% by weight, most preferably at most 5% by weight.

(3) Production of thin-walled products To produce thin-walled products from the mixture obtained as described above, the T-Guy film method and inflation method, which are commonly used in the field of thermoplastic resins, are widely used to produce films. It can be obtained by extruding it into a film or sheet using a conventional extruder. At this time, if extrusion is carried out at a high temperature, the ethylene copolymer (A) and the ethylene copolymer (B
) is partially or completely crosslinked and small gel-like particles are generated, making it impossible to obtain a uniformly thin product.

For these reasons, the extrusion temperature is usually 250°C or lower. In particular, it is preferable to carry out the process in the same temperature range as in the case of the above-mentioned melt crosstalk.

In any of the above cases, after manufacturing the thin-walled objects, the thin-walled objects with good transparency are made by rapidly cooling them in a water-cooling roll or a water bath to prevent adhesion between the thin-walled objects or between the thin-walled objects and a take-up roll. can get. The thickness of the thin wall thus obtained is between 0.2 and 1000 microns, preferably between 0.2 and 500 microns, particularly preferably between 0.2 and 200 microns.

It is necessary that the thin-walled product obtained in this manner is not crosslinked. That is, the extracted residual aroma is preferably 15% by weight or less, preferably 10% by weight or less, and particularly preferably 5% by weight or less, as described above.

(C) Thermoplastic resin Furthermore, representative examples of thermoplastic resins used for injection molding, pressure molding, etc. in the present invention include propylene resin (pp), butadiene rubber, acrylonitrile-butadiene rubber, or styrene-butadiene rubber with 7-acrylonitrile. Acrylonitrile-butadiene terpolymer resin (ABS resin) obtained by graft copolymerizing 7-acrylonitrile and styrene, and terpolymer resin (ABS resin) obtained by graft copolymerizing 7-acrylonitrile and styrene onto chlorinated polyethylene AC5 resin), polyphenylene oxide resin (PPO resin), polyethylene terephthalate (PET), polybutylene terephthalate (POT), and polycarbonate resin (PC resin). They are used in a wide variety of fields, and their manufacturing methods and various physical properties are well known (for example, in the Encyclopedia of Polymer Science and Technology).
5science and Technology)”
Interscience Publisher
ce PublicSh-er, A division
of John Wiley & 5ons, Inc.
) Published from 1964 to 1871], the molecular weight of these thermoplastic resins varies depending on the type, but generally ranges from 10,000 to 1,000,000. The structure, manufacturing method, physical properties, etc. of these thermoplastic resins are described in JP-A Nos. 58-99951, 58-101149, 58-134144, and 5.
8-1313E143, 58-191751, 5θ-99358, 58-99.998, and 5B-2101197, as well as Japanese Patent Application Nos. 59-8538 and 59-26108. , 59-
No. 213108, No. 59-29959, No. 59-41
No. 982, No. 58-60749, No. 59-85103
No. 59-1301E12, No. 59-901f15
No. 59-101800.

These thermoplastic resins alone may be injection molded, pressure molded, etc., but a composition obtained by adding an inorganic filler to the thermoplastic resin may be injection molded, pressure molded, etc.

The inorganic filler is one that does not decompose during mixing and injection molding for producing the composition.

Inorganic fillers include metals such as aluminum, copper, iron, lead and nickel, oxides of these metals and metals such as magnesium, calcium, barium, zinc, zirconium, molybdenum, silicon, antimony, titanium, and their hydrates. Examples include compounds such as hydroxides, sulfates, carbonates, silicates, double salts thereof, and mixtures thereof. Among these inorganic fillers, those in powder form have a diameter of 1 mm or less (preferably 0.5 mm or less).
Preferably, fibrous ones have a diameter of 1 to 5.
00 microns (preferably 1-300 microns) and a length of 0.1-8 mm (preferably 0.1-5 m+s)
) is preferable, and flat plate-shaped ones have a diameter of 21 mm.
The following (preferably lam or less) are preferred.

However, these inorganic fillers are generally widely used in the decomposition of synthetic resins and rubber, and representative examples are described in the specifications of the above-mentioned Japanese Patent Application Nos. 59-8535 and 59-853B. ing.

Generally, in the fields of electrical equipment and electronic equipment, materials exhibiting flame retardancy are generally desired. Therefore, among the inorganic fillers, antimony oxide and the like. Flame retardants that are widely blended into synthetic resins and those that generate moisture during molding, but that generate moisture at higher temperatures (preferably at temperatures 50°C or more higher than the molding temperature). For example, it is desirable to incorporate some or all of these materials using magnesium hydroxide as an inorganic filler.

When used as a composition in which a thermoplastic resin is blended with an inorganic filler, the composition ratio of the inorganic filler in the composition is at most 80% by weight, preferably 75% by weight or less, particularly 70% by weight or less. suitable. Even if an attempt is made to produce a composition in which the composition ratio of the inorganic filler exceeds 80% by weight, it is difficult to obtain a uniform composition, and even if a uniform composition is obtained, the following It is not possible to obtain a good product when manufacturing a molded product by injection molding, air pressure molding, etc. (D) Molding method The molded product of the present invention is produced by using the above-mentioned ethylene copolymer (A) and ethylene. A laminate obtained by laminating an uncrosslinked or crosslinked thin material or thin material mainly composed of the copolymer (B) and various substances described below is inserted into a molded product in advance, and the thermoplastic resin is Alternatively, the composition may be processed by injection molding, compression molding (stamping molding), thermoforming (for example, vacuum molding, pressure molding), or blow molding, which are generally widely used in the field of synthetic resins.

It can be manufactured by a molding method such as a lamination molding method.

(1) Injection molding method To manufacture using this method, the thin-walled product or laminate is inserted in advance between the male and female molds of an injection molding machine, and the mold is closed. After that, a thermoplastic resin or its composition is filled into the mold from the gate part of the male mold,
Obtained by opening the mold after cooling. The injection pressure should be 100Kg/crn" or higher at the nozzle of the cylinder of the injection molding machine used.
200-2000Kg/crn' is desirable,
In particular, 200 to 1500 Kg/cm' is suitable.

(2) Aged molding method (vacuum forming method and pressure forming method) Manufacturing by vacuum forming method is as follows: At least a thin-walled article or a molded article of a thin-walled article and other materials laminated in sequence as described below, and a thermoplastic resin or In this case, a laminate consisting of a molded product of the composition (hereinafter referred to as ``laminate'') is fixed with a metal frame or nail shape and heated with a heating device.

When the sag of the laminate is generally molded and heated, it becomes stretched inside the wafer that holds it down. When this stretching phenomenon is observed, the best timing to mold the laminate is when the molded product is in a good heating state with few wrinkles or uneven thickness. At this time, the frame of the laminate is pulled out, placed on the upper part of the mold, and the process is carried out from the mold side under a reduced pressure of less than one atmosphere.

On the other hand, in the pressure forming method, the laminate, which has become easier to mold, is pulled out at the top of the mold, and a chamber (box) for pressurized air is placed over the top of the mold to create a pressure of 2 to 8 atmospheres (preferably 3 to 8 atmospheres).
It is obtained by pressing it against the mold side with a pressure of 5 atm) and lifting the mold.

(3) Stamping molding method The laminate is introduced into a drawing die placed in a vertical press machine,
5-80Kg/crn” (preferably 10-e
OKg/crn', preferably 10-50Kg/c
rn') (7) It is sufficient to heat and pressurize under pressure.The pressurizing time is usually 10 seconds or more, and 10 to 60 seconds is common. At this time, the pressure in the first stage is relatively low (for example,
After applying pressure for 10 to 40 seconds at 5 to 20 Kg/crn”,
Relatively high pressure in the second stage (e.g. 40-50Kg/
A molded product with a smooth surface can be obtained by applying pressure for 5 seconds or more.

(4) Other molding methods In addition to injection molding, aging molding, and stamping molding, compression molding using a press machine,
There is a hollow molding method. In these molding methods, similar to the injection molding method, the thin material or laminate is inserted into the mold surface in advance, and a thermoplastic resin or its composition is molded using a commonly used method to obtain an integrally molded product. be able to. Furthermore, regarding the laminate molding method, it can be obtained by laminating and integrating a thermoplastic resin or its composition on the thin object or laminate by a method such as a dry lamination method, hot lamination method, or extrusion lamination method. .

In producing a molded article having a printed circuit board of the present invention, injection molding method and stamping molding method are preferable.
Injection molding is particularly preferred because molded products can be easily produced and molded products with complex shapes can be produced.

(E) Conductive Metal Layer Methods for obtaining the conductive metal layer of the present invention include a method using a metal foil, a method of depositing metal, a method of electroless plating, and an electroless plating method and an electrolytic plating method as described below. One method is to use them together.

(1) Types of metals Metals include metals such as aluminum, gold, silver, iron, copper, nickel, and platinum, and alloys containing these as main components (50% by weight or more) (for example, stainless steel)
can be given.

(2) Foil The thickness of this metal foil is usually 5 to 500 microns,
10 to 300 microns is preferable, especially 1
5 to 100 microns is preferred. Among the metals, electrolytic copper foil with a thickness of 15 to 50 microns is preferably used.

(3) Vapor deposition As a method for vapor depositing the metal, commonly used vacuum heating vapor deposition such as resistance heating, electron beam heating, induction heating, or thermal radiation heating, or sputtering can be applied. Particularly for fine circuits, platinum and gold are often used, and when forming a circuit by etching after forming a thin film, copper, aluminum, and alloys containing these as main components are preferably used.

The thickness of the deposited conductive thin film can be freely selected depending on the conditions of the equipment used, but is usually 100! (
angstrom) to 100 microns, especially 1000. 20 microns is preferred.

Furthermore, copper, nickel,
It is also possible to electroplate a metal such as gold to protect the surface and prevent corrosion, or to apply solder on the conductive path through a solder bath.

A so-called full additive method is also possible in which a circuit is formed by vapor deposition carried out in the present invention on the surfaces of the metal or alloy plate and ceramic layer and on the inner surfaces of the through holes.

In addition, the conductive metal layer can be manufactured using an electroless plating method or a combination of an electroless plating method and an electrolytic plating method as described in detail in Japanese Patent Application No. 130-99139.

(F) Printed board The printed board used in the present invention may be made of the thin material obtained as described above and a conductive metal layer, but may also be made of these and other substances described below.

(1) Other substances Other substances include metal or alloy plates of the conductive metal layer, glass Fam cloth or nonwoven fabric, and films of heat-resistant thermoplastic resins such as polyamide-imide, polyimide, and polyester. The thickness of the metal or alloy is usually between 0.02 and 3.01, especially 0.1
~2.0 mm is preferred. The thickness of the glass fiber cloth or non-woven cloth is 5 microns to 5 mm, especially 20 microns to 1. hm is desirable. Further, the thickness of the film of the heat-resistant plastic resin is 3 microns to 1.0 mm, preferably 10 microns to 200 microns.

(2) Manufacture of printed circuit board The printed circuit board of the present invention is produced by heating and pressurizing the above-mentioned thin material as described below, and applying the above-mentioned "
Vapor deposition, electroless plating method, or a combination of electroless plating method and electrolytic plating method"
The conductive metal layer may be provided by a method (hereinafter referred to as "Method (A)"), or the metal foil and the thin material may be subjected to heat and pressure treatment.

Alternatively, at least one other substance may be placed on one or both sides of the thin-walled object, and these materials may be heated and pressurized, and a conductive metal layer may be provided on one side of the resulting crosslinked object by method (A). Place a metal foil on one side of an object and another substance on the other side, or place a metal foil and another substance on one side of a thin object (with the metal foil on the surface), and place another substance on the other side and heat/process it. Pressure treatment may also be applied.

(3) Heat/pressure treatment The thin-walled product obtained as described above exhibits the same behavior as a normal thin-walled product because crosslinking has hardly progressed. In order to impart heat resistance to the thin-walled product, it is important to heat and pressurize it in the range of 100 to 400°C. Heating temperature is 1
10 to 20 minutes in the range of 00 to 160℃, 1 [io
0.5-10 minutes in the range of ~240℃, 240-400℃
In the range of °C, by heating and pressurizing for 0.1 to 5 minutes, a crosslinking reaction (condensation reaction) occurs within the resin, and the adhesiveness and heat resistance are significantly improved. As for the pressurizing conditions,
Generally it is 0.1Kg/cm' (gauge pressure) or more,
1 to 100 Kg/cm' is desirable, particularly 2 to 20 Kg/cm'.

Furthermore, in order to obtain uniform adhesion, a method of applying pressure with a slight load under vacuum and reduced pressure is also used.

Since the thin-walled article obtained by the present invention exhibits thermocompression adhesion (adhesiveness) at a temperature of 100° C. or higher, the effects of the present invention are further enhanced by performing the crosslinking treatment and adhesion to the metal layer simultaneously. That is, a mixture of ethylene copolymer (A) and ethylene copolymer (B) exhibits thermoplasticity at a temperature of 250°C or lower, but if the mixture is heated to a temperature of loGI°C or higher,
Pressure treatment causes a crosslinking reaction, and at the same time exhibits adhesive properties.

When air is involved between a metal foil or other material and a thin object, it is necessary to use a hot press, hot roll, etc. to bond the thin material. Even if the heating temperature is 300°C or lower, a product with sufficient adhesiveness can be obtained, but if heat resistance is required, it is preferable to press the adhesive at as high a temperature as possible (usually 200 to 300°C).

The extracted residual aroma of the thin-walled product heated and pressurized in this manner is usually at least 60%, preferably 70% or more, and particularly preferably 75% or less.

(G) Molded article having a printed circuit board To manufacture a molded article having a printed circuit board of the present invention,
A thermoplastic resin or a composition thereof can be produced on the printed circuit board obtained as described above by the above-described molding method. Alternatively, a thermoplastic resin or its composition may be molded onto a thin object or a thin object and at least one other substance, and a conductive metal layer may be formed on the surface of the thin object or other material of the resulting molded object by insert molding or other methods. It can be manufactured by providing

A molded product having a typical printed circuit board obtained according to the present invention will be briefly described with reference to the drawings.

A cross section of a molded product having a typical printed circuit board is shown in FIG. 1. Thin material 4 and conductive metal layer 3
1-1 to 1-6 show partially enlarged cross-sections in the case where these and other materials (heat-resistant film 5, glass fiber cloth, or non-woven cloth 6) are laminated.

FIG. 1-1 shows a case where a thin material 4 is interposed between a thermoplastic resin or its composition (hereinafter referred to as "resin layer") l and a conductive metal layer 3. Figure 2 shows a resin layer 1 with a thin material 4. This is a case in which a heat-resistant film 5, a thin material 4, and a conductive metal layer 3 are laminated in sequence, and in FIG. and a case where the conductive metal layers 3 are sequentially laminated. Figures 1-4 to 1-8 show cases in which the conductive metal layer 3 is formed by etching or the like before manufacturing the molded product, and a circuit is formed after the molded product is manufactured by the above-mentioned molding method, or when the molded product is manufactured using the above-mentioned molding method. 4 or a partially enlarged cross-sectional view of a molded product having a printed circuit board obtained by manufacturing a molded product using a molding method in which a resin layer l is applied to a thin material and at least one other substance, and then forming a circuit by etching or the like. be.

These drawings are as shown in FIGS. 1-1 to 1-3 above, in which a thin material 4 is interposed between the resin layer l and the conductive metal layer 3, and FIG. A case in which a heat-resistant film 5, glass fiber cloth, or unlined cloth 6 is interposed between the objects 4 is shown in FIGS. 1-5 and 1-6, respectively.

Furthermore, a molded product obtained by forming a circuit on a printed circuit board in advance and molding this printed circuit board with a thermoplastic resin or its composition, or a printed circuit board on which a circuit is not formed (not having a conductive metal layer) FIG. 1 shows a cross section of a molded product obtained by forming a circuit by plating or the like on the molded product obtained by molding the resin layer and the resin layer. Also the first
FIGS. 1-4 and 1-5 show partially enlarged cross-sections of a molded product having a printed circuit board shown as a cross-sectional view in the figures.

In addition, by forming the circuit in advance and then laminating it, it is also possible to form various three-dimensional circuits as shown below.

Fig. 2-1 shows the case where the circuit surface 3 and the resin layer 1 are in contact (a part of the thin material 4 is in contact with a part of the circuit and the resin layer), Fig. 2-2 Figures 2 and 2-3 show the case where a laminated circuit (printed circuit board) having through holes is formed in advance, and this printed circuit board and the resin layer 1 are laminated. 2-4 shows a case where thin materials 4 are laminated on both sides of the resin layer 1, and a through hole is connected between them. In this case, it is also possible to have circuits on both the front and back sides of the molded product, and to form integrated circuits using through holes.

Alternatively, as shown in FIGS. 1-4, a method may be adopted in which a thin material 4 is placed on the inner surface of the molded product and a conductive layer is formed only on the circuit portion by an additive method or the like.

In the above drawings, l is a resin layer (layer of thermoplastic resin or its composition), and 2 is a printed circuit board. Further, 3 is a conductive metal layer (a metal layer formed by metal foil, sparter, vapor deposition, plating, etc.), and 4 is a thin material manufactured from a mixture of ethylene polymer (A) and ethylene polymer CB). This is the layer of Further, 5 is a heat-resistant film, and 6 is a glass fiber cloth or nonwoven fabric such as glass cloth, glass mat, or glass fiber.

The present invention will now be explained in more detail with reference to Examples.

In addition, in the examples and comparative examples, the peel strength is JIS
Conductive metal layer (copper foil) in accordance with C-8481
The conductive metal layer was peeled off at 80 degrees (pulling speed: 50 sv/min), and the peel strength was measured.

The thermoplastic resin, inorganic filler, and mixture of ethylene copolymer (A) and ethylene copolymer (B) used in Examples and Comparative Examples are shown below.

[(A) Thermoplastic resin]

The following thermoplastic resin was used as the thermoplastic resin.

(1) Olefin polymers As olefin polymers, propylene homopolymer with an MFI of 2.0 g/10 minutes (hereinafter referred to as rPP(A) J), propylene-ethylene with an MFI of 15 g/10 minutes Block copolymer [ethylene content
15% by weight, hereinafter referred to as rPP(B)J] was used.

(1) Polycarbonate resin Medium density polycarbonate resin (v,
1.2/crn', MFI 4.5/10 minutes, hereinafter referred to as rPCJ).

(3) Acrylonitrile-butadiene-styrene ternary copolymer resin (ABS resin) As the acrylonitrile-butadiene-styrene ternary copolymer resin, the ABS resin (hereinafter rABsJ
) was used.

(Acrylonitrile-chlorinated polyethylene-styrene ternary copolymer resin (ACB)) As the acrylonitrile-chlorinated polyethylene-styrene terpolymer resin, ACS (1 ), a grafted product (hereinafter referred to as rAcsJ) was produced in the same manner as
'J was mixed with a dibutylmalate stabilizer as in JP-A-58-191751.

Further, in the same manner as the mixture (2) used in the Example of No. 58-191751, chlorinated polyethylene, acrylonitrile-styrene copolymer resin, and a stabilizer were mixed, and the resulting mixture was used.

(5) Aromatic polyester As an aromatic polyester, polyethylene terephthalate (hereinafter referred to as rPETJ) has an intrinsic viscosity of 0.65.
and polybutylene terephthalate (hereinafter referred to as rPBT J) having an intrinsic viscosity of 0.85.

(8) Modified PPO (grafted product) Modified PPO produced as follows was used.

First, 2,6-xylenol was polycondensed by an oxidative coupling method, and poly-2,8-dimethylphenylene-1,
4-ether [intrinsic viscosity (measured in chloroform at 30°C, unit dfL/g) 0.53, hereinafter referred to as rPPOJ] was produced. 100 parts by weight of PPO, 25 parts by weight of styrene monomer, 10 parts by weight of styrene homopolymer [
Melt flow index (according to JIS K-7210, measured under conditions of temperature 2.18 kg and load 10 kg) of 13.0 g 710 minutes] and 2.1 parts by weight of di-tertiary-butyl peroxide were mixed in a Henschel mixer. After mixing for 10 minutes using a twin screw extruder (dia.
A styrene graph) PPO mixture (hereinafter referred to as "modified PPOJ") was produced using a styrene graph (30a+o, resin temperature 270°C).

[(B) Inorganic filler]

As inorganic fillers, talc with an average particle size of 3 microns (aspect ratio of about 7), mica with an average particle size of 3 microns (aspect ratio of about 8), glass fiber (single la
m diameter 11 microns, cut length 3 mm, hereinafter referred to as rGF
J) and calcium carbonate (hereinafter referred to as r'cacO3J) having an average particle size of 0.8 microns were used.

[(C) Mixture of ethylene copolymer] Mixture of ethylene copolymer (A) and ethylene copolymer (B) 1.1. is 30G g 710 minutes Theal ethylene-acrylic acid copolymer (density 0.954 g/cm",
Acrylic acid copolymerization ratio 20% by weight, hereinafter referred to as rEAA J
) and an ethylene-vinyl acetate copolymer with a vinyl acetate copolymerization ratio of 28% by weight (saponification degree 97.5%, M, 1.
75g/10min, density 0.951g/, cm”
, hereinafter referred to as "saponified material") [mixing ratio 50:50 (weight ratio)], hereinafter referred to as "mixture (1)"
], 2, 200 g/10 minutes (density 0.950 g)
/ cm'', methacrylic acid copolymerization ratio 25% by weight
) and the above saponification degree [mixing ratio 50:50 (
weight ratio), hereinafter referred to as "mixture (■)"].

A ternary copolymer of ethylene-ethyl acrylate-maleic anhydride (ethyl acrylate copolymerization ratio: 30.7% by weight, maleic anhydride copolymerization ratio: 1.7% by weight) with ) toni,■,ga
A terpolymer of ethylene-methyl methacrylate-hydroxy methacrylate (copolymerization ratio of methyl methacrylate 20.7% by weight) with a yield of 123 g/10 minutes.

A mixture of hydroxy methacrylate (copolymerization ratio 11.7% by weight) (mixing ratio 50:50 (weight ratio), hereinafter referred to as "Mixture (m) J") and ethylene in which M, 1. is 105 g/10 min. Ternary copolymer of methyl methacrylate-maleic anhydride (copolymerization ratio of methyl methacrylate: 20.5% by weight, copolymerization ratio of maleic anhydride: 3.1% by weight) and ternary copolymer of ethylene-methylmethacrylate-glycidyl methacrylate Polymer (copolymerization ratio of methyl methacrylate: 18.6% by weight)
, glycidyl methacrylate (copolymerization ratio: 12.7% by weight) [mixing ratio: 30:7G (weight ratio), hereinafter referred to as "mixture (■)"] was used. These mixtures were manufactured by tri-blending the respective copolymers or terpolymers for 5 minutes using a Henschel mixer. Mixtures (I) or IV) obtained as described above.
and an extruder equipped with a T-die (diameter 40III11, die width 30cm,
A film having a thickness of 100 microns was formed using a rotational speed of 85 rotations/min under the conditions where the cylinder temperature is shown in Table 1. The extracted residual aroma of the obtained film was measured. In both cases, it was 0%.

Table 1 Examples 1-14, Comparative Examples 1 and 2 Each film thus obtained was heated at 250°C and
Printed circuit boards were manufactured by laminating them with electrolytic copper foil (thickness: 35 microns) under pressure of 20 Kg/am'' (gauge pressure) using a heat press machine at 00° C. for 10 minutes each.

Each printed circuit board obtained in this way was put into an injection molding machine (
The electrolytic copper foil of the printed circuit board was inserted so as to be in contact with the male mold surface of the mold (clamping force: 200 tons). After closing the mold, the injection pressure is 90 Kg/crn' and the resin temperature is as shown in Table 1, and the thermoplastic resin (type shown in Table 2) is
However, in Example 12, ABS containing 30% by weight of the talc, and in Example 13, 30% by weight of the G
ABS containing F.

In Example 14, A containing 30% by weight of CaC03
BS) was insert injection molded to a thickness of 2mm.
A grip for a telephone receiver having a shape of 2.5 cm in width, 4 cm in width and 10 cm in length was manufactured.

(Margins below) Table 2 Examples 15 to 19 The electrolytic copper foil and 400 g/m'' plain-woven glass cloth (
A printed circuit board was manufactured under the same conditions as described above, with a thickness of 75 microns interposed between each of Example 15) or 400 g/m'' chiplant mat (Example 16).

Mixture of the electrolytic copper foil described above, thickness 50 microns (ff)
A printed circuit board was manufactured under the same conditions as described above (Example 17), in which a film of polyimide with a thickness of 25 microns and a film of the mixture (rV) with a thickness of 50 microns were laminated in this order (Example 17). A printed circuit board was manufactured in the same manner as in Example 17 (Example 18), except that a 25 micron thick polyester (trade name: Mylar, manufactured by DuPont, USA) was used instead of the polyimide film used in Example 18. Electrolytic steel foil with a thickness of 17 microns, a film of mixture CI) with a thickness of 25 microns, a thickness of 2
A printed circuit board having a polyimide film of 5 microns and a film of mixture (I) having a thickness of 25 microns laminated in this order was manufactured under the same conditions as described above (Example 19).

The thus obtained printed circuit board is subjected to insert injection molding in the same manner as above using thermoplastic resin whose type is shown in Table 3 at the resin temperature shown in Table 3, and a telephone having the same shape as above is manufactured. manufactured the grip part for the handset.

Table 3 Implementation g420.21. Comparative Example 3 A film of the mixture (m) having a thickness of 100 microns was masked in areas other than the circuit using a screen printer.

The obtained film was plated at 72° C. with a chemical plating solution having the following composition in an aqueous solution of No. 11 to obtain a copper plating film of about 20 microns on both sides of the sheet.

Cu5O/ 5H2010g EDTA・2Na・2H20.30gHCHO(3
8%) 3m NaOH 12g After plating was completed, the masking was washed off, washed with water, and dried (Example 20).

The surface of the mixture (■) (Example 21) or EAA (Comparative Example 3) film, each having a thickness of 100 microns, was coated with a vacuum evaporation device (manufactured by JEOL Ltd., trade name JEE-).
Platinum was deposited using a 4X model in a 2X 10'-hole to obtain a metal film with a thickness of 5000 mm.

The copper-plated or platinum-deposited films obtained in the above manner were treated with AB at a resin temperature of 230°C in the same manner as described above.
132 parts by weight of S, 25 parts by weight of hexanechlorocyclopentadiene dimer and 13 parts by weight of antimony trioxide (average particle size 1.0 microns) were triblended for 5 minutes using a Henschel mixer. The 8 compound (pellet) obtained by melt-kneading the mixture was subjected to insert injection molding to produce a grip part for a telephone receiver having the same shape as above.

Example 22 A film of the mixture (m) with a thickness of 100 microns was injection molded with ABS at a resin temperature of 230° C., and the thickness was 2 mm, as shown in a partially enlarged cross-sectional view in Figure 1-1.
, a part of a camera body with a width of 3 CI, a length of 5 cm, and a width of 8 cm was manufactured.

A mixture of parts of the bodies thus obtained (II
The surface on which the film I) was inserted was plated with copper (thickness: 17 microns) in the same manner as in Example 20.

Examples 23 to 25 A printed circuit board was manufactured by hot pressing a film of a copper foil having a thickness of 17 microns in advance and a film of a mixture CI having a thickness of 100 microns in the same manner as in Example 1 (Example 2).
3) Copper foil with a thickness of 17 microns, a film of mixture (I) with a thickness of 50 microns, the plain woven glass cloth used in Example 15, and a film of the mixture with a thickness of 50 microns, laminated in this order. A printed circuit board was produced (Example 24), and an EAA film (Comparative Example 4) and a saponified film (Comparative Example 5) each having a thickness of 100 microns were plated in the same manner as in Example 20. Ta. Further, a commonly used epoxy resin was applied to an electrolytic copper foil (thickness: 35 microns) and dried (Comparative Example 6).

The surface temperature of the printed circuit board and ABS obtained as described above was 180°C (170°C in Example 25).
Under the conditions, the first stage is 3
Stamping was carried out in two stages by holding the pressure at 50 Kg/c rn'' for 20 seconds in the 0 second and second stages to produce a grip for a telephone handset having the same shape as above.

' Furthermore, in Example 25, an electrolytic copper foil with a thickness of 35 microns, a film of mixture (IV) with a thickness of 100 microns, a sheet of modified modified PPO (thickness 3 sm), a mixture (IV) with a thickness of 100 microns, IV) film and electrolytic copper foil with a thickness of 35 microns at 20Kg/ct at 250℃
Lamination (crosslinking) having the cross section shown in FIGS. 2-4 was carried out while holding the product under RF pressure for 30 seconds to produce a handset grip having the same shape as above. A drill was used to drill through holes of 0.5 m and 1.0 mm in diameter in the obtained laminate, and through plating was performed in the same manner as in Example 20 using the chemical plating solution used in Example 20. A copper plating film having a thickness of approximately 5 microns was manufactured by performing this in the hole portion (Example 25).

The peel hardness of the electrical devices and electronic devices obtained as described above was measured. The results are shown in Table 5. In this case, the interface of the peeled surface is shown in Table 4. In this column, "metal layer" means a conductive metal layer (such as copper foil), and ""Film" means mixture CI) or rV)
, EAA and a saponified film, and "resin" means an injection molded thermoplastic resin or a layer of thermoplastic resin containing an inorganic filler.
Table 4 shows partially enlarged cross-sections of the obtained electrical equipment and electronic equipment corresponding to Figures 1-6 and 2-1 to 2-4.

(Leaving space below) Table 4 (Part 1) Table 4 (Part 2) From the results of the above examples and comparative examples, the molded product having the printed circuit board of the present invention has a circuit integrated into the inner surface of the molded product. Not only is it possible to design a very compact device because it is formed of a metal, but it also has good heat resistance and can be directly soldered to a single circuit, and it also prevents the circuit from peeling off from the device due to impact, etc. In addition, the wiring can be formed three-dimensionally by insert molding, and since the wiring is not floating inside the device, accidents such as short circuits will not occur, so it is clear that it will be widely used in the future.

The molded product having the printed circuit board of the present invention exhibits the following effects (features) including its manufacturing process.

(1) Because the conductive metal layer (printed circuit board) and thermoplastic resin layer or thermoplastic resin layer containing inorganic filler are integrated by the above molding method, the printed circuit board is fixed to the molded product as in the conventional method. Not only is this step omitted, but there is also no complication associated with that step.

(2) Since a circuit can be formed inside the molded product, the product can be made smaller and lighter.

(3) Since three-dimensional wiring becomes possible, the number of complicated circuits can be reduced, and the number of connections using connectors and the like is therefore reduced, thereby reducing accidents.

(4) All conventionally used thermoplastic resins can be used to manufacture molded products (electrical equipment, electronic equipment, etc.), making it possible to develop a wide range of products.

(5) Since the mixture has good heat resistance and it is possible to apply solder to the surface of the layer of the mixture, connection by solder is possible.

(8) The mixture has electrical properties (eg, insulating properties).

Excellent withstand voltage and discharge tangent performance).

The molded product having the printed circuit board of the present invention can be used as a part of various devices and molded products to exhibit the above-mentioned effects. Representative devices and molded products are shown below. .

1) Home appliances such as washing machines, refrigerators, microwave ovens, TV sets, video cameras, cassette recorders with radios, and speaker units.

(2) Automobile parts (e.g. instrument panel, lights, wipers, doors) (3) OA equipment (e.g. word processors, printers, wet or dry copying machines, facsimiles, etc.)
Computers, desktop calculations 41) (4) Also cameras, telephone exchanges, telephones, fire alarms, clocks

[Brief explanation of the drawing]

FIG. 1 and FIG. 2 are both partial cross-sectional views of a molded product having a printed circuit board of the present invention. Moreover, FIGS. 1-1 to 1-6 and FIGS. 2-1 to 2-4 are partially enlarged sectional views of the molded product having the printed circuit board shown in FIG. 1 or 2. 1... Layer 2 of thermoplastic resin or its composition.
...Printed circuit board 3...Laminated material in which conductive metal layers or these and other substances are laminated 4...Thin material 5...Heat resistant sex film

Claims (1)

[Claims] A molded article having a printed circuit board, (A) consisting of at least ethylene and at least one unit selected from the group consisting of carboxylic acid units, dicarboxylic acid units, anhydride units thereof, and half ester units, and containing ethylene units; 1 to 99% by weight of an ethylene copolymer in an amount of 30 to 99.5% by weight; and (B) at least ethylene units and at least one unit selected from the group consisting of hydroxyl units, amino units and glycidyl units. and the content of ethylene units is 30 to 99
．． A print comprising a thermoplastic resin or a composition thereof laminated with a thin material having a thickness of 3 microns to 5 mm and having at least a crosslinked product of a mixture of 5% by weight of an ethylene copolymer and 99 to 1% by weight. Molded product with a substrate.