JPH0446939A - Carrier tape - Google Patents

Abstract

PURPOSE:To prepare a carrier tape having a linear thermal expansion coefficient as low as that of a metal and excellent in heat resistance and dimensional stability by forming a specific polyether copolymer resin compsn. into a film, subjecting the film to specific thermal treatments, and cutting the film into tapes. CONSTITUTION:A polyether copolymer resin compsn. obtd. by compounding a polyether copolymer comprising repeating units of formulas I and II in a molar ratio of I/(I+II) of 0.15-0.40 and having a melt viscosity of 400 deg.C of 3,000-100,000P with an inorg. filler (e.g. talc) in an amt. of 10-50wt.% of the compsn. is formed into a film, thermally treated at a temp. between the crystallization point and m.p. of the copolymer, thermally treated at a temp. between the glass transition point of it and the temp. of the first thermal treatment, and cut into tapes.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a carrier tape obtained from a Botether copolymer resin composition. Excellent quality, TAB
The present invention relates to a carrier tape made of a polyether copolymer resin composition, which can be suitably used for base films and the like.

[Prior art and the problem to be solved by the invention] In recent years,
In order to develop materials with excellent heat resistance, mechanical properties, and dimensional accuracy, various films such as polyamide, polyimide, polynisdel, and polysulfone have been developed or are already commercially available, and are used for parts of electronic and electrical equipment and machines. It is used as a material for a wide range of purposes.

However, Kapton, which is said to be the best polyimide at present, has high hygroscopicity, so its film has poor dimensional stability.

In addition, polyetherketone polymer, which is a thermoplastic resin, is a material with excellent heat resistance, flame retardance, and chemical resistance, so it is expected to be used as an electrical insulating material in the electrical and electronic fields. has been done.

However, even in this polyetherketone polymer, the glass transition temperature is low and the heat resistance is still insufficient for practical use.

The present invention has been made based on the above circumstances.

The object of the present invention is to obtain a polyether copolymer and a specific amount of Ilj-free! By forming a film from a polyether copolymer resin composition containing a filler and a filler, a thermoplastic resin composition with a linear expansion coefficient as low as that of metal, high heat resistance, and excellent various properties can be produced. Carrier tape is what we provide.

[Means to solve the problem] The structure of the present invention for achieving the above object is as follows.

It consists of a repeating unit represented by the following formula (I); (I) and a repeating unit represented by the following formula (■); :(I)/((I)
+ (II))] is 0.15 to 0.40, and the melt viscosity at 400°C is 3. t100~100
．． A polyether copolymer resin composition in which a polyether copolymer having a 0.000 void and an inorganic filler are blended such that the content of the inorganic filler is 0 to 50% by weight based on the total amount of both. After forming a film, heat treatment is performed at a temperature between the crystallization temperature and melting point of the polyether copolymer, and further heat treatment is performed between the glass transition temperature of the polyether copolymer and the heat treatment temperature. This carrier tape is made by cutting the obtained film into strips.

The carrier tape of the present invention is obtained by heat-treating a film formed from a specific polyether copolymer resin composition and then cutting the film into strips.

The polyether copolymer resin composition contains a polyether copolymer and a specific proportion of an inorganic filler, and the formed film is heat-treated in two stages. This carrier tape has a coefficient of linear expansion as low as that of metal, high heat resistance, and has excellent properties.

This will be explained in detail below.

One of the important points regarding the polyether copolymer which is the raw material for the carrier tape of the present invention is that the polyether copolymer has a repeating unit represented by the formula (I). and a repeating unit represented by the formula (II), and the content ratio of the repeating unit represented by the formula (I) [molar ratio, (I)/((I)+(1)] or 0.15
~0.40, and the composition ratio (molar ratio) of the repeating unit represented by formula (n) is from 0.85 to 0.60.

The composition ratio of the repeating unit represented by the formula (I) is 0.
If it is less than 15, the glass transition temperature of the polyneedle copolymer will be low, resulting in a decrease in heat resistance, or the melting point will be high, leading to deterioration in moldability. On the other hand, if it exceeds 0.40, the crystallinity of the polyether polymer will be lost and the heat resistance and solvent resistance will decrease.

Further, in the polyether copolymer used in the present invention, it is important that the melt viscosity (zero shear viscosity) at a temperature of 400° C. is 3,000 to 100,000 voids.

This is because a low molecular weight polyether copolymer having a melt viscosity of less than 3.000 voids cannot achieve sufficient heat resistance and mechanical strength.

In addition, when the melt viscosity exceeds 100,000 voids, the moldability such as forming into a film deteriorates.

The polyether copolymer used in the present invention has, for example, a crystal melting point of about 330 to 400°C, has high crystallinity, has a sufficiently high molecular weight, and exhibits sufficient heat resistance. It has excellent solvent properties and mechanical strength, and can be suitably used as a new material in the electrical/electronic equipment field, mechanical field, etc.

Such a polyether copolymer can be produced as follows.

-Production method of polyether copolymer-Polyether copolymer is produced by reacting dihalogenobenzonitrile, 4,4"-biphenol, and an alkali metal compound in the presence of a neutral polar solvent in a specific usage ratio. After that, the reaction product can be produced by carrying out a copolymerization reaction with a specific amount of 4,4°-dihalogenobenzophenone.

Specific examples of the dihalogenobenzonitrile that can be used include, for example, 2,6-dihalogenobenzonitrile represented by the following linear formula: (wherein, X is a halogen atom); .4-dihalogenobenzonitrile and the like.

Among these, 2,6-dichlorobenzonitrile, 2,6-difluorobenzonitrile, 2,4
-dichlorobenzonitrile, 2°4-difluorobenzonitrile, and 2°6-dichlorobenzonitrile is particularly dangerous.

The dihalogenobenzonitrile and 4 represented by the following formula;
, 4'-dophenol in the presence of an alkali metal compound and a neutral polar solvent.

The alkali metal compound to be used is as described in 4.4 above.
Any substance may be used as long as it can convert '-biphenol into an alkali metal salt, and there are no particular limitations, but alkali metal carbonates and alkali metal hydrogen carbonates are preferred.

Examples of the alkali metal carbonates include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate,
Examples include cesium carbonate.

Among these, preferred are sodium carbonate and potassium carbonate.

Examples of the alkali metal hydrogen carbonate include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate,
Examples include rubidium hydrogen carbonate and #i' cesium hydrogen oxide.

Among these, preferred are sodium hydrogen carbonate and potassium hydrogen carbonate.

Examples of the neutral polar solvent include N,N dimethylformamide, N,N-diethylformamide, N,N-
Dimethylacetamide, N.

N-diethylacetamide, N,N-sibropylacetamide, N,N-dimethylbenzoic acid amide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-
Isopropyl-2-pyrrolidone, N-isobutyl-2-
Pyrrolidone, N-n-propyl-2-pyrrolidone, N-
n-butyl-2-pyrrolidone, N-cyclohexyl-2
=pyrrolidone, N-methyl-3-methyl-2-pyrrolidone, N-ethyl-3-methyl-2-pyrrolidone, N-methyl-3,4,5-trimethyl-2-pyrrolidone, N-
Methyl-2-piperidone, N-ethyl-2-piperitone,
N-isopropyl-2-piperidone, N-methyl-6-
Methyl-2-piperidone, N-methyl-3-ethylpiperidone, dimethyl sulfoxide, diethyl sulfoxide, l-methyl-1-oxosulfolane, l-ethyl-1
-oxosulfolane, l-phenyl-1-oxosulfolane, N,N''-dimethylimidazolidinone, diphenylsulfone, and the like.

An example of the production method includes a reaction product obtained by reacting the dihalogenobenzonitrile with the 4,4'-biphenol in the presence of the alkali metal compound and the neutral polar solvent; React with 4°-dihalogenobenzophenone.

The 4,4°-dihalogenobenzophenone to be used is a compound represented by the following formula: -difluorobenzophenone and 4,4'-dichlorobenzophenone can be particularly preferably used.

The molar ratio of the total amount of dihalogenobenzonitrile and 4.4°-dihalogenobenzophenone to the amount of 4,4°-biphenol used is usually 0.98 to 1.02.
．． Preferably it is 1.00 to 1.01. The molar ratio of the alkali metal compound to 4.4'-biphenol is
Usually 1.03-2.50, preferably 1.05-2.50
It is 1.25.

Is there any particular restriction on the amount of the neutral polar solvent to be used? Usually, it is the total amount of the dihalogenobenzonitrile, the 4,4' biphenol, and the alkali metal compound per 200 mM of the neutral polar solvent. The amount is adjusted to 0.5 to 1 mole.

To obtain the polyether copolymer, for example, the dihalogenobenzonitrile, the 4,4'-biphenol, and the alkali metal compound are simultaneously added to the neutral polar solvent, and the alkali metal compound is added to the neutral polar solvent. After reacting dihalogenobenzonitrile with the 4,4° biphenol,
Furthermore, the above-mentioned 4,4°-dihalogenobenzophenone is added, and the temperature is usually 150-380°C, preferably 180-380°C.
A series of reactions are carried out at a temperature in the range of 30°C.If the reaction temperature is less than 150°C, the reaction rate is too slow to be practical, and if it exceeds 380°C, side reactions may occur. be.

Also, the reaction time for this series of reactions is normal.

The time is 0.1 to 10 hours, preferably 0.5 to 5 hours.

After completion of the reaction, the polyether copolymer is separated and purified from the resulting neutral polar solvent solution containing the polyether copolymer according to a known method to obtain a polyether copolymer. I can do it.

In addition, the polyether copolymer used in the present invention is
It can also be obtained by simultaneously adding dihalogenobenzonitrile, biphenol, alkali metal salt, and dihalogenobenzophenone to a neutral polar solvent.

The polyether copolymer used in the present invention is 4
Melt viscosity at 00°C: 3.000 to lO, 000
It has a crystalline melting point of 330 to 400°C.

In the carrier tape of the present invention, the content of the alkali metal salt contained in the polyether copolymer, which is the raw material for the film, is as low as possible, for example, 50 ppm or less. or desirable.

This is because if a polyether copolymer contains an alkali metal salt exceeding 5 Opps, a carrier tape formed from such a polyether copolymer may become alkali-resistant if used for a long period of time. This is because leaching of metal salts may corrode surrounding metals.

In order to reduce the alkali metal salt in the polyether copolymer after completion of polymerization, the boether copolymer is washed with an acidic aqueous solution containing an organic acid or an inorganic acid and adjusted to pH 3.5 or less. It's beautiful.

Examples of the organic acids include monocarboxylic acids such as chloroacetic acid, acetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, and propionic acid, and dicarboxylic acids such as oxalic acid and malonic acid. Among these, dicarboxylic acids such as oxalic acid are preferred, and oxalic acid is particularly preferred.These organic acids can be used alone, or two or more of them can be used in combination. I can bring it.

Examples of the inorganic acid include hydrochloric acid, sulfuric acid, and phosphoric acid. Among these, hydrochloric acid is preferred.

It is preferable to adjust the concentration of a solution containing these acids to a pH of 3.5 or less, or to determine the type of acid.

The time for washing the polyether copolymer with the acidic aqueous solution is sufficient to reduce the alkali metal salt content in the polyether copolymer to 50 ppm or less. In addition,
In order to promote the desalination effect by washing, the mixture of the acidic aqueous solution and the polyether copolymer may be heated or heated under pressure during washing.

After washing with an acidic aqueous solution, it is recommended that the polyether copolymer be thoroughly washed with pure water, ion-exchanged water, distilled water, etc. in order to remove the acid from the polyether copolymer.

- Polyether copolymer resin composition - Next, the carrier tape of the present invention specifies the polyether copolymer, preferably the sufficiently desalted polyether copolymer, and an inorganic filler. It is formed from a polyether copolymer resin composition mixed in different proportions.

Examples of the inorganic filler in this invention include carbonates such as calcium carbonate, magnesium carbonate, and dolomite, sulfates such as calcium sulfate and magnesium sulfate, sulfites such as calcium sulfite, talc, clay, mica, asbestos, and glass fibers. , glass peas, silicates such as calcium silicate, montmorillonite, and bentonite, ceramics such as silicon dioxide, silicon carbide, and silicon nitride, and their whiskers. Among the various non-ALL fillers, for example, calcium carbonate, silicon dioxide, alumina, clay (kaolin, bentonite, clay, etc.).

Talc, metal oxides (MgO, ZnO, Ti02), etc. are preferred.

The inorganic filler may be in the form of particles, plates, or fibers, but in this invention, the particle size is 5 gm.
It is sufficient if the size is smaller than that, and preferably a finer one is used.

These Ia-free and jI-free fillers may be used alone or in combination of two or more.

An important point in the polyether copolymer resin composition used in the present invention is that the proportion of the inorganic filler in the total of the polyether copolymer and the inorganic filler is 10 to 50% by weight, Preferably 15-40% by weight
It is to be.

If the blending ratio of the inorganic filler is less than 10% by weight, the expansion rate will increase and the difference from the metal will increase. Moreover, if it exceeds 50% by weight, moldability may deteriorate.

The polyether copolymer resin composition is prepared by mixing 10 to 50% by weight of an appropriately selected inorganic filler to the polyether copolymer balater obtained by the above-mentioned manufacturing method, and blending. After that, it is kneaded in an extruder and made into pellets.

Furthermore, a polyether copolymer resin composition can also be obtained by employing a method of producing a polyether copolymer in the presence of an inorganic filler.

However, if the mixing ratio of the inorganic filler exceeds 50%, the moldability decreases and it becomes difficult to form a film.

1. Manufacture of carrier tape - The carrier tape of the present invention can be obtained by forming the polyether copolymer resin composition into a film, and subjecting the film to heat treatment and reheat treatment in a stretched or unstretched state. .

Film formation is carried out at a temperature 10 to 100°C higher than the crystal melting point using a conventional method such as extrusion molding or press molding.
Preferably, it is carried out at a temperature 30 to 70°C higher than the crystal melting point and rapidly cooled, whereby a non-quality film with good transparency can be obtained.

For example, the polyether copolymer resin composition is supplied to an extruder, the resin temperature is set at 350 to 450°C,
By extruding the polyether copolymer resin composition from a slit-shaped die in a molten state, and cooling and solidifying it, an unstretched non-quality film of the polyether copolymer resin composition can be produced.

Or press at a temperature of 350 to 450 using a heat press machine.
By producing a press film at 0.degree. C., an unstretched, non-quality film of the polyether copolymer resin composition can be obtained.

Next, a stretched film can be produced by orienting these unstretched films by uniaxial stretching or two-wheel stretching.

The stretching method may be either simultaneous biaxial stretching or sequential stretching on each axis.

The stretching temperature is a temperature between the glass transition temperature and the crystal melting point,
For example, it is carried out at 180 to 250°C.

The stretching ratio is preferably 1.2 to 3 times, particularly 1.
．． It is preferable that it is 3 to 2.5 times.

If the stretching ratio is less than 1.2 times, a sufficient stretching effect (improving effect on film properties such as tensile strength and tensile modulus) may not be achieved. The effect may not improve further.

The heat treatment in the method of the present invention is carried out by heating at a temperature between the crystallization temperature and crystal melting point of the polyether copolymer, resulting in a crystallized film.

Regardless of the stretching, the heat treatment is performed under tension, and the crystallization temperature, that is, the temperature at which the polymer amorphized by the above-mentioned film formation is higher than the crystallization temperature and lower than the crystal melting point by heat treatment (temperature elevation), For example, it is carried out at 190-370°C.

As a preferred example, the stretched film may be fixed to a metal frame or the like, and heat treated under tension at 190 to 370°C for 1 to 600 seconds.

There are no particular restrictions on the heating method, and various means can be employed.

In the method of the present invention, the heat-treated film obtained by this heat treatment is further heat-treated again at around the heat treatment temperature.

This reheat treatment is preferably performed under tension or without tension as required, and at a temperature between the glass transition temperature of the polyether copolymer resin composition and the heat treatment temperature.

By performing this reheat treatment, the heat shrinkage rate of the heat-treated film is reduced, making it possible to obtain a film with excellent dimensional stability.

The carrier tape of the present invention is TAB (TapeAu
For example, the film after the reheat treatment is cut into strips with a diameter of 15 mm, and a carrier tape is degreased using a solvent such as trichloroethane. Apply thermosetting adhesive to one side,
After punching out the sprocket holes and device holes, a 35 pm thick copper foil or the like is heat-pressed onto the adhesive coated surface, excluding the sprocket holes. After this is further cured, a circuit is formed on the tape by etching, followed by mounting with tin (Sn) plating and IC bonding ink.

There is almost no dimensional change in the carrier tape during this process,
No warping or twisting occurs after bonding the copper foil.

[Examples] Next, the present invention will be described in more detail based on Examples.

(Example 1) Equipped with a Dean-Starck trap filled with toluene, a stirring device, and an argon gas blowing pipe! lt 20
0! 2,6-cyclopenzonitrile 1 in the L reactor.
, 548 g (9 mol), 4,4°-biphenol 5
．． 58 (l g (30 mol), potassium carbonate 4.56
1 g (33 mol) and N-methyl-2-pyrrolidone 50! L was added, and the temperature was raised from room temperature to 195°C over 1 hour while blowing argon gas.

After raising the temperature, a small amount of toluene was added and the produced water was removed by azeotropy.

Next, after the reaction was stopped at a temperature of 195°C for 30 minutes, 4.4'-difluorobenzophenone 4.582
g (21 mol) to N-methyl-2-pyrrolidone 70
The solution dissolved in the solution was added, and the reaction was continued for an additional hour.

After the reaction, the product was pulverized with a blender, washed with water and methanol in that order, and dried to obtain 10.0 kg of white powdery polyether copolymer (yield: 98
%) was obtained.

When the properties of this polyether copolymer were measured, the melt viscosity (zero shear viscosity) at a temperature of 400°C
has 16,000 voids and a glass transition temperature of 185°C.
The crystal melting point was 348° C., and the thermal decomposition initiation temperature was 560° C. (5% weight loss in air).

According to infrared absorption spectrum analysis, this polyether copolymer had the following repeating units.

(I) (II) (I)/<(I)+(II))=0.3 Talc (FF-R, average particle size 0.7 pm) manufactured by Asada Seifun ■ was added to this polyether copolymer. , and blended so that the content is 20% by weight.

Twin screw extrusion a at 390℃ (manufactured by Ikegai Iron Works: PCM-3)
0), and then formed into pellets.

Using this pellet, extrusion molding is performed using a T-die,
An unstretched film was prepared and sequentially biaxially stretched 1.5 times in length and 1.5 times in width at a temperature of 190°C.

Thereafter, these unstretched and stretched films were each fixed to a metal frame and heat-treated at 300° C. for 60 seconds under one foot length to obtain a biaxially oriented heat-treated film with a thickness of about 75 gm. The coefficient of linear expansion of this film is 1.9X1
It was 0-%/℃ [SEI 0 electron ■ TMA
Measured at 100].

Furthermore, a reheat treatment was performed at 300℃ for 60 seconds to obtain a 35mm
It was slit to the width.

After degreasing these unstretched and stretched films with trichloroethane, a thermosetting adhesive was applied to one side of each film, and sprocket holes and device holes were punched out.

The adhesive coating surface has a thickness of 35 mm excluding the sprocket holes.
After heating and pressing μm copper foil and further hardening, it is etched to form a circuit on the film, Sn plating, IC
Implemented bonding.

During this process, there was almost no dimensional change in the unstretched and stretched carrier tapes, and no warping or twisting occurred after bonding the copper foil.

(Comparative Example 1) The polyether copolymer of Example 1 was formed into a film without adding an inorganic filler and crystallized.
When the copper foil was heated and pressed in the same manner as above, the film curled, making it impossible to manufacture TAB.

(Example 2) Polyether copolymers having different composition ratios were produced by changing the charging bolt of the raw materials in Example 1 as shown below.

2.6-cyclobenzonitrile...1.290 g (7.5 mol) 4.4
゛-Difluorobenzophenone・・・・・・・・4,910 g (2
2.5 mol) Potassium carbonate...4,976 g (
: 16 mol) According to the results of infrared absorption spectrum analysis, the composition of the obtained copolymer was (I)/((I)+(I).
I ) ) = 0.25, and the melt viscosity (400 °C
) 1:l, 000 voids, crystal melting point 379°C1 thermal decomposition onset temperature 562°C, glass transition temperature 182°C.

Using this copolymer, talc was blended in the same manner as in Example 1, and then film formation, biaxial stretching, and heat treatment were performed under the same conditions to create a heat-treated film.

Further, this film was subjected to IC bonding in the same process as in Example 1, but no problems occurred during the process.

[Effects of the Invention] The base film made of the thermoplastic polyether copolymer of the present invention has a coefficient of linear expansion as low as that of metals, has high heat resistance, and has excellent dimensional stability at high and high temperatures. , is extremely useful in electrical and electronic fields such as TAB base films.

Claims (1)

[Claims] (1) The following formula (I); ▲There are mathematical formulas, chemical formulas, tables, etc.▼The repeating unit represented by (I) and the following formula (II); ▲Mathematical formula,
There are chemical formulas, tables, etc. ▼ Consisting of repeating units represented by (II), composition ratio of repeating units represented by formula (I) [molar ratio: (I)/{(I) + (II)} ] is 0
．． 15 to 0.40 and a melt viscosity at 400° C. of 3,000 to 100,000 poise and an inorganic filler, the content ratio of the inorganic filler to the total amount of both. After forming a film of a polyether copolymer resin composition blended so that the amount is 10 to 58% by weight, heat treatment is performed at a temperature between the crystallization temperature and melting point of the polyether copolymer, and A carrier tape characterized in that it is obtained by cutting into strips a film obtained by reheating the polyether copolymer at a temperature between the glass transition temperature of the polyether copolymer and the heat treatment temperature.