JPH0436998A - Top tape film - Google Patents

Abstract

PURPOSE:To form a top tape film equipped with a long life of its coating liquid and with a large degree of freedom by composing a complex crystal from at least two types of crystalline complex bodies, and specifying at least one of the complex bodies. CONSTITUTION:A top tape film 1 to be used as a carrier tape is so constructed that a heat seal type adhesive layer 3 containing 7,7,8,8-tetracyanoxydimethane complex crystal is formed on one side of a base film 2, wherein the complex crystal consists of at least two types of crystalline complex bodies, and at least one of the complex bodies is alkyl radical substituted 7,7,8,8- tetracyanoxydimethane complex body. This 7,7,8,8-tetracyanoxydimethane complex body as at least of one the TCNQ complex bodies having different crystal forms, which presents good dissolutiveness in a versatile solvent and a larger hydrophobic property than TCNQ complex body, widens the degree of freedom in solvent design when used as a coating liquid and largely prolongs the lifetime of coating liquid compared with where a TCNQ complex body not substituted with alkyl radical.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a top tape film for a plastic carrier tape used for storing and transporting minute surface-mounted parts such as various electronic parts and precision parts. It is.

[Conventional technology]

Generally, the top tape film for carrier tape is
The base film is a polyester film with a thickness of 10 to 50 μm or an extruded film with both polyester/polyolefin layers, and a heat seal with a thickness of 10 to 30 μm is made of styrene-butadiene-styrene broxol copolymer resin, ethylene-vinyl acetate copolymer resin, etc. Those in which the adhesive layer is provided by a film lamination method or a coating method are widely used.

With this top tape film, after parts are stored in the cavities of the carrier tape, the lid is placed on top and both ends of the film are heat-sealed to the carrier tape to prevent parts from falling off during storage and transport. When mounting components using an automatic mounting machine such as a chip mounter, it is used after being peeled off from the carrier tape.

This top tape film is unwound and wound up several times during the manufacturing and usage processes, so it is easily charged with static electricity due to friction and contact.
When peeling the top tape film from the gear rear tape, there is a problem where the stored parts electrostatically adhere to the top tape film side and fall off from the carrier tape cavity.
In addition, complementary MO3-1c, TTL (1-transistor
transistor logic), MOS-FE'F (field effect transistor), bipolar transistor,
/ Semiconductor elements that are sensitive to static electricity, such as T-kidiodes,
If the top tape film comes into contact with the top tape film, it will be damaged by static electricity due to discharge, so conventionally, the top tape film is coated with a surfactant-based antistatic agent.
It is used by kneading it into a sealing adhesive layer or coating it on the surface of a film.

Also, I Knob Tape Fill! In order to obtain the antistatic effect of , it is said that the surface resistance needs to be 10 9 Ω or less per medium area, preferably 10 7 Ω or less, in order to prevent parts from falling off when the film is peeled off.

An effective way to provide such an antistatic effect is to add conductive powder such as carbon blank or fine metal powder to the adhesive layer.
Since it is necessary to check or visually inspect the marking characters on the parts through the film surface, transparency is required, so it cannot be practically adopted. Therefore, as a method to increase the conductivity of the surface of the I-Tsubu tape film, there is an antistatic method using a transparent or translucent surfactant, i.e., an anionic surfactant, a cationic surfactant, a nonionic surfactant, and a nonionic surfactant.
A commonly used method is to impart hydrophilicity and ionicity to the surface of an L-tube tape film by incorporating a surfactant such as an amphoteric active agent into the adhesive layer of the film or coating the surface of the film.

Surfactants used in such antistatic agents include aliphatic quaternary ammonium salt type cationic surfactants, carboxybetaine type amphoteric surfactants, and anionic surfactants such as higher alcohol phosphate ester sodium salts. Nonionic surfactants such as antistatic agents, polyoxyethylene sorbitan fatty acid esters, and polyoxyethylene alkyl amines are used, but these antistatic agents are in powder form.

It is commercially available in the form of an aqueous solution or an oil solution, and is used by kneading it into the heat-sealing adhesive layer or coating it on the back side of the film.

However, in general, 11 surfactants, on the film surface,
C00-M', -O3(h-M", (the above M
baIt, Na.

element atoms such as K), CN(CH3)2) "X
-(X is a halogen element atom such as C1 or Br), OL
Hydrophilic groups such as (CH2CHzO) are arranged toward the atmosphere, and their hygroscopicity lowers electrical resistance. C145~85%RH)
The surface resistance is 109 Ω or more per unit area, and it is not useful for preventing electrostatic damage of semiconductor elements, and the compatibility of the adhesive resin and antistatic agent is a problem when kneaded into the adhesive layer. Therefore, if the compatibility is poor, it may bleed onto the surface of the adhesive layer and deteriorate the heat-sealing performance. Also, if the film surface is coated, it may dissolve in moisture and lose its antistatic effect. There are problems such as easy loss, and it has been desired to develop a 1 to 3.5 mm tape film that has both satisfactory antistatic ability and transparency.

Recently, 7,7,8,8-tetracyanoxydimethane complex (hereinafter referred to as TCNQ complex) has been developed as an I-tube tape film that has both antistatic ability and transparency, for example, as disclosed in Japanese Unexamined Utility Model Publication No. 1-1.12599. ) has been proposed. Products using this TCNQ complex have a conductive mechanism based on a network conductive path created by the precipitation of needle-like crystals, so their surface resistance is not affected by atmospheric humidity, etc., and is relatively high. There is an advantage that a top tape film having conductivity and transparency with a light transmittance of 80% or more can be obtained.

[Problem to be solved by the invention]

However, in the conventional top tape film using this TCNQ complex, the network-like conductive path is due to the contact of precipitated needle-like crystals, so the state of crystal growth depends on the volatilization rate of the solvent and the temperature during drying. distribution is easily affected;
Therefore, the number of conductive paths in an area of about m is non-uniform, which results in large variations in surface resistance and makes it impossible to obtain a uniform surface resistance. Heat sealing is required for 0.2 to 1.0 seconds at a high temperature of 130 to 170°C, so heat resistance is required. %R.
There was a problem in that under the conditions of (H), the junction points of the needle-shaped crystals deteriorated, the conductive paths were significantly reduced, and the conductivity was significantly lowered.

That is, as the TCNQ complex, for example, N-n butylysoquinolinium TCNQ complex is used alone, and in a solvent solution of polymer 7 trisox, 3 to 100 parts by weight of the solid content of the polymer matrix is added. When part by weight is dissolved and a thin film is formed on the surface of a transparent substrate using a guvia coater, roll coater, or spin coater, the T C N Q complex is precipitated as fine needle-like crystals within the thin film. , as shown in FIG. 5, a conductive path in the form of a network chain grows to provide conductivity. However, in this case, the state of crystal growth is affected by the volatilization rate of the solvent and the temperature distribution during drying, so the number of conductive paths per unit area becomes uneven, resulting in large variations in surface resistance, and the formation of a network. It was found that the bonding points of the crystals in the conductive path, which is a chain, deteriorated under high temperature and high humidity conditions, resulting in a significant increase in resistance.

The TCNQ complex has N. N rainbow medylborumamide,
It is insoluble or sparingly soluble in most solvents other than strong polar proton solvents such as dimethyl sulfoxide and cyclohexanone at room temperature, and these strong polar proton solvents should not be used when used as a coating fluid in actual processing. Naturally, the degree of freedom in designing the coating solution is extremely small, and at the same time, these strong polar proton solvents are generally more expensive than general-purpose solvents, so the cost of the resulting top tape film is low. There was a problem that I. was expensive. Furthermore, these strong polar proton solvents have high water absorption properties due to their polarity, and when the solvent absorbs water, this water has the function of a catalyst that promotes the disintegration of the TCNQ complex. There was a problem in that when the solution was stored for a long period of time, the surface resistance increased significantly.

The present invention aims to solve these conventional problems, and has a small variation in surface resistance, a small decrease in conductivity even under high temperature and high temperature conditions, a long life of the coating solution, and a flexible selection of solvents. The objective is to provide a top tape film that has a greater degree of freedom and is lower in cost.

[Means to solve the problem]

The present invention contains 7,7,8.8 tetracyanoxydimethane complex crystals on one side of the base film.-1-
A top tape film for carrier tapes having a sole adhesive layer formed thereon, wherein the complex crystals are composed of at least two types of crystalline complexes, and at least one type of the complexes is an alkyl group-substituted 7,7,8,8 - A top tape film characterized by being a tetracyanoxydimethane complex.

Further, in the present invention, 7 is provided on one side of the base film.

7, 8. For carrier tapes 1 to 1 formed with transparent conductive polymer film containing 8-tetracyanoxydimethane complex
A tube tape film, wherein the complex crystal is composed of at least two types of crystalline complexes, at least one of the complexes is an alkyl group-substituted 7,7,8,8-tetracyanoxydimethane complex, This is a top tape film characterized by having a heat-sealable adhesive layer on the other side of the base film.

〔Example〕

Embodiments of the present invention will be described with reference to the drawings. In order to obtain a top tape film 1 having excellent antistatic ability, as shown in FIG.
8.8-Tetracyanoxydimethane complex (hereinafter referred to as TCNQ)
A top tape film for a carrier tape having a heat-sealable adhesive layer containing crystals (abbreviated as "complex"), wherein the complex crystals are composed of at least two types of crystalline complexes, and at least one of the complexes is Alkyl group substitution 7,
7.88 tetracyanoxydimethane complex, or has a heat seal adhesive 3 on one side of the heath film 1, and a TCNQ complex on the other side of the heath film opposite to the adhesive layer 3. Transparent conductive polymer film 2 containing
The I-tube tape film 1 is characterized in that the complex crystal is composed of at least two types of crystalline complexes, and at least one of the complexes is an alkyl group-substituted TCNQ complex, A certain carrier tape 5
L. which can be used by adhering to the flange-like peripheral edge 51 of
This is a knob tape film.

As a result of careful consideration of the crystal forms of the TCNQ complexes used, their combinations, and the types of substituents, we found that, for example, two or more types of crystal forms, such as needle-like and plate-like forms, can be found in polymeric 7-trisox, such as adhesives. By blending different TCNQ complexes, crystals with a shape different from the crystal shape described above are densely precipitated in the polymer membrane matrix, and a TCNQ complex whose conventionally known crystal shape is only needle-shaped is used. The number of contact points between the crystals in a unit area increases compared to the case where the crystals contact each other within a unit area, and the volume resistivity and surface resistance of the conductive polymer film can be lowered. In addition to reducing the resistance value and reducing the increase in resistance under high temperature or high temperature conditions, at least one of the TCNQ complexes with different crystal forms has good solubility in general-purpose solvents, and compared to the TCNQ complex. By using argyl group-substituted 7,7,8.8-tetracyanoxydimethane complex (hereinafter abbreviated as R-TCNQ) with high hydrophobicity, the degree of freedom in solvent design when used as a coating liquid is increased. , the life of the coating liquid could be significantly extended compared to the case where an alkyl group-unsubstituted TCNQ complex was used.

The R T CN Qtu body used in the present invention is alkyl group-substituted 7,7,8.8-tetracyanoxydimethane (R-
It is known that the volume resistivity can vary over a wide range from 10'' to 106 Ω·cm depending on the type of TCNQ') and a suitable donor (D'). Here, the alkyl group means a lower alkyl group having 1 to 3 carbon atoms, specifically methyl-T CN Q' and ethyl-T CN Q'.

n-propyl-1"CN Q', iso-propyl-TC
It is NQ'. In R-TCNQ complexes in which these alkyl groups are higher alkyl groups having 4 or more carbon atoms, their hydrophobicity and solubility in general-purpose solvents are improved, but on the other hand, the molecular structure of the alkyl groups becomes bulky, resulting in crystallization of the complex. This is not preferable because it has poor properties and crystallization is less likely to occur when applied to a film, resulting in a decrease in H conductivity.

Similarly, perfluoroalkyl groups and organosilyl groups can be considered as hydrophobic functional groups other than alkyl groups.
It is very difficult to introduce these functional groups, and therefore the resulting [-TCNQ complexes are not only very expensive, but also less preferred because of the bulkiness of the molecule, which reduces its conductivity.

Many compounds such as tetrathiafulvalene are known as the 1-ener (D) of the present invention, including gynoline, isoquinoline, naphthoquinoline, 2,2-bipyridyl, .4 bipyridyl or a compound in which the N-position thereof is substituted with an alkyl group having 1 to 8 carbon atoms is preferable, and a compound in which the N-position of quinoline or isoquinoline is substituted with an alkyl group having 1 to 8 carbon atoms is more preferable.

The R-TCNQ complex used in the present invention includes N-methyl (
iso)quinolinium-methyl-TCNQ complex, N-methyl(iso)quinolinium-ethyl-TCNQ complex, N-
Methyl(iso)quinolinium-n-propyl-TCNQ
Complex, N-ethyl(iso)quinolinium-ethyl-TC
NQ complex N complex (iso)quinolinium-ethyl-T
CN Q tu body, N-ethyl(iso)quinolinium-
n-propyl-TCNQ complex, N-n-propyl (iso)
Quinolinium-methyl-TCNQ complex N-complex Child propyl(iso)quinolinium-ethyl TCNQ complex, N-n-
Propyl(iso)quinolinium-n-propyl-TCN
Q complex, N-isobe 1 cobyl(iso)quinolinium-
Methyl-TCN Q t? f-isomer, N-iso-propyl (
iso)quinolinium-ethyl-TCNQ complex, N-iso-propyl(iso)quinolinium-n-propyl-TC
NQ complex, N-n-butyl(iso)quinolinium methyl-T CN Q complex, N-n-butyl(iso)quinolinium-ethyl-T CN Q complex, N-n-butyl(iso)quinolinium-n-propyl -TCNQ complex, N-n
-Butyl(iso)quinolinium-iso-propyl-TC
NQ complex, N-isobutyl(iso)quinolinium-methyl-TCNQ complex, N-iso-butyl(iso)quinolinium ethyl-TCNQ complex, N-iso-butyl(iso)
Quinolinium-n-propyl-TCNQ complex, N-iso-
Butyl(iso)quinolinium-iso-propyl-TCN
Q complex, N-n-amino (iso)quinolinium-methyl-TCNQ complex, N-n-amino (iso)quinolinium-ethyl-TCNQ complex, N-n-amino (iso)
Quinolinium-n-propyl-T CN Q complex, N-n
-amino (iso)quinolinium-iso-propyl-T
CNQ complex, N-iso-amyl(iso)quinolinium-
Methyl-TCNQ complex, N-iso-amyl(iso)quinolinium-ethyl-TCNQ complex, N-isoamyl(iso)quinolinyl, n-propyl TCNQ complex, N-iso-amyl(iso)quinolinium-iso~propyl-T
CNQ complex, N-n octyl (iso) quinolinium-methyl-TCNQ complex, N-n-octyl (iso) quinolinium-ethyl-TCNQ complex, N-n-octyl (iso) quinolinium-n-propyl-TCNQIH body, N
-Octyl(iso)quinolinium-isopropyl-TC
NQ complex, etc., and if necessary, an alkyl mole in which the alkyl (iso) quinolinium of the alkyl (iso) quinolinium-based R-TCNQ complex is replaced with each donor of alkyl moporinium and alkyl-α-picolinium. A phorinium-based R-TCNQ complex and an alkyl-α-picolinium-based R-TCNQ complex are also used. There are two types of R-TCNQ complexes, the molar ratio of the electron donor (D") and the electron acceptor R-TCNQ': 1:1 and 1:2. The R-TCNQ complex used as a receptor is preferably a 1:2 complex because it has higher conductivity. In this case, (iso)quinoline in the above examples means quinoline and isoquinoline. RTCN
1 mole of Q anion radical and electrically neutral R-TCN
It consists of 1 mole of Q. In the present invention, in order to further stabilize the conductivity, the R-TCNQo of the neutral molecule is set to 0.
It is preferable to add 1 to 10% in excess.

The effect of the complex used in the present invention can be obtained by mixing two or more types of complexes with different crystal forms, including the above-mentioned complexes. Examples include (1) a mixed complex comprising at least one alkyl(iso)quirinium-based R-TCNQ complex in the exemplary complex and at least one alkylmorpholinium-based R-TCNQ complex; (2) the above-mentioned complex; At least one alkyl(iso)quirinium-based R-TCNQ complex in the exemplary complex and an alkyl-
(3) a mixed complex comprising at least one α-picolinium-based R-TCNQ complex; (3) at least one of the alkylmorporinium-based R-TCNQ complexes in the exemplary complex;
and (4) each combination of the two types of rl-TCNQ complexes shown in Examples (1) to (3) above. , a mixed complex in which one of the complexes is a TCNQ complex in which one is unsubstituted with an alkyl group. The TCNQ complex used here may be the R-TCNQ complex exemplified above in which the alkyl group is unsubstituted. Further, even among the above-mentioned R-TCNQ complexes of the same series, there are ones with different crystal forms, so these may be combined.

Furthermore, specific combinations include (i) N-n-butyl(iso)quinolinium-methyl-
On TCNQCN, mixed complex with N-n-butyl-N-methylmorpholinium-methyl-TCNO, complex, (ii) N-n-butyl(iso)quinolinium-methyl-TCNQtV body, and N-n- Phyl-α-picolinium-methyl-mixture on TCNQCN<Hg form, (iii) Nn-butyl-N-methylmorpholinium-
Mixed complex of N-n-butyl α-vinylinium-medy-TCNQ complex on methyl-TCNQCN, (iv) Mixed complex of N-n-butyl (iso)quinolinium ~ methyl-TCNQ complex and N-n-octyl (iso) ) mixed complex on quinolinium-methyl-TCNQCN, (v) mixed complex on N-n-butyl(iso)quinolinium TCNQ complex and N-n-butyl-N-methylmorpholinium-methyl-TCNQCN, (vi ) A mixed complex of N-n-butyl(iso)quinolinium-methoxybar'rCNQ complex and N-n-butyl-Nmethylmorpholinium TCNQ complex, etc., and crystal forms other than these examples include Three or more different types of R-TCNQ and TCNQCN may be combined. Also, the RT CN Q 1! In cases where the required conductivity cannot be satisfied because the conductivity of the body tends to be lower than that of unsubstituted TCNQCN, the above (i) ~(v
For each combination of l), on unsubstituted TCNQCN, for example, N-n-butyl (iso) which has high conductivity and is relatively inexpensive.
The desired conductivity may be obtained by adding a quinolinium TCNQ complex. Furthermore, the above example (■)
.

One of the above combinations of R-TCNQCN used as in (vi) is an unsubstituted alkyl group TCNQC with a different crystal form.
Even if I go up to N, it still stinks. Next, the effect of the blending ratio when R-TCNQ and TCNQCN, which have different crystal forms, are combined will be explained.

The blending ratio of R-TCNQ and TCNQ complex mixture to the polymer matrix is, for example, 10
N-butyl(iso)quinolinium-methyl-TCNQ 89 body and N-butyl-N-methylmorporinium- Methyl-TCNQCN and N
-n-butyl(iso)quinolinium-methyl-TCNQ
Nn-butyl-N-methylmorporinium on CN T C
When a polymer film with a coating thickness of 0.1 μm was formed by coating a substrate with each combination of NQ complex and its blending ratio changed, two types of R
- TCNQCN on TCNQCN and R-TCNQCN on TCNQCN
The relationship between the above compounding ratio and the surface resistance of the obtained substrate is the first
As shown in Figure a and Figure 1b. The blending ratios of R-TCNQCN and R-TCN Q complex and TCNQCN having different crystal forms may be selected so that the lowest surface resistance can be obtained by mixing. According to the experimental results of the present inventors, two types of R-TCNQ with different crystal forms
And R-TCNQCN upper compounding ratio is 1, +
It is in the range of 9 to 9:1, preferably in the range of 2:8 to 8:2.

In the present invention, the complex is used by blending it into a polymer matrix, but these polymer matrices need to have high adhesion to the substrate used and high transparency. Furthermore, since it is preferable that the adhesive layer and the transparent polymer film be formed by coating, the polymer 7 socks must be soluble in a general-purpose solvent. Examples of such polymer matrices include acrylic resins such as polymethyl methacrylate (PMMA), epoxy resins (BP), phenolic resins (PF), saturated copolymerized polyesters, alkyd resins, nylon 11, and ]2.
Polyvinyl butyral (PVB), polyurethane (PU
), polycarbonate-1-(PC), silicone resin (S
R), polyvinyl chloride (PVC), polystyrene (P
S), polyvinyl acetate, polyvinyl alcohol (PVA
), 1.2-polybutadiene (12-PB), styrene-butadiene-styrene copolymerization (S-13-3), styrene-isoprene-styrene copolymerization (S-I-3),
Styrene-ethylene-butylene-styrene copolymer resin (
S-EB-3), ethylene-ethyl acrylate copolymer resin (EEA).

Examples include ethyl-non-vinyl acetate copolymer resin (EV A), ionomer resin, etc., but when heat-sealing Tosobudave to carrier Dave, the adhesive layer instantly melts or softens and adheres to the rear tape in the middle. On the other hand, if the transparent conductive polymer film layer on the opposite side of the adhesive layer is melted by the pressure bonding of the heat sealer, it will cause a sticking phenomenon in which the top tape film adheres to the thermocompression head of the heat sealer. Since heat resistance is required to prevent the adhesive layer from rising and hindering work, it is necessary to consider the polymer matrix used for the adhesive layer and the polymer matrix used for the transparent conductive polymer film layer separately. .

That is, the resins used for the adhesive layer include saturated copolymerized polyester, PVB, PVC, EVA, EEA, polyhinyl acetate, Lm-PB ionomer resin, 5
-B-3,5-I-3S, -EB-3, nylon ■1
A single substance or a mixture of two or more of 12 and 12 are suitable.Resins used for the transparent conductive polymer film layer include thermosetting polyurethane, saturated copolymer polyester with a high glass transition point, epoxy resin, and phenol resin. , PMM
A. It is preferable to use a single substance or a mixture of two or more of PC, silicone resin, etc., and a curing agent such as isocyanate, acid anhydride, amine compound, etc. is appropriately blended into these resins for the purpose of improving their heat resistance. In addition, when an isocyanate-l-based curing agent is used, in order to accelerate the curing, heat aging at 60°C for 72 hours is performed to prevent the resulting top tape films from blocking each other. It is also contemplated to add an antiblocking agent such as a block copolymer containing perfluoroalkyl groups.

The solvent for dissolving the polymer matrix and the mixed complex to obtain a solution includes dimethylpolamide, dimethylacetamide, brobylenecarbofluorine, γ-butyrolactone, dimethylsulfoxide, sulborane, and formamide. , N-methyl-2-pyrrolidone, aceF
・In addition to nitrile, propionitrile, cyclohexanone, and methyl ethyl ketona, general-purpose solvents include aromatic hydrocarbon solvents such as benzene, toluene, and xylene, halogenated hydrocarbon solvents such as methylene chloride, chloroform, and dichloroethane, methanol, and ethanol. Alcohol-based solvents such as tetrahydrofuran, 1,4 diol V
Ether solvents such as San, ethyl acetate, butyl acetate,
Single or mixed solvents such as ester solvents such as amyl acetate may be selected taking into consideration volatility during coating film formation, and from the viewpoint of stability of the complex, dehydration and
It is preferable to use distilled and purified products.

The polymer matrix is dissolved in the solvent, and based on 100 parts by weight of the polymer matrix, two or more R-TCNQ complexes or RTCNQ complexes and TCN that are responsible for the crystal form are added.
Complex mixture of Q complex (hereinafter referred to as TCNQ mixed complex)
2 to 200 parts by weight, preferably 5 to 100 parts by weight, are dispersed and dissolved.

At this time, blade-type stirring and kneading devices such as a spiral mixer, a planetary mixer, a disperser, and a hybrid mixer are preferably used.

Note that after this, it is desirable to thoroughly disperse and dissolve the mixture using a ball-type kneading device such as a ball mill, vibration mill, or sand mill.

If these kneading devices are made of steel or prepared alloys, there is a risk that the complex will form gyrate and deteriorate, resulting in a significantly high surface resistance. It is preferable to use This mixed solution of polymer matrix, solvent, and the TCNQ mixed complex (hereinafter referred to as TQ coating liquid) can be coated on a base film using a gravure coater or the like, but the coating head of this coating machine also For the same reason as above, it is better to use chrome plating. In order to coat the TQ coating liquid to the thickness described below, it is desirable to set the viscosity to 100 cP or less, preferably 1 to 1.00 cP, and the solid content to a range of 1 to 20% by weight.

Said TQ Coating] - As a base film for coating the liquid, a highly transparent general-purpose plastic film such as polyethylene film 11. Polyvinyl chloride film, polypropylene film, polystyrene film, polystyrene film, polyethylene terephthalate film, polycarbonate film, polyaryl L No. 1 film, polyvinylidene fluoride film, polyamide film, etc. are used. In order to form a transparent conductive adhesive layer or a transparent conductive polymer film on at least one surface of these plastic films, the surface is subjected to corona discharge treatment in order to improve the adhesion of the adhesive and polymer film. Alternatively, it is preferable to perform plasma treatment.

In addition, the transparent conductive adhesive layer and the transparent conductive polymer film formed by the TQ coating liquid should be as thin as possible, since the transparency of the resulting L-knob tape film will decrease if the thickness is too large. Preferably, in the case of the transparent conductive polymer film, the thickness is in the range from Zabumicron to 10 μm, preferably in the range of 0.1 to 2 pm, but in the case of the transparent conductive adhesive layer, this thickness is the adhesive strength. However, if a film thickness of 3 μm or more is required due to the adhesive strength, the R-TCNQ complex and TCNQ complex to be used should be relatively thick. Since it is expensive and the transparency of the resulting top tape film is low, an adhesive layer that does not contain the complex is provided as the first layer, and an adhesive layer containing the complex is provided as the second layer (thickness of submicron). 2 μm).

Hereinafter, in comparison with examples and comparative examples of the present invention,
I will explain in detail.

[Example-1] A polyester film with a thickness of 25 μm was used as a transparent base material.
Lumirror T Type" (trade name, manufactured by Toshiku Co., Ltd.) was used as the hair film. As an adhesive, a saturated copolymer polyester [Erythyl tJ E-3221J (Unitika fil
Product name)
100 parts by weight of 221J was dissolved in 233.3 parts by weight of a mixed solvent of toluene/methyl ethyl ketone (50150) using a high-speed disperser to form a coating with a viscosity of 1.50 cP. Yon (I completed 8 laps of WA. Next, ``Ellie''
Chill U E-3221-1100 parts by weight was mixed with 500 parts by weight of a mixed solvent of cyclohexanone/1-luene (70/30).
5.3 parts by weight of N-butylisoquinolinium methyl-TCNQ complex (manufactured by Nitto Kagaku Kogyo ■, prototype) and N-n were dissolved using a high-speed disperser.
-Butyl-N-methylmorpholinium-methyl-TCN
2.7 parts by weight of Q complex (manufactured by Nitto Kagaku Kogyo 0L, prototype) was added, stirred and dissolved using a disperser, sand milled, and further filtered using filter paper (Whatman Filter Paper 3). Is it a coating with a viscosity of 20cP? Finished 8 laps of Yongya B. The two of you? Yoonya AB
A gravure plate with a line count of 180 meshes and a depth of 35 μm was installed in a two-color gravure coater, and one side of the polyester film was coated and dried in the order of A and -B with each coating solution. The thickness of the dried coating film obtained was 3 μm for the coating solution and 0.1 μm for the coating film B. DCloo on the resulting Tonobu tape film.
When V was applied and the surface resistance was measured, the average value per unit area was 2.2×]06Ω, and the maximum value was 2.8×1.
O'Ω, minimum value 1.7 x 10''Ω, very stable, its light transmittance is 86%, haze is less than 10, polychlorinated by the 1-width heat seal head. When it was pressure-bonded to a vinyl carrier tape for 1 second at an adhesive temperature of 140° C., its peel adhesion strength was 38 g f /i++, which caused no problems in use.

[Example-2] A polyester film with a thickness of 25 μm was used as a transparent base material.
"Lumirror T Type" (Toshi ■ type surface product name) was used as a hair film. Polymer 7 Trisox is a saturated copolymerized polyester with a glass transition point of 90°C and a ring and ball softening point of 185°C.
(Unitika (product name manufactured by 11) > 10 overlapping parts, mixed solvent of cyclohexanone/toluene (70/30) 500
(by weight using a high-speed disperser), and in this, N-n-butyl isoquinolini・'nomumey-ru-T CN Q complex (manufactured by Nitto Kagaku Kogyo 0 Rumor, prototype) 5
．． 3 parts by weight and l'J −+i mebutyl N-methylmorpholinium methyl-TCNQ complex (11 Higashi Kagaku Kogyo f
After stirring and dissolving using a disperser, 2.7 parts by weight of 2.7 parts by weight (manufactured by JL Co., Ltd., prototype) were added, and after stirring and dissolving using a disperser, sand milling was performed, and further filtration was performed using a filter paper (WYL/Mann Filter Paper YO 3).

To 100 parts by weight of the obtained liquid was added 0.25 parts by weight of I-IJ l/n-diisocyanin-I-trimethylproban adduct I prepolymer "21[]ne1id" (trade name of Nippon Polyurethane Industries Co., Ltd.). After adding 0.1 part by weight of the anti-blocking agent "Modipar F-1" (trade name manufactured by Nippon Oil & Fats Co., Ltd. (11)), it was stirred again with a disperser to obtain a viscosity of 20 cP.
A coating solution C was prepared. The crystal structure of the R-TCNQ complex deposited in the transparent conductive film in solution C is as shown in the second diagram.

First, a gravure plate with a coating Tt&A used in Example 1 having a line count of 180 meshes and a depth of 35 μm was installed in a gravure coater, and one side of the polyester film was coated and dried, and then the other side of the adhesive layer was coated and dried. Coating liquid C was applied to the surface and coating and drying were carried out in the same manner as liquid A. The thickness of the obtained dry coating film was
? Night A was 3 μrn, and coating liquid C was 0.1 μrn. When DClooV was applied to the transparent conductive film of the l-tube tape film obtained here and the surface resistance was measured, the average value per unit area was 2.5X]O'"Ω, and the maximum value was 3.0X10'"Ω , the minimum value is 2゜0XIO'Ω, which is very stable, and its light transmittance is 87%, and the haze is less than 10. Chizuki 4
When pressure bonded for 1 second at 0°C, the peel adhesion strength was 37 gf/mi, which caused no problems in use.

[Example-3] Two types of R-TCN used in coating liquid C were added to 10 parts by weight of the saturated copolymerized polyester used in Example-2.
Among the Q complexes, the N-n-butylisoquinolinium J, -methyl-T CN Q tf) is substituted with an alkyl group
-n-butylisoquinolinium TCNQ complex was used, and otherwise the treatment was carried out in the same manner as in Example-1. When the top tape film obtained here was measured in the same manner as in Example-1, its surface resistance was 7.7X on average per unit area.
10'Ω Most Inuhani 8.71X10' Ω, minimum value 7.5X
It was 1.05Ω.

[Comparative Example-1] N-n-butylisoquinolinium methyl-TC was added to 10 parts by weight of the saturated copolymerized polyester used in Example-2.
8.0 parts by weight of NQ complex (manufactured by Nitto Kagaku Kogyo ■, prototype) alone was added, and the solvent used was a mixed solvent of cyclohexanone/toluene (70/30), other conditions were the same as in Example 2. And so. When the top tape film obtained here was measured in the same manner as in Example-1, its surface resistance was an average value of 1.4 x 1.0' per unit area.
Ω, maximum value 2.5X107Ω, minimum value 0.9X107Ω
Met.

[Comparative Example-2] Two types of R-TCN used in coating liquid C were added to 10 parts by weight of the saturated copolymerized polyester used in Example-2.
In place of the Q complex, 5.3 parts by weight of an unsubstituted N-n-butylisoquinolinium TCNQ complex (Nitto Kagaku Kogyo Co., Ltd., prototype) and an Nn-butyl-N-methylmorporinium TCNQ complex ( Nitto Chemical Industry (stock system, prototype) 2
．． 7 parts by weight, a mixed solvent of cyclohexanone/methyl ethyl ketone (80/20) was used, and the other conditions were the same as in Example 2. A transparent conductive film with a dry film thickness of 0.1 μm was prepared. formed. When the top tape film obtained here was measured in the same manner as in Example-1, its surface resistance per unit area was an average value of 4.8 x 105 Ω, a maximum value of 5.0 x 10 5 Ω, and a minimum value of 4.
．． 7X], O19.

The top tape films obtained in Example 2 and Comparative Example 1 were held in a high temperature, high humidity atmosphere of 95% at 65° C., and changes in surface resistance were measured.

As shown in Figure 4, the results showed that the top tape film obtained in Example 2 had a small increase in surface resistance;
While the surface resistance of 109 Ω per unit area, which is necessary for practical static prevention, was maintained even after 120 hours.
In the top tape film obtained in Comparative Example-1, 48
Once the time has passed, the resistance value per unit area will be 1.
The conductivity increased to more than 0" and the conductivity decreased significantly.

Next, "Two-layer Example-2 and Example-3 and Comparative Example 2
Each coating solution obtained in step 1 was put into an atmosphere at 25°C and 155% RH, and each coating solution was applied at predetermined intervals in the same manner as above to form a 0.1 μm transparent conductive film. FIG. 3 shows the results of measuring the change in surface resistance. As a result, in Example-3, the resistance increase was small and 1
Even after 5 days, the surface resistance of 107 Ω per unit area, which is sufficient for practical antistatic prevention, was maintained, and in addition, the surface resistance of Example-
Comparative Example 2 maintained a surface resistance of 107 Ω per unit area even after 30 days, while Comparative Example 2 maintained a surface resistance of 107 Ω or more per unit area after 10 days, and 109 Ω or more per unit area after 15 days. It was surface resistance.

〔Effect of the invention〕

By using at least two or more types of complexes having different crystal forms, the present invention provides lower surface resistance, less variation, and higher temperature resistance than when a conventional TCNQ complex is used alone. In addition to being excellent in stability at high temperatures and high temperatures, by using at least one of the complexes with different crystal forms as an alkyl group-substituted TCNQ complex, its storage stability in solution is greatly improved, and it can be used as a general-purpose solvent. Because it can be used, it can be manufactured at a lower cost, making it possible to produce a practically excellent l-tube tape film.

[Brief explanation of drawings]

Figure 1 is an enlarged vertical cross-sectional view of the top tape film of the present invention when it is used, and Figure 1a is a composite of two types of complexes with different crystal forms, with the number of mixed phases of R-TCNQ complexes added to the polymer matrix constant. The relationship between the mixing ratio and surface resistance is shown. 11) For example, the relationship between the mixing ratio of two types of complexes with different crystal forms and the surface resistance is shown, assuming that the number of mixed complexes of R-TCNQ and TCNQ complexes mixed with respect to the polymer MaI litox is constant. Figure 2 shows RTCNQ deposited in the transparent conductive film obtained in Example-2 of the present invention.
It is a polarized micrograph (magnification: 200 times) showing the crystal structure of the complex. FIG. 3 shows changes in surface resistance of each coating solution of Example-2, Example-3, and Comparative Example-2 at 25°C and 55%RH. FIG. 4 shows the change over time in the surface resistance of the top tape films obtained in Example 2 and Comparative Example 1 at high temperatures. Figure 5 is a polarized micrograph (magnification = 200x) showing the crystal structure of the TCNQ complex deposited in the transparent conductive film when the Nn-butylisoquinolinium, ATCNQ complex is used alone. be. DESCRIPTION OF SYMBOLS 1...Top tape film, 2...Base film, 3...Heat seal adhesive layer, 4...Transparent conductive film layer, 5...Carrier tape, 5...Periphery of carrier tape, 6...Cavity.

Claims (2)

[Claims] (1) A top tape film for a carrier tape in which a heat-sealable adhesive layer containing 7,7,8,8-tetracyanoxydimethane complex crystals is formed on one side of the base film, the complex crystals being A top tape film comprising at least two crystalline complexes, at least one of which is an alkyl group-substituted 7,7,8,8-tetracyanoxydimethane complex. (2) A top tape film for a carrier tape in which a transparent conductive polymer film containing a 7,7,8,8-tetracyanoxydimethane complex is formed on one side of the base film, the complex crystals comprising: consisting of at least two crystalline complexes, at least one of which is alkyl-substituted 7
, 7,8,8-tetracyanoxydimethane complex,
A top tape film comprising a heat-sealable adhesive layer on the other side of the base film.