JP2005081766A - Conductive packaging material, its manufacturing method, and vessel for electronic part - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive packaging material showing excellence in anti-static property, transparency and adhesion between a base material and a conductive layer, and to provide a manufacturing method giving the conductive packaging material in an easy way, and a vessel for an electronic part formed of the conductive packaging material. <P>SOLUTION: The conductive packaging material has a base material and a conductive layer, the conductive layer being formed by applying a carbon nanotube-containing composition containing a conductive polymer (a), a solvent (b) and a carbon nanotube (c) to the base material. The manufacturing method of the conductive packaging material includes a process of applying the carbon nanotube-containing composition to the base material and drying it to form the conductive layer. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a conductive packaging material, a method for producing the same, and a container for electronic parts comprising the conductive packaging material.

  2. Description of the Related Art Conventionally, vacuum molded trays, embossed carrier tapes, and the like molded from resins such as polyester have been known as packaging containers for electronic components using ICs and LSIs. Resin-molded products such as resin sheets that serve as the base plate for vacuum forming trays and embossed carrier tapes generally have high specific surface resistance, so problems such as functional breakdown of electronic components due to charging and deterioration of electronic components due to dust adhesion Wake up.

  For this reason, as an improvement measure, a method in which an antistatic agent such as a surfactant is applied to the surface of the packaging container (JP-A-62-260313, Patent Document 1) has been proposed. However, this packaging container exhibits an antistatic effect immediately after application of the antistatic agent, but the antistatic agent flows out by water, or the antistatic agent is removed by surface friction, so that long-term use is difficult. In addition, these antistatic agents change in conductivity depending on humidity, and cannot exhibit sufficient antistatic performance particularly under low humidity conditions.

  Further, a packaging container coated with a conductive paint (Japanese Patent Laid-Open No. 5-42969 (Patent Document 2), Japanese Patent Laid-Open No. 7-216199 (Patent Document 3), Japanese Patent Laid-Open No. 7-214739 (Patent Document 4), etc.) Has also been proposed. However, in this packaging container, the target substrate is limited in terms of the adhesion between the conductive paint and the substrate, and the coating tends to be non-uniform, so that it is vulnerable to surface friction and the conductive layer is peeled off. There is a risk of destroying electronic components.

  A packaging container in which a conductive agent such as carbon black is kneaded into a molding resin (Japanese Patent Laid-Open No. 8-183868, Patent Document 5) has also been proposed. However, in order to have sufficient conductive performance, carbon black of 10% by mass or more is necessary, there is no transparency, physical properties such as strength are lowered, and moldability is further deteriorated. On the other hand, when the amount added is small, there is a problem that the conductivity becomes insufficient and the antistatic performance cannot be exhibited.

  In order to solve these various problems, the present inventors have developed a conductive material comprising a composition containing an acidic group-substituted soluble aniline-based conductive polymer having a sulfonic acid group and / or a carboxyl group and a binder polymer. The carrier tape for electronic component conveyance bodies which forms a layer in a base material was proposed (Unexamined-Japanese-Patent No. 10-166831, patent document 6). Since this composition is water-soluble, it can form a coating film by a simple method and is excellent in conductivity and transparency. However, since the conductive polymer used in the invention is water-soluble, there is a problem that water resistance is insufficient.

  In order to solve the problem regarding water resistance, the present inventors may react with a water-soluble conductive polymer having a sulfonic acid group and / or a carboxylic acid group and the sulfonic acid group and / or the carboxylic acid group of the polymer. The composition (International Publication No. 97/07167, patent document 7) containing the compound (crosslinkable compound) which has at least 2 or more functional groups which can be proposed was proposed. However, when coating on a film or a resin base material, the cross-linking temperature of the composition is preferably from room temperature to 100 ° C. or less in consideration of the influence on the base material. Since the temperature of 110 degreeC-200 degreeC is required for temperature, the kind of base material which can be apply | coated is restrict | limited and there exists a problem that an application range will be limited.

  Furthermore, the present inventors use a water-resistant conductive composition comprising a water-soluble conductive polymer having a sulfonic acid group and / or a carboxylic acid group, a solvent and a silane coupling agent in order to solve the problem regarding water resistance. Water-resistant packaging materials and electronic component containers (Japanese Patent Application Laid-Open No. 2003-25508, Patent Document 8) molded therewith have been proposed. In addition, a highly antistatic laminate comprising a thermoplastic polymer, a conductive polymer, a surfactant and a crosslinking agent, and a molded article using the same have been proposed (Japanese Patent Laid-Open No. 2000-79662 and Patent Documents). 9). These inventions provide a packaging material having water resistance that can be produced at a low temperature, but further improvement in conductivity is required, and there is also a problem that colorless transparency due to coloring is impaired.

  Incidentally, carbon nanotubes are known as materials having excellent conductivity. Since carbon nanotubes were first discovered by Iijima et al. In 1991 (S. Iijima, Nature, 354, 56 (1991)) (Non-Patent Document 1), their physical properties were evaluated and their functions were elucidated. Research and development related to this is also actively conducted. However, since carbon nanotubes are manufactured in an entangled state, there is a problem that handling becomes very complicated. When mixed in a resin or solution, the carbon nanotubes further agglomerate, and there is a problem that the original characteristics of the carbon nanotubes cannot be exhibited.

For this reason, attempts have been made to uniformly disperse or dissolve carbon nanotubes in a solvent or resin by physically treating or chemically modifying carbon nanotubes.
For example, a method has been proposed in which single-walled carbon nanotubes are sonicated in a strong acid to cut and disperse the single-walled carbon nanotubes (RE Smalley et al., Science, 280, 1253 (1998)). (Non-patent document 2). However, since the treatment is carried out in a strong acid, the operation becomes complicated, and it is not an industrially suitable method, and the dispersion effect is not sufficient.

  Therefore, the single-walled carbon nanotubes cut as proposed above are open at both ends and terminated with an oxygen-containing functional group such as a carboxylic acid group, and the carboxylic acid group is converted into an acid chloride. Then, it is proposed to react with an amine compound to introduce a long-chain alkyl group and solubilize in a solvent (J. Chen et al., Science, 282, 95 (1998)) (Non-patent Document 3). However, in this method, long-chain alkyl groups are introduced into single-walled carbon nanotubes by covalent bonds, which leaves problems such as damage to the graphene sheet structure of carbon nanotubes and the characteristics of carbon nanotubes themselves. Yes.

Another attempt is to introduce a substituent containing ammonium ions into the pyrene molecule by utilizing the fact that the pyrene molecule is adsorbed on the surface of the carbon nanotube by a strong interaction. A method for producing water-soluble single-walled carbon nanotubes by sonication and non-covalently adsorbing to single-walled carbon nanotubes has been reported (Nakajima et al., Chem. Lett., 638 (2002)). Patent Document 4). According to this method, damage to the graphene sheet or the like is suppressed due to non-covalent chemical modification, but there is a problem that the conductive performance of the carbon nanotube is lowered because of the non-conductive pyrene compound.
JP-A-62-260313 JP-A-5-42969 JP 7-216199 A Japanese Patent Laid-Open No. 7-214739 JP-A-8-183868 Japanese Patent Laid-Open No. 10-168312 International Publication No. 97/07167 Pamphlet JP 2003-25508 A JP 2000-79662 A S. Iijima, Nature, 354, 56 (1991) R. E. Smalley et al., Science, 280, 1253 (1998) J. et al. Chen et al., Science, 282, 95 (1998). Nakajima et al., Chem. Lett. 638 (2002)

  Therefore, an object of the present invention is to provide a conductive packaging material excellent in antistatic properties, transparency, and adhesion between the substrate and the conductive layer, and a production method capable of obtaining such a conductive packaging material by a simple method. Another object is to provide a container for electronic parts comprising the conductive packaging material.

  In addition, another object of the present invention is to provide a conductive packaging material having excellent water resistance, a production method capable of obtaining such a conductive packaging material by a simple method, and an electronic component comprising the conductive packaging material. To provide a container.

  As a result of diligent research to solve these problems, the present inventor has obtained a conductive packaging material having a conductive layer formed by applying a composition containing a conductive polymer, a solvent, and carbon nanotubes, and this As a result, the present inventors have found that an electronic component container obtained by processing is suitable for this purpose.

That is, the conductive packaging material of the present invention has a base material and a conductive layer, and the conductive layer is a layer containing a conductive polymer (a) and a carbon nanotube (c). To do.
Here, the conductive layer comprises a conductive polymer (a), a solvent (b), and a carbon nanotube (c), and if necessary, a polymer compound (d), a basic compound (e), a surfactant ( It is desirable that the layer be formed by applying a carbon nanotube-containing composition containing f), a silane coupling agent (g), and colloidal silica (h) to a substrate.
The conductive polymer (a) is preferably a water-soluble conductive polymer, and more preferably a water-soluble conductive polymer having a sulfonic acid group and / or a carboxyl group.

The electronic component container of the present invention is obtained by processing the conductive packaging material of the present invention.
Moreover, the method for producing a conductive packaging material of the present invention comprises applying a carbon nanotube-containing composition containing a conductive polymer (a), a solvent (b), and a carbon nanotube (c) on a substrate, and drying the composition. Then, a conductive layer is formed.

The conductive packaging material of the present invention is excellent in antistatic properties, does not deteriorate in conductivity even at low humidity, and is excellent in transparency and adhesion between the substrate and the conductive layer.
Moreover, the container for electronic parts of the present invention is excellent in antistatic properties, does not deteriorate in conductivity even under low humidity, and is excellent in transparency and adhesion between the substrate and the conductive layer.
Moreover, according to the manufacturing method of the electroconductive packaging material of this invention, such an electroconductive packaging material can be obtained by a simple method.

Hereinafter, the present invention will be described in detail.
<Conductive packaging material>
The conductive packaging material of the present invention has a base material and a conductive layer in contact therewith.

<Conductive layer>
The conductive layer in the present invention is a layer containing a conductive polymer (a) and a carbon nanotube (c).
Here, the conductive layer in the present invention was formed by coating a carbon nanotube-containing composition containing a conductive polymer (a), a solvent (b), and a carbon nanotube (c) on a substrate. A layer is preferable in terms of conductivity.

(Conductive polymer (a))
The conductive polymer (a) is a π-conjugated polymer containing phenylene vinylene, vinylene, thienylene, pyrrolylene, phenylene, iminophenylene, isothianaphthene, furylene, carbazolylene or the like as a repeating unit.
Among these, a so-called water-soluble conductive polymer is preferably used in the present invention in terms of solubility in the solvent (b). Here, the water-soluble conductive polymer has an acidic group, an alkyl group substituted with an acidic group, or an alkyl group containing an ether bond on the skeleton of a π-conjugated polymer or a nitrogen atom in the polymer. A conductive polymer. The water-soluble conductive polymer exhibits good conductivity even at a very low concentration, and thus sufficiently exhibits conductive performance without deteriorating the properties of the polymer compound (d) (binder polymer) which is another component. be able to.

In the present invention, among water-soluble conductive polymers, water-soluble conductive polymers having a sulfonic acid and / or a carboxyl group are preferable in terms of solubility in the solvent (b), conductivity, and film-forming properties. Used for.
Examples of the water-soluble conductive polymer having a sulfonic acid and / or a carboxyl group include, for example, JP-A-61-197633, JP-A-63-39916, JP-A-01-301714, JP-A-05-504153. JP, 05-503953, JP 04-32848, JP 04-328181, JP 06-145386, JP 06-56987, JP 05-226238. JP, 05-178890, JP 06-293828, JP 07-118524, JP 06-32845, JP 06-87949, JP 06-256516, Japanese Laid-Open Patent Publication Nos. 07-41756, 07-48436, 04-26833 JP, Hei 09-59376, JP 2000-172384, JP-A No. 06-49183, JP-was disclosed in JP-A-10-60108 water-soluble electroconductive polymer is preferably used.

  Specific examples of the water-soluble conductive polymer having a sulfonic acid and / or carboxyl group include unsubstituted and substituted phenylene vinylene, vinylene, thienylene, pyrrolylene, phenylene, iminophenylene, isothianaphthene, furylene and carbazolylene. A sulfonic acid group and / or carboxyl group, or a sulfonic acid group and / or carboxyl on a skeleton of a π-conjugated polymer containing at least one selected from the group consisting of repeating units as a repeating unit or a nitrogen atom in the polymer And a water-soluble conductive polymer having an alkyl group substituted with a group or an alkyl group containing an ether bond. Among these, water-soluble conductive polymers having a skeleton containing thienylene, pyrrolylene, iminophenylene, phenylene vinylene, carbazolylene, and isothianaphthene are particularly preferably used.

  A preferable water-soluble conductive polymer having a sulfonic acid group and / or a carboxyl group has at least one repeating unit selected from the following formulas (2) to (10) in a total number of repeating units of 20 to 20 It is a water-soluble conductive polymer containing 100%.

(In the formula (2), R ¹ and R ² are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —OCH ₃ , —CH _{3. , -C 2 H 5, -F,} -Cl, -Br, -I, -N (R 35) 2, -NHCOR 35, -OH, -O -, -SR 35, -OR 35, -OCOR 35, ^{_{-NO 2, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO, and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Alternatively, it is an alkylene, arylene or aralkylene group, and at least one of R ¹ and R ² is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH and —R. ³⁵ is a group selected from the group consisting of COOH.)

(In the formula (3), R ³ and R ⁴ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —OCH ₃ , —CH _{3. , -C 2 H 5, -F,} -Cl, -Br, -I, -N (R 35) 2, -NHCOR 35, -OH, -O -, -SR 35, -OR 35, -OCOR 35, ^{_{-NO 2, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO, and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Or an alkylene, arylene, or aralkylene group, and at least one of R ³ and R ⁴ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH, and —R. ³⁵ is a group selected from the group consisting of COOH.)

(In the formula (4), R ^{5 to} R ⁸ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —OCH ₃ , —CH _{3. , -C 2 H 5, -F,} -Cl, -Br, -I, -N (R 35) 2, -NHCOR 35, -OH, -O -, -SR 35, -OR 35, -OCOR 35, ^{_{-NO 2, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO, and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Alternatively, it is an alkylene, arylene or aralkylene group, and at least one of R ^{5 to} R ⁸ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH and —R. ³⁵ is a group selected from the group consisting of COOH.)

(In the formula (5), R ^{9 to} R ¹³ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —OCH ₃ , —CH _{3. , -C 2 H 5, -F,} -Cl, -Br, -I, -N (R 35) 2, -NHCOR 35, -OH, -O -, -SR 35, -OR 35, -OCOR 35, ^{_{-NO 2, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO, and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Alternatively, it is an alkylene, arylene or aralkylene group, and at least one of R ^{9 to} R ¹³ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH and —R. ³⁵ is a group selected from the group consisting of COOH.)

(In the formula (6), R ¹⁴ is selected from the group consisting of —SO ₃ ⁻ , —SO ₃ H, —R ⁴² SO ₃ ⁻ , —R ⁴² SO ₃ H, —COOH and —R ⁴² COOH, R ⁴² is an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms.)

(In the formula (7), R ^{52 to} R ⁵⁷ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —OCH ₃ , —CH _{3. , -C 2 H 5, -F,} -Cl, -Br, -I, -N (R 35) 2, -NHCOR 35, -OH, -O -, -SR 35, -OR 35, -OCOR 35, ^{_{-NO 2, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO, and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Alternatively, it is an alkylene, arylene or aralkylene group, and at least one of R ^{52 to} R ⁵⁷ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH and —R. ³⁵ is a group selected from the group consisting of COOH, Ht ^{is, NR 82, S, O,} Se and Te A heteroatom group selected from Li Cheng group, R ⁸² represents hydrogen and straight-chain or branched alkyl group having 1 to 24 carbon atoms, or substituted, the unsubstituted aryl group, carbonization of R ⁵² to R ⁵⁷ The hydrogen chains are bonded to each other at any position to form a divalent chain that forms a cyclic structure of at least one or more 3- to 7-membered saturated or unsaturated hydrocarbons together with carbon atoms substituted by such groups. The cyclic bond chain thus formed may contain a carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, imino bond at any position, and n is a heterocycle and a substituent. This represents the number of condensed rings sandwiched between benzene rings having R ^{53 to} R ⁵⁶ , and is an integer of 0 or 1-3.)

(In the formula (8), R ^{58 to} R ⁶⁶ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —OCH ₃ , —CH _{3. , -C 2 H 5, -F,} -Cl, -Br, -I, -N (R 35) 2, -NHCOR 35, -OH, -O -, -SR 35, -OR 35, -OCOR 35, ^{_{-NO 2, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO, and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Alternatively, it is an alkylene, arylene or aralkylene group, and at least one of R ^{58 to} R ⁶⁶ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH and —R. a group selected from the group consisting of ³⁵ COOH, benzene and n having substituents R ⁵⁸ and R ⁵⁹ It represents the number of condensed rings sandwiched between a benzene ring having a substituent R ⁶¹ to R ⁶⁴ with the ring and is an integer of 0 or 1-3.)

(In the formula (9), R ^{67 to} R ⁷⁶ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —OCH ₃ , —CH _{3. , -C 2 H 5, -F,} -Cl, -Br, -I, -N (R 35) 2, -NHCOR 35, -OH, -O -, -SR 35, -OR 35, -OCOR 35, ^{_{-NO 2, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO, and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Alternatively, it is an alkylene, arylene or aralkylene group, and at least one of R ^{67 to} R ⁷⁶ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH and —R. ³⁵ is a group selected from the group consisting of COOH, benzene and n having a substituent R ⁶⁷ to R ⁶⁹ And represents the number of condensed rings sandwiched benzoquinone ring and is an integer of 0 or 1-3.)

(In the formula (10), R ^{77 to} R ⁸¹ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —OCH ₃ , —CH _{3. , -C 2 H 5, -F,} -Cl, -Br, -I, -N (R 35) 2, -NHCOR 35, -OH, -O -, -SR 35, -OR 35, -OCOR 35, ^{_{-NO 2, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO, and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Alternatively, it is an alkylene, arylene or aralkylene group, and at least one of R ^{77 to} R ⁸¹ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH and —R. ³⁵ is a group selected from the group consisting of COOH, X ^a- is chloride, bromide, yo Elementary ion, fluorine ion, nitrate ion, sulfate ion, hydrogen sulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, methanesulfonate ion, p-toluenesulfone At least one anion selected from the group of 1 to 3 anions consisting of an acid ion, a trifluoroacetate ion, and a trifluoromethanesulfonate ion, a represents the ionic valence of X, (It is an integer, p is the doping rate, and its value is 0.001-1.)

  Moreover, polyethylene dioxythiophene polystyrene sulfate is also used as a water-soluble conductive polymer having a preferred sulfonic acid and / or carboxyl group. This water-soluble conductive polymer has a structure in which polystyrene sulfonic acid is added as a dopant, although no sulfonic acid group is introduced into the skeleton of the conductive polymer. This polymer can be produced by polymerizing 3,4-ethylenedioxythiophene (Baytron M manufactured by Bayer) with an oxidizing agent such as iron toluenesulfonate (Baytron C manufactured by Bayer). This polymer is also available as Baytron P manufactured by Bayer.

  Among the above water-soluble conductive polymers having a sulfonic acid and / or carboxyl group, the water-soluble conductive containing 20 to 100% of the repeating unit represented by the following formula (11) in the total number of repeating units of the whole polymer. A polymer is more preferably used.

(In the formula (11), y represents an arbitrary number of 0 <y <1, and R ^{15 to} R ³² are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , _{^{-R 35 SO 3 H, -OCH 3}} , -CH 3, -C 2 H 5, -F, -Cl, -Br, -I, -N (R 35) 2, -NHCOR 35, -OH, -O ^{-, -SR 35, -OR 35,} -OCOR 35, -NO 2, -COOH, -R 35 COOH, -COOR 35, -COR 35, selected from the group consisting of -CHO, and -CN, wherein, R ³⁵ is an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene or aralkylene group, and at least one of R ^{15 to} R ³² is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ^— , -R ³⁵ SO ₃ H, -COOH and -R ³⁵ COOH.

  Here, the water-soluble conductive polymer having a content of repeating units having a sulfonic acid group and / or a carboxyl group with respect to the total number of repeating units of the polymer of 50% or more has solubility in a solvent such as water or a water-containing organic solvent. Since it is very good, it is preferably used. The content of the repeating unit having a sulfonic acid group and / or a carboxyl group is more preferably 70% or more, still more preferably 90% or more, and particularly preferably 100%.

  In addition, the substituent added to the aromatic ring is preferably an alkyl group, an alkoxy group, a halogen group or the like from the viewpoint of conductivity and solubility, and particularly preferably a water-soluble conductive polymer having an alkoxy group. Among these combinations, the most preferable water-soluble conductive polymer is represented by the following formula (12).

(In the formula (12), R ³³ is one group selected from the group consisting of a sulfonic acid group, a carboxyl group, and alkali metal salts, ammonium salts and substituted ammonium salts thereof, and R ³⁴ is a methyl group. , Ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, dodecyl group, tetracosyl group, methoxy group, ethoxy group, n-propoxy group A group selected from the group consisting of iso-butoxy group, sec-butoxy group, tert-butoxy group, heptoxy group, hexoxy group, octoxy group, dodecoxy group, tetracosoxy group, fluoro group, chloro group and bromo group X represents an arbitrary number of 0 <X <1, and n represents the degree of polymerization and is 3 or more.)
Here, R ³³ is preferably at least partly a free acid type sulfonic acid group and / or a carboxyl group from the viewpoint of improving conductivity.

  As the water-soluble conductive polymer in the present invention, polymers obtained by various synthetic methods such as chemical polymerization or electrolytic polymerization can be used. For example, the synthesis methods described in Japanese Patent Application Laid-Open Nos. 7-196791 and 7-324132 proposed by the present inventors are applied. That is, an aqueous solution obtained by polymerizing an acidic group-substituted aniline represented by the following formula (13), its alkali metal salt, ammonium salt and / or substituted ammonium salt with an oxidizing agent in a solution containing a basic compound. Conductive polymer.

(In the formula (13), R ^{36 to} R ⁴¹ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —OCH ₃ , —CH _{3. , -C 2 H 5, -F,} -Cl, -Br, -I, -N (R 35) 2, -NHCOR 35, -OH, -O -, -SR 35, -OR 35, -OCOR 35, ^{_{-NO 2, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO, and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Alternatively, it is an alkylene, arylene or aralkylene group, and at least one of R ^{36 to} R ⁴¹ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH and —R ^35. A group selected from the group consisting of COOH.)

  A particularly preferable water-soluble conductive polymer was obtained by polymerizing an alkoxy group-substituted aminobenzenesulfonic acid, its alkali metal salt, ammonium salt and / or substituted ammonium salt with an oxidizing agent in a solution containing a basic compound. A water-soluble conductive polymer is used.

  It is desirable that at least a part of the acidic group contained in the water-soluble conductive polymer in the present invention is a free acid type from the viewpoint of improving conductivity. As the water-soluble conductive polymer in the present invention, those having a mass average molecular weight of 2000 to 3 million in terms of GPC polyethylene glycol are excellent in conductivity, film formability and film strength, and are preferably used. More preferred are those having a mass average molecular weight of 3,000 or more and 1,000,000 or less, and most preferred are those having a weight average molecular weight of 5,000 or more and 500,000 or less.

  Although the conductive polymer (a) can be used as it is, a polymer to which an external dopant is added by performing a doping treatment method using an acid by a known method can be used. For example, the doping process can be performed by performing a process such as immersing the conductive polymer (a) in an acidic solution. Specific examples of the acidic solution used for the doping treatment include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; organic acids such as p-toluenesulfonic acid, camphorsulfonic acid, benzoic acid, and derivatives having these skeletons; polystyrene sulfonic acid An aqueous solution containing a polymer acid such as polyvinyl sulfonic acid, poly (2-acrylamido-2-methylpropane) sulfonic acid, polyvinyl sulfuric acid and derivatives having these skeletons, or a mixed solution of water and an organic solvent. These inorganic acids, organic acids, and polymer acids may be used alone or in admixture of two or more at any ratio.

(Solvent (b))
The solvent (b) includes a conductive polymer (a) and a carbon nanotube (c), and a polymer compound (d), a basic compound (e), a surfactant (f), a silane cup, which are used as necessary. There is no particular limitation as long as it dissolves or disperses the ring agent (g) and the colloidal silica (h). Solvent (b) includes water; alcohols such as methanol, ethanol, isopropyl alcohol, propyl alcohol, and butanol; ketones such as acetone, methyl ethyl ketone, ethyl isobutyl ketone, and methyl isobutyl ketone; ethylene glycol, ethylene glycol methyl ether, ethylene Ethylene glycols such as glycol mono-n-propyl ether; propylene glycols such as propylene glycol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether and propylene glycol propyl ether; amides such as dimethylformamide and dimethylacetamide; Pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone; dimethyl sulfoxide; Hydroxyesters such as γ-butyrolactone, methyl lactate, ethyl lactate, methyl β-methoxyisobutyrate, methyl α-hydroxyisobutyrate and the like; anilines such as aniline and N-methylaniline are preferably used.

  When a water-soluble conductive polymer is used as the conductive polymer (a), the solvent (b) is water in terms of solubility of the water-soluble conductive polymer, solubility of the carbon nanotube (c), and dispersibility. Alternatively, a water-containing organic solvent is preferably used.

(Carbon nanotube (c))
The carbon nanotube (c) is not particularly limited, and the carbon nanotube (c) is a single-walled carbon nanotube, a multi-layered carbon nanotube in which several layers are concentrically overlapped, or a coiled carbon nanotube. Can be used.

  The carbon nanotube (c) will be described in more detail. A plurality of cylinders each having a thickness of several atomic layers with a rounded graphite-like carbon atom surface formed into a nested structure. Illustrated. Further, carbon nanohorns having a shape in which one side of the carbon nanotube is closed, a cup-shaped nanocarbon material having a hole in the head thereof, and the like can also be used.

The method for producing the carbon nanotube (c) is not particularly limited. Specifically, catalytic hydrogen reduction of carbon dioxide, arc discharge method, laser evaporation method, CVD method, vapor phase growth method, HiPco method in which carbon monoxide is reacted with an iron catalyst at high temperature and high pressure to grow in the gas phase, etc. Is mentioned.
The carbon nanotube (c) obtained by the above production method is preferably a single-walled carbon nanotube, and moreover, by various purification methods such as a washing method, a centrifugal separation method, a filtration method, an oxidation method, and a chromatographic method, Highly purified carbon nanotubes are preferably used because they sufficiently exhibit various functions.

  Further, as the carbon nanotube (c), those which are pulverized using a ball-type kneading apparatus such as a ball mill, a vibration mill, a sand mill and a roll mill, and those which are cut short by chemical and physical treatment are used. be able to.

(Polymer compound (d))
By including the polymer compound (d) in the carbon nanotube-containing composition of the present invention, the adhesion of the conductive layer to the substrate and the strength of the conductive layer are further improved.
The polymer compound (d) is not particularly limited as long as it can be dissolved or dispersed (emulsion formation) in the solvent (b). Specifically, polyvinyl alcohols such as polyvinyl alcohol, polyvinyl formal, and polyvinyl butyral. Polyacrylamides such as polyacrylamide, poly (Nt-butylacrylamide), polyacrylamide methylpropanesulfonic acid; polyvinylpyrrolidones, polystyrene sulfonic acid and its soda salts, cellulose, alkyd resin, melamine resin; Urea resin, phenol resin, epoxy resin, polybutadiene resin, acrylic resin, urethane resin, vinyl ester resin, urea resin, polyimide resin, maleic acid resin, polycarbonate resin, vinyl acetate resin, chlorinated polyethylene Resins, chlorinated polypropylene resins, styrene resins, acryl / styrene copolymer resin, a vinyl acetate / acrylic copolymer resin, polyester resin, styrene / maleic acid copolymer resin, fluorine resin and copolymers and the like. Further, these polymer compounds (d) may be a mixture of two or more of them in an arbitrary ratio.

  Among these polymer compounds (d), a water-soluble polymer compound or a polymer compound that forms an emulsion in an aqueous system is preferably used in terms of solubility in a solvent, stability of a composition, and conductivity, Preferably, a polymer compound having an anion group is used. Among them, it is preferable to use one or two or more of water-based acrylic resin, water-based polyester resin, water-based urethane resin, and water-based chlorinated polyolefin resin.

(Basic compound (e))
By adding the basic compound (e) to the carbon nanotube-containing composition, the solubility of the conductive polymer (a) is improved and the carbon nanotube (c) is solubilized or dispersed in the solvent (b). Has the effect of promoting In particular, the basic compound (e) has an effect of dedoping a water-soluble conductive polymer and further improving the solubility in the solvent (b). Further, by forming a salt with an acidic group such as a sulfonic acid group or a carboxyl group, the solubility in water is particularly improved, and the solubilization or dispersion of the carbon nanotube (c) in the solvent (b) is promoted. Is done.

The basic compound (e) is not particularly limited, but, for example, ammonia, fatty amines, cyclic saturated amines, cyclic unsaturated amines, ammonium salts, inorganic bases and the like are preferably used. .
The structural formula of amines used as the basic compound (e) is shown in the following formula (14).

(In the formula (14), R ^{45 to} R ⁴⁶ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms (C _{1 to} C ₄ ), CH ₂ OH, CH ₂ CH ₂ OH, CONH ₂ or NH. ₂ )

  The structural formula of ammonium salts used as the basic compound (e) is shown in the following formula (15).

(In the formula (15), R ^{48 to} R ⁵¹ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms (C _{1 to} C ₄ ), CH ₂ OH, CH ₂ CH ₂ OH, CONH ₂ or NH. ₂ and X ⁻ represents OH ⁻ , 1/2 · SO ₄ ²⁻ , NO ₃ ⁻ , 1 / 2CO ₃ ²⁻ , HCO ₃ ⁻ , 1/2 · (COO) ₂ ²⁻ , or R′COO ^−. R ′ represents an alkyl group having 1 to 3 carbon atoms (C _{1 to} C ₃ ).

As cyclic saturated amines, piperidine, pyrrolidine, morpholine, piperazine, derivatives having these skeletons, and ammonium hydroxide compounds thereof are preferably used.
As the cyclic unsaturated amines, pyridine, α-picoline, β-picoline, γ-picoline, quinoline, isoquinoline, pyrroline, derivatives having these skeletons, and ammonium hydroxide compounds thereof are preferably used.
As the inorganic base, hydroxide salts such as sodium hydroxide, potassium hydroxide and lithium hydroxide are preferably used.

Two or more basic compounds (e) may be mixed and used. For example, the conductivity can be further improved by using a mixture of amines and ammonium salts. Specifically, NH ₃ / (NH ₄ ) ₂ CO ₃ , NH ₃ / (NH ₄ ) HCO ₃ , NH ₃ / CH ₃ COONH ₄ , NH ₃ / (NH ₄ ) ₂ SO ₄ , N (CH ₃ ) ₃ / CH ₃ COONH ₄ , N (CH ₃ ) ₃ / (NH ₄ ) ₂ SO _{4 and the} like. These mixing ratios can be used at an arbitrary ratio, but amines / ammonium salts = 1/10 to 10/0 are preferable.

(Surfactant (f))
When the surfactant (f) is added to the carbon nanotube-containing composition in the present invention, the solubilization or dispersion of the carbon nanotube (c) is further promoted, and the flatness, coating property, conductivity and the like are improved.

  Specific examples of the surfactant (f) include alkylsulfonic acid, alkylbenzenesulfonic acid, alkylcarboxylic acid, alkylnaphthalenesulfonic acid, α-olefinsulfonic acid, dialkylsulfosuccinic acid, α-sulfonated fatty acid, N-methyl-N. -Oleyl taurine, petroleum sulfonic acid, alkyl sulfuric acid, sulfated oil, polyoxyethylene alkyl ether sulfuric acid, polyoxyethylene styrenated phenyl ether sulfuric acid, alkyl phosphoric acid, polyoxyethylene alkyl ether phosphoric acid, polyoxyethylene alkyl phenyl ether phosphorus Anionic surfactants such as acids, naphthalenesulfonic acid formaldehyde condensates and their salts; primary to tertiary fatty amines, quaternary ammoniums, tetraalkylammoniums, trialkylbenzylammonium amines Rualkylpyridinium, 2-alkyl-1-alkyl-1-hydroxyethylimidazolinium, N, N-dialkylmorpholinium, polyethylene polyamine fatty acid amide, urea condensate of polyethylene polyamine fatty acid amide, urea condensate of polyethylene polyamine fatty acid amide Cationic surfactants such as quaternary ammonium and salts thereof; N, N-dimethyl-N-alkyl-N-carboxymethylammonium betaine, N, N, N-trialkyl-N-sulfoalkylene ammonium betaine, Betaines such as N, N-dialkyl-N, N-bispolyoxyethylene ammonium sulfate betaine, 2-alkyl-1-carboxymethyl-1-hydroxyethylimidazolinium betaine, N, N-dialkylaminoal Amphoteric surfactants such as aminocarboxylic acids such as lencarboxylate; polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene polystyryl phenyl ether, polyoxyethylene-polyoxypropylene glycol, polyoxyethylene-poly Oxypropylene alkyl ether, polyhydric alcohol fatty acid partial ester, polyoxyethylene polyhydric alcohol fatty acid partial ester, polyoxyethylene fatty acid ester, polyglycerin fatty acid ester, polyoxyethylenated castor oil, fatty acid diethanolamide, polyoxyethylene alkylamine, Non-ionic surfactants such as triethanolamine fatty acid partial esters, trialkylamine oxides; and fluoroalkylcarbo Acid, perfluoroalkyl carboxylic acids, perfluoroalkyl benzene sulfonic acids, fluorine-based surfactants such as perfluoroalkyl polyoxyethylene ethanol is used. Here, the alkyl group preferably has 1 to 24 carbon atoms, and more preferably 3 to 18 carbon atoms. In addition, even if it uses 2 or more types of surfactant, it does not matter at all.

(Silane coupling agent (g))
A silane coupling agent (g) can be further contained in the carbon nanotube-containing composition of the present invention. It is considered that the silane coupling agent (g) reacts with the acidic group of the water-soluble conductive polymer and is hydrolyzed with the silane coupling agent (g) to form a crosslinked structure. The water resistance of the conductive layer obtained from the carbon nanotube-containing composition containing the silane coupling agent (g) is significantly improved. As the silane coupling agent (g), a silane coupling agent (g) represented by the following formula (1) is used.

(In the formula (1), R ⁴² , R ⁴³ and R ⁴⁴ are each independently hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, X is a group selected from the group consisting of an amino group, an acetyl group, a phenyl group, and a halogen group.

1 and m are numbers from 0 to 6, and Y is a group selected from the group consisting of a hydroxyl group, a thiol group, an amino group, an epoxy group, and an epoxycyclohexyl group. )

Specifically, those having an epoxy group include γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropylmethyldimethoxysilane, γ-glycidyloxypropyltriethoxysilane, and the like.
Examples of those having an amino group include γ-aminopropyltriethoxysilane, β-aminoethyltrimethoxysilane, and γ-aminopropoxypropyltrimethoxysilane.
Examples of those having a thiol group include γ-mercaptopropyltrimethoxysilane and β-mercaptoethylmethyldimethoxysilane.
Examples of those having a hydroxyl group include β-hydroxyethoxyethyltriethoxysilane and γ-hydroxypropyltrimethoxysilane.
Examples of those having an epoxycyclohexyl group include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

(Colloidal silica (h))
Colloidal silica (h) can be further used in combination with the carbon nanotube-containing composition in the present invention. The surface hardness and weather resistance of the conductive layer obtained from the carbon nanotube-containing composition combined with colloidal silica (h) are remarkably improved.

  Although colloidal silica (h) in this invention is not specifically limited, What is disperse | distributed to the mixed solvent of water, an organic solvent, or water and an organic solvent is used preferably. Examples of the organic solvent include, but are not limited to, alcohols such as methanol, ethanol, isopropyl alcohol, propyl alcohol, butanol, and pentanol; ketones such as acetone, methyl ethyl ketone, ethyl isobutyl ketone, and methyl isobutyl ketone; ethylene glycol, Ethylene glycols such as ethylene glycol methyl ether and ethylene glycol mono-n-propyl ether; propylene glycols such as propylene glycol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether and propylene glycol propyl ether are preferably used. .

  Further, as the colloidal silica (h), those having a particle diameter of 1 nm to 300 nm are used, preferably those having a particle diameter of 1 nm to 150 nm, more preferably 1 nm to 50 nm. If the particle size is too large, the hardness is insufficient and the solution stability of the colloidal silica itself is also lowered.

(Carbon nanotube-containing composition)
The use ratio of the conductive polymer (a) and the solvent (b) is preferably 0.001 to 50 parts by mass of the conductive polymer (a) with respect to 100 parts by mass of the solvent (b), more preferably. 0.01 to 30 parts by mass. When the conductive polymer (a) is less than 0.001 part by mass, the conductivity is inferior, and the carbon nanotube (c) is solubilized or dispersed efficiently. On the other hand, when it exceeds 50 parts by mass, the conductivity reaches a peak and does not increase greatly, and the viscosity increases, so that the efficiency of solubilization or dispersion of the carbon nanotube (c) is lowered.

  The use ratio of the carbon nanotube (c) and the solvent (b) is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to 20 parts by mass of the carbon nanotube (c) with respect to 100 parts by mass of the solvent (b). 001 to 10 parts by mass. When the carbon nanotube (c) is less than 0.0001 part by mass, the performance due to the carbon nanotube (c) such as conductivity is lowered. On the other hand, when it exceeds 20 parts by mass, the efficiency of solubilization or dispersion of the carbon nanotube (c) is lowered.

  The use ratio of the polymer compound (d) and the solvent (b) is preferably 0.1 to 400 parts by mass of the polymer compound (d), more preferably 100 parts by mass of the solvent (b). 0.5 to 300 parts by mass. When the polymer compound (d) is 0.1 parts by mass or more, the film formability, moldability, and strength are further improved. On the other hand, when the polymer compound (d) is 400 parts by mass or less, the water-soluble conductive polymer (a) and the carbon nanotube ( The decrease in solubility of c) is small, and high conductivity is maintained.

  The use ratio of the basic compound (e) and the solvent (b) is preferably 0.1 to 10 parts by mass of the basic compound (e), more preferably 100 parts by mass of the solvent (b). 0.1 to 5 parts by mass. When the basic compound (e) is in this range, the solubility of the water-soluble conductive polymer is improved, solubilization or dispersion of the carbon nanotube (c) in the solvent (b) is promoted, and the conductivity is improved. To do.

  The use ratio of the surfactant (f) and the solvent (b) is preferably such that the surfactant (f) is 0.0001 to 10 parts by mass, more preferably 100 parts by mass of the solvent (b). 0.01 to 5 parts by mass. When the surfactant (f) exceeds 10 parts by mass, the coatability is improved, but a phenomenon such as inferior conductivity occurs, and the efficiency of solubilization or dispersion of the carbon nanotube (c) decreases.

  The use ratio of the silane coupling agent (g) and the solvent (b) is preferably 0.001 to 20 parts by mass of the silane coupling agent (g) with respect to 100 parts by mass of the solvent (b). Preferably it is 0.01-15 mass parts. When the silane coupling agent (g) is less than 0.001 part by mass, the improvement in water resistance and / or solvent resistance is relatively small. On the other hand, when it exceeds 20 parts by mass, solubility, flatness, transparency, and conductivity are increased. Sexuality may worsen.

  The use ratio of the colloidal silica (h) and the solvent (b) is preferably 0.001 to 100 parts by mass, more preferably 0.001 to 100 parts by mass of the colloidal silica (h) with respect to 100 parts by mass of the solvent (b). 01 to 50 parts by mass. If colloidal silica (h) is 0.001 mass part or more, the improvement width of water resistance, weather resistance, and hardness will become large. On the other hand, when it exceeds 100 parts by mass, the solubility, flatness, transparency, and conductivity may be deteriorated.

  Further, the carbon nanotube-containing composition in the present invention may be added to a plasticizer, a dispersant, a coating surface modifier, a fluidity modifier, an ultraviolet absorber, an antioxidant, a storage stabilizer, an adhesion aid, an increase agent, if necessary. Various known substances such as a sticking agent can be added and used.

  In addition, the carbon nanotube-containing composition in the present invention can contain a conductive substance in order to further improve the conductivity. Examples of the conductive material include carbon-based materials such as carbon fiber, conductive carbon black, and graphite, metal oxides such as tin oxide and zinc oxide, and metals such as silver, nickel, and copper.

  For the preparation of the carbon nanotube-containing composition, a stirring or kneading apparatus such as an ultrasonic wave, a homogenizer, a spiral mixer, a planetary mixer, a disperser, or a hybrid mixer is used. In particular, it is preferable to mix the conductive polymer (a), the solvent (b), the carbon nanotube (c), and other components and irradiate them with ultrasonic waves. In this case, the ultrasonic irradiation and the homogenizer are used in combination ( It is preferable to carry out the treatment using an ultrasonic homogenizer.

The conditions for the ultrasonic irradiation treatment are not particularly limited, but it is sufficient if the ultrasonic wave intensity and the processing time are sufficient to uniformly disperse or dissolve the carbon nanotube (c) in the solvent (b). . For example, the rated output in the ultrasonic oscillator is preferably 0.1 to 2.0 watt / cm ² per unit bottom area of the ultrasonic oscillator, more preferably in the range of 0.3 to 1.5 watt / cm ² . The oscillation frequency is preferably 10 to 200 KHz, more preferably 20 to 100 KHz. Further, the time of the ultrasonic irradiation treatment is preferably 1 minute to 48 hours, more preferably 5 minutes to 48 hours. After this, it is desirable to further thoroughly disperse or dissolve using a ball-type kneader such as a ball mill, a vibration mill, a sand mill, or a roll mill.

The film thickness of the conductive layer is preferably in the range of 0.01 to 100 μm, more preferably in the range of 0.1 to 50 μm.
The conductive layer in the present invention has excellent conductivity as it is, but after applying the carbon nanotube-containing composition on the surface of the base material to form the conductive layer, a doping treatment with an acid is performed. Conductivity can be further improved by leaving or heating at room temperature.
The doping treatment method using an acid is not particularly limited, and a known method can be used. For example, the doping process can be performed by performing a process such as immersing a conductor in an acidic solution. Specifically, the acidic solution includes inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, organic acids such as p-toluenesulfonic acid, camphorsulfonic acid, benzoic acid and derivatives having these skeletons, polystyrene sulfonic acid, polyvinyl It is an aqueous solution containing a polymer acid such as sulfonic acid, poly (2-acrylamido-2-methylpropane) sulfonic acid, polyvinylsulfuric acid and derivatives having these skeletons, or a mixed solution of water and an organic solvent. In addition, these inorganic acids, organic acids, and polymer acids may be used alone or in admixture of two or more at any ratio.

<Base material>
As a base material in the conductive packaging material of the present invention, a polymer compound, plastic, wood, paper material, ceramics, fiber, non-woven fabric, carbon fiber, carbon fiber paper, and films, foams, porous films, elastomers And a glass plate etc. are used. For example, polymer compounds, plastics and films include polyethylene, polyvinyl chloride, polypropylene, polystyrene, ABS resin, AS resin, methacrylic resin, polybutadiene, polycarbonate, polyarylate, polyvinylidene fluoride, polyester, polyamide, polyimide, polyaramid, Examples include polyphenylene sulfide, polyether ether ketone, polyphenylene ether, polyether nitrile, polyamide imide, polyether sulfone, polysulfone, polyether imide, polybutylene terephthalate, polyurethane, its film, foam and elastomer. Since these films form a conductive layer on at least one surface thereof, the film surface is preferably subjected to corona surface treatment or plasma treatment for the purpose of improving the adhesion of the conductive layer.

<Method for producing conductive packaging material>
The conductive packaging material of the present invention is obtained by coating a carbon nanotube-containing composition containing a conductive polymer (a), a solvent (b), and a carbon nanotube (c) on a base material and drying the conductive polymer. Manufactured by forming layers.

  The conductive layer in the present invention is formed on the surface of the substrate by a method used for general coating. For example, gravure coater, roll coater, curtain flow coater, spin coater, bar coater, reverse coater, kiss coater, phanten coater, rod coater, air doctor coater, knife coater, blade coater, cast coater, screen coater, etc. Spraying methods such as spray coating such as air spray and airless spray, and dipping methods such as dipping are used.

  After coating the carbon nanotube-containing composition on the surface of the substrate, it can be left at room temperature, but the conductive layer can also be heat-treated. By the heat treatment, the crosslinking reaction between the carbon nanotube (c), the polymer compound (d), the basic compound (e), and the conductive polymer (a) is further promoted, and water resistance can be imparted in a shorter time. Moreover, since the quantity of the solvent (b) which remains can be reduced more and electroconductivity improves further, it is preferable. The heat treatment temperature is preferably 20 ° C. or more and 250 ° C. or less, and particularly preferably heating at 40 ° C. to 200 ° C. When the temperature is higher than 250 ° C., the conductive polymer (a) itself is decomposed, and the conductivity may be remarkably lowered.

<Electronic parts container>
The electronic component container of the present invention is obtained by processing the conductive packaging material of the present invention.
The form of the electronic component container of the present invention is not particularly limited. Specific examples include trays, electronic component carrier tapes, electronic component carrier tape cover tapes, electronic component packaging bags, and the like.

  As a form of the packaging bag for electronic parts, an arbitrary form such as a pillow packaging bag, a three-side seal bag, a four-side seal bag, or the like can be selected. Moreover, there is no restriction | limiting in particular as a method for producing an electronic component container, For example, the injection molding method, the blow molding method, the drape molding method, and the vacuum forming method are used, and a bending process can also be utilized.

The electronic component container of the present invention can contain a conductive substance in order to further improve its conductivity. Examples of the conductive substance include conductive carbon black, carbon-based substances such as graphite, metal oxides such as tin oxide and zinc oxide, and metals such as silver, nickel, and copper. The conductive packaging material and electronic component of the present invention The container may further include layers having various functions such as a protective layer, a heat ray blocking layer, a gas barrier layer, an adhesive layer, an antireflection layer, and a weather resistant layer.

The conductive layer in the conductive packaging material and the electronic component container of the present invention has a surface resistance under low humidity conditions (temperature 25 ° C., relative humidity 15%) from the viewpoint of preventing breakdown due to static electricity and preventing performance deterioration due to dust adhesion. The value is preferably 10 ¹ to 10 ¹² Ω, and more preferably 10 ³ to 10 ¹⁰ Ω.

  The conductive packaging material and the electronic component container of the present invention may be repeatedly used after being washed with water after use. Therefore, it is necessary to provide water resistance so that the performance such as conductivity is not deteriorated by washing with water. From the viewpoint of water washing, as a measure of water resistance, the ratio (SR1 / SR0) of the surface resistance value (SR1) after being immersed in pure water at 40 ° C. for 1 hour with respect to the surface resistance value (SR0) at the time of no treatment. The ratio is preferably 5 or less, more preferably 3 or less. The carbon nanotube-containing composition used for producing such a water-resistant conductive packaging material and electronic component container contains a polymer compound (d) and / or a silane coupling agent (g). This is what is used.

  The conductive packaging material and the electronic component container of the present invention may be stretch-molded such as biaxially stretched, and a material having a small rate of change in conductivity after stretching is required. In particular, since the conductive polymer (a) in the present invention is a polymer compound, it has excellent molding followability, and has a characteristic that there is very little decrease in conductivity after molding. From the viewpoint of conductivity, the ratio (SR2 / SR0) of the surface resistance value (SR2) after stretching 150% to the surface resistance value (SR0) at the time of no treatment is preferably 10 or less, particularly 5 or less. It is more preferable.

  The conductive packaging material and the electronic component container of the present invention preferably have a visible light transmittance of 80% or more, and more preferably 85% or more in order to enable visual recognition and electronic device recognition of electronic components to be packaged. Preferably there is.

The conductive packaging material and the electronic component container of the present invention can be subjected to uneven processing such as embossing. In this case, the carbon nanotube-containing composition can be applied either before or after the uneven processing. Since the conductive polymer (a) in the present invention is a high molecular compound, it has excellent molding followability, and has the property that there is very little decrease in conductivity after such uneven processing as described above.
It is preferable that the ratio (SR3 / SR0) of the surface resistance value (SR3) of the concave portion after the concavo-convex processing such as embossing to the surface resistance value (SR0) when the electronic component container is not processed is 10 or less, and further 5 The following is more preferable.

  In the conductive packaging material of the present invention described above, the conductive layer containing the conductive polymer (a) and the carbon nanotube (c) that can exhibit good conductivity even at a very low concentration. Therefore, it is possible to sufficiently exhibit electrical conductivity and excellent antistatic properties. In addition, since the conductivity can be sufficiently expressed even if the amount of the carbon nanotube (c) is small, it is not necessary to increase the amount of the carbon nanotube (c), and the transparency is excellent. Moreover, since the conductive polymer (a) works as a binder, the adhesion between the substrate and the conductive layer is excellent.

Moreover, if it has the electroconductive layer formed by applying the carbon nanotube containing composition containing electroconductive polymer (a), solvent (b), and carbon nanotube (c), carbon nanotube (c) The carbon nanotube (c) is uniformly dispersed in the conductive layer without impairing the properties of itself, and the conductivity of the conductive layer becomes higher and the antistatic property is further improved.
Further, if the conductive layer in the conductive packaging material of the present invention contains a water-soluble conductive polymer and a silane coupling agent (g), a crosslinked structure is formed, so that film formability, water resistance, hardness Excellent in weather resistance.

  In the method for producing a conductive packaging material of the present invention, a carbon nanotube-containing composition containing a conductive polymer (a), a solvent (b), and a carbon nanotube (c) is applied on a substrate. Since the conductive layer is formed by being worked and dried, the carbon nanotube (c) can be uniformly dispersed in the conductive layer without impairing the properties of the carbon nanotube (c) itself. Moreover, the conductive packaging material of the present invention can be obtained by a simple method.

That is, in the carbon nanotube-containing composition in the present invention, since the carbon nanotube (c) is added to the solvent (b) together with the conductive polymer (a), the characteristics of the carbon nanotube (c) itself are not impaired. The carbon nanotubes (c) can be dispersed or solubilized in the solvent (b) and do not separate or aggregate even during long-term storage. The reason for this is not clearly understood, but the conductive polymer (a) and the carbon nanotube (c) are adsorbed to each other by the π-π interaction by π electrons, so that the carbon nanotube (c) becomes the conductive polymer (a). It is presumed that it is dispersed or solubilized together.
Then, the carbon nanotube (c) is prepared by coating the carbon nanotube-containing composition in which the carbon nanotube (c) is dispersed or solubilized in the solvent (b) on the substrate to form a conductive layer. It is possible to obtain a conductive layer in which is uniformly dispersed.

  The present invention will be described in more detail with reference to examples, but the following examples are not intended to limit the scope of the present invention.

<Manufacture of conductive polymer>
(Production Example 1, conductive polymer (A-1))
Synthesis of poly (2-sulfo-5-methoxy-1,4-iminophenylene):
100 mmol of 2-aminoanisole-4-sulfonic acid was stirred and dissolved in a 4 mol / L triethylamine aqueous solution at 25 ° C., and an aqueous solution of 100 mmol ammonium peroxodisulfate was added dropwise thereto. After completion of the dropping, the mixture was further stirred at 25 ° C. for 12 hours, and then the reaction product was filtered, washed and dried to obtain 15 g of polymer powder. The volume resistance value of this conductive polymer (A-1) was 9.0 Ω · cm.

(Production Example 2, conductive polymer (A-2))
Synthesis of poly (2-sulfo-1,4-iminophenylene):
100 mmol of m-aminobenzenesulfonic acid was dissolved by stirring in a 4 mol / liter trimethylamine aqueous solution at 25 ° C., and an aqueous solution of 100 mmol ammonium peroxodisulfate was added dropwise thereto. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 12 hours, and then the reaction product was filtered, washed, and dried to obtain 10 g of polymer powder. The volume resistance value of this conductive polymer (A-2) was 12.0 Ω · cm.

(Production Example 3, conductive polymer (A-3))
Synthesis of sulfonated polyaniline:
Poly (2-sulfo-1,4-iminophenylene) was synthesized according to a known method “J. Am. Chem. Soc., (1991), 113, 2665-2666”. The sulfonic acid content of the obtained polymer was 52% with respect to the aromatic ring. Moreover, the volume resistance value of this conductive polymer (A-3) was 50 Ω · cm.

(Production Example 4, conductive polymer (A-4))
Synthesis of undoped polyaniline:
100 mmol of aniline was stirred and dissolved in a 1 mol / L aqueous sulfuric acid solution at 25 ° C., and an aqueous solution of 100 mmol ammonium peroxodisulfate was added dropwise thereto. After completion of dropping, the mixture was further stirred at 25 ° C. for 12 hours, and then the reaction product was filtered, washed and dried to obtain 8 g of polymer powder. The obtained polymer in a dope state was pressure-molded with a tablet molding machine, cut into a shape having a diameter of 10 mm and a thickness of 1 mm, and the conductivity was measured by a four-terminal method, which was 1.0 S / cm or less. . The polymer was dispersed and stirred in 1 mol / L ammonia water at 25 ° C. for 1 hour, filtered, washed and dried to obtain 5 g of dedoped polymer powder.

<Preparation of carbon nanotube-containing composition>
(Carbon nanotube-containing composition 1)
5 parts by mass of the conductive polymer (A-1) of Production Example 1 and 0.4 parts by mass of carbon nanotubes (multi-walled carbon nanotubes manufactured by the CVD method, manufactured by ILJIN) were mixed with 100 parts by mass of water at room temperature. Thus, a carbon nanotube-containing composition 1 was prepared.

(Carbon nanotube-containing composition 2)
5 parts by weight of the conductive polymer (A-1) of Production Example 1 above, 0.1 parts by weight of carbon nanotubes, acrylic resin “Dianar MX-1845” (Mitsubishi Rayon Co., resin content 40% by weight) which is an aqueous emulsion 20 parts by mass was mixed with 100 parts by mass of water at room temperature to prepare a carbon nanotube-containing composition 2.

(Carbon nanotube-containing composition 3)
A carbon nanotube-containing composition 3 was prepared by mixing 3 parts by mass of the conductive polymer (A-2) of Production Example 2 above, 0.1 part by mass of carbon nanotubes, and 1 part by mass of ammonia with 100 parts by mass of water at room temperature. .

(Carbon nanotube-containing composition 4)
1 part by mass of the conductive polymer (A-1) of Production Example 1 above, 0.2 part by mass of carbon nanotubes, 1 part by mass of triethylamine, acrylic resin “Dyanal MX-1845” (manufactured by Mitsubishi Rayon Co., Ltd.) 20 A carbon nanotube-containing composition 4 was prepared by mixing 100 parts by mass of water with 100 parts by mass of water at room temperature.

(Carbon nanotube-containing composition 5)
1 part by mass of the conductive polymer (A-3) of Production Example 3 above, 0.4 part by mass of the carbon nanotube, 0.5 part by mass of dodecylbenzenesulfonic acid, 100 parts by mass of a water / methanol mixed solvent (mass ratio 9/1) The part was mixed at room temperature to prepare a carbon nanotube-containing composition 5.

(Carbon nanotube-containing composition 6)
3 parts by mass of the conductive polymer (A-1) of Production Example 1 above, 0.4 parts by mass of carbon nanotubes, and 0.5 parts by mass of γ-glycidoxypropyltrimethoxysilane were mixed with 100 parts by mass of water at room temperature. Thus, a carbon nanotube-containing composition 6 was prepared.

(Carbon nanotube-containing composition 7)
1 part by mass of the conductive polymer (A-1) of Production Example 1 above, 0.4 part by mass of the carbon nanotube, 0.5 part by mass of γ-glycidoxypropyltrimethoxysilane, 5 parts by mass of colloidal silica (particle diameter: 10 nm) A carbon nanotube-containing composition 7 was prepared by mixing 10 parts by mass of an acrylic resin “Dianar MX-1845” (manufactured by Mitsubishi Rayon Co., Ltd.), which is an aqueous emulsion, with 100 parts by mass of water at room temperature.

(Carbon nanotube-containing composition 8)
Carbon nanotube-containing composition 8 is prepared by mixing 0.1 part by mass of carbon nanotubes and 20 parts by mass of acrylic resin “Dianar MX-1845” (manufactured by Mitsubishi Rayon Co., Ltd.), which is an aqueous emulsion, with 100 parts by mass of water at room temperature. did.

(Carbon nanotube-containing composition 9)
0.5 part by mass of the conductive polymer (A-4) of Production Example 4 above, 0.4 part by mass of the carbon nanotube, and 5 parts by mass of the polyester resin “Byron-200” (manufactured by Toyobo Co., Ltd.) are added at 100 parts by mass of N-methylpyrrolidone. The part was mixed at room temperature to prepare a carbon nanotube-containing composition 9.

<Preparation of conductive composition>
(Conductive composition 1)
A conductive composition 1 was prepared by mixing 3 parts by mass of the conductive polymer (A-1) of Production Example 1 with 100 parts by mass of water at room temperature.

(Conductive composition 2)
1 part by mass of the conductive polymer (A-1) of Production Example 1 and 10 parts by mass of an acrylic resin “Dianar MX-1845” (manufactured by Mitsubishi Rayon Co., Ltd.), which is an aqueous emulsion, are mixed with 100 parts by mass of water at room temperature. Thus, a conductive composition 2 was prepared.

(Conductive composition 3)
A conductive composition 3 was prepared by mixing 3 parts by mass of the conductive polymer (A-1) of Production Example 1 and 0.5 parts by mass of γ-glycidoxypropyltrimethoxysilane with 100 parts by mass of water at room temperature. did.

(Conductive composition 4)
1 part by mass of the conductive polymer (A-1) of Production Example 1 above, 0.5 part by mass of γ-glycidoxypropyltrimethoxysilane, 5 parts by mass of colloidal silica (particle diameter: 10 nm), acrylic resin which is an aqueous emulsion Conductive composition 4 was prepared by mixing 10 parts by weight of “Dynaral MX-1845” (manufactured by Mitsubishi Rayon Co., Ltd.) with 100 parts by weight of water at room temperature.

<Evaluation method>
(Visible light transmittance)
The visible light transmittance of the conductive packaging material was measured using UV-3100 manufactured by Shimadzu Corporation.
(Surface resistance value)
The surface resistance value of the conductive layer of the conductive packaging material was measured under the conditions of 25 ° C. and 15% RH. When the surface resistance value is 10 ⁸ Ω or more, the two-probe method (Dia Instruments Hirester UP, electrode distance: 20 mm) is used. When the surface resistance value is 10 ⁷ Ω or less, the four-probe method (diameter Instruments Lorester GP, distance between each electrode: 5 mm) was used.

(Appearance of painted surface)
After immersing the conductive packaging material in warm water at 40 ° C., the state of the conductive layer was visually observed.
○: No change from before immersion (with gloss and transparency).
X: The component is eluted.

(Blocking resistance)
In an atmosphere of 40 ° C. and 80% RH, the conductive layer of the conductive packaging material and the base material (conductive layer non-formed surface) of another conductive packaging material are stacked, and a load of 100 g / cm ² is applied. After standing for 24 hours, the state when the two conductive packaging materials were peeled was evaluated.
○: No resistance during peeling.
X: There is a large resistance during peeling.

(Surface resistance after stretching)
Using a biaxial stretching device, stretch the conductive packaging material (100 mm x 100 mm x 500 μm) by 150% in a uniaxial direction under the conditions of temperature, 100 to 150 ° C, preheating time 15 seconds, and tensile speed 5 m / mim. did. The surface resistance value (SR2) of the conductive layer of the conductive packaging material after stretching is obtained under the conditions of 25 ° C. and 15% RH, and the surface resistance value (SR0) of the conductive layer of the conductive packaging material before stretching. The ratio (SR2 / SR0) was obtained.

<Conductive packaging material>
[Example 1]
The carbon nanotube-containing composition 1 is applied to a substrate (unstretched PET (polyethylene terephthalate) sheet, 100 mm × 100 mm × 500 μm) by a bar coater method (using bar coat No. 5), dried at 80 ° C. for 5 minutes, and conductive A conductive layer was formed to obtain a conductive packaging material. About this electroconductive packaging material, surface resistance value (SR0) and visible light transmittance | permeability were measured, and the coating surface external appearance and blocking resistance were evaluated. The conductive packaging material was stretched 150% in the uniaxial direction using a biaxial stretching apparatus. The surface resistance value (SR2) of the conductive layer after stretching was measured. These results are shown in Table 1.

[Examples 2, 4 to 6]
A conductive packaging material was obtained in the same manner as in Example 1 except that the carbon nanotube-containing composition 1 was changed to the carbon nanotube-containing composition shown in Table 1. About this electroconductive packaging material, surface resistance value (SR0) and visible light transmittance | permeability were measured, and the coating surface external appearance and blocking resistance were evaluated. Further, the surface resistance value (SR2) of the conductive layer after stretching was measured. These results are shown in Table 1.

[Examples 3 and 7]
Except for changing the carbon nanotube-containing composition 1 to the carbon nanotube-containing composition shown in Table 1 and changing the base material to an unstretched PC (polycarbonate) sheet (100 mm × 100 mm × 500 μm), the same procedure as in Example 1 was performed. Thus, a conductive packaging material was obtained. About this electroconductive packaging material, surface resistance value (SR0) and visible light transmittance | permeability were measured, and the coating surface external appearance and blocking resistance were evaluated. Further, the surface resistance value (SR2) of the conductive layer after stretching was measured. These results are shown in Table 1.

[Example 8]
The carbon nanotube-containing composition 9 was applied to a substrate (unstretched PET (polyethylene terephthalate) sheet, 100 mm × 100 mm × 500 μm) by the bar coater method (using bar coat No. 5) and dried at 80 ° C. for 5 minutes. After being immersed in a 1 mol / L sulfuric acid aqueous solution for 5 minutes, it was dried at 80 ° C. for 5 minutes to form a conductive layer to obtain a conductive packaging material. About this electroconductive packaging material, surface resistance value (SR0) and visible light transmittance | permeability were measured, and the coating surface external appearance and blocking resistance were evaluated. The conductive packaging material was stretched 150% in the uniaxial direction using a biaxial stretching apparatus. The surface resistance value (SR2) of the conductive layer after stretching was measured. These results are shown in Table 1.

[Comparative Examples 1-3]
A conductive packaging material was obtained in the same manner as in Example 1 except that the carbon nanotube-containing composition 1 was changed to the conductive composition shown in Table 1. About this electroconductive packaging material, surface resistance value (SR0) and visible light transmittance | permeability were measured, and the coating surface external appearance and blocking resistance were evaluated. Further, the surface resistance value (SR2) of the conductive layer after stretching was measured. These results are shown in Table 1.

[Comparative Example 4]
Conductivity was the same as in Example 1 except that the carbon nanotube-containing composition 1 was changed to the conductive composition 4 and the base material was changed to an unstretched PEN (polyethylene naphthalate) sheet (100 mm × 100 mm × 500 μm). A packaging material was obtained. About this electroconductive packaging material, surface resistance value (SR0) and visible light transmittance | permeability were measured, and the coating surface external appearance and blocking resistance were evaluated. Further, the surface resistance value (SR2) of the conductive layer after stretching was measured. These results are shown in Table 1.

[Comparative Example 5]
Conductivity was the same as in Example 1 except that the carbon nanotube-containing composition 1 was changed to the carbon nanotube-containing composition 8 and the base material was changed to an unstretched PEN (polyethylene naphthalate) sheet (100 mm × 100 mm × 500 μm). A packaging material was obtained. About this electroconductive packaging material, surface resistance value (SR0) and visible light transmittance | permeability were measured, and the coating surface external appearance and blocking resistance were evaluated. Further, the surface resistance value (SR2) of the conductive layer after stretching was measured. These results are shown in Table 1.

[Example 9]
A conductive packaging material was obtained in the same manner as in Example 6. The surface resistance value (SR0) of this conductive packaging material was measured. Then, this electroconductive packaging material was immersed in 40 degreeC pure water for 1 hour, the surface resistance value (SR1) was measured, and water resistance was evaluated.

[Example 10]
A conductive packaging material was obtained in the same manner as in Example 7. The surface resistance value (SR0) of this conductive packaging material was measured. Then, this electroconductive packaging material was immersed in 40 degreeC pure water for 1 hour, the surface resistance value (SR1) was measured, and water resistance was evaluated.

[Comparative Example 6]
A conductive packaging material was obtained in the same manner as in Comparative Example 1. The surface resistance value (SR0) of this conductive packaging material was measured. Then, this electroconductive packaging material was immersed in 40 degreeC pure water for 1 hour, the surface resistance value (SR1) was measured, and water resistance was evaluated.

[Comparative Example 7]
A conductive packaging material was obtained in the same manner as in Comparative Example 2. The surface resistance value (SR0) of this conductive packaging material was measured. Then, this electroconductive packaging material was immersed in 40 degreeC pure water for 1 hour, the surface resistance value (SR1) was measured, and water resistance was evaluated.

[Comparative Example 8]
A conductive packaging material was obtained in the same manner as in Comparative Example 3. The surface resistance value (SR0) of this conductive packaging material was measured. Then, this electroconductive packaging material was immersed in 40 degreeC pure water for 1 hour, the surface resistance value (SR1) was measured, and water resistance was evaluated.

[Comparative Example 9]
A conductive packaging material was obtained in the same manner as in Comparative Example 4. The surface resistance value (SR0) of this conductive packaging material was measured. Then, this electroconductive packaging material was immersed in 40 degreeC pure water for 1 hour, the surface resistance value (SR1) was measured, and water resistance was evaluated.

<Tray>
[Example 11]
Using a vacuum molding machine, 5 rows of 10 mm × 90 mm, 10 mm deep recesses were formed from the conductive packaging material obtained in Example 6 under preheating conditions of 120 ° C., 10 seconds, 60 ° C., 15 seconds. A tray having the same was molded. The surface resistance value (SR0) before molding and the surface resistance value (SR3) of the concave portion of the tray were measured. The tray was immersed in pure water at 40 ° C. for 1 hour, the surface resistance value (SR1) was measured, and the water resistance was evaluated. Moreover, the coating surface appearance was evaluated. These results are shown in Table 3.

[Example 12]
A tray was molded in the same manner as in Example 11 except that the conductive packaging material obtained in Example 7 was used instead of the conductive packaging material obtained in Example 6. The surface resistance value (SR0) before molding and the surface resistance value (SR3) of the concave portion of the tray were measured. The tray was immersed in pure water at 40 ° C. for 1 hour, the surface resistance value (SR1) was measured, and the water resistance was evaluated. Moreover, the coating surface appearance was evaluated. These results are shown in Table 3.

<Carrier tape (container)>
[Example 13]
Using a vacuum molding machine, one row of 10 mm × 10 mm, 5 mm deep recesses from the conductive packaging material obtained in Example 6 under preheating conditions of 120 ° C., 10 seconds, 60 ° C., 15 seconds A 50 × 50 cm sheet was prepared, one row of recesses was cut into a width of 20 mm, and these were joined to form a carrier tape model. The surface resistance value (SR0) before molding and the surface resistance value (SR3) of the concave portion of the carrier tape after molding were measured. The carrier tape was immersed in pure water at 40 ° C. for 1 hour, the surface resistance value (SR1) was measured, and water resistance was evaluated. Moreover, the coating surface appearance was evaluated. These results are shown in Table 4.

[Example 14]
A carrier tape was molded in the same manner as in Example 13 except that the conductive packaging material obtained in Example 7 was used instead of the conductive packaging material obtained in Example 6. The surface resistance value (SR0) before molding and the surface resistance value (SR3) of the concave portion of the carrier tape after molding were measured. The carrier tape was immersed in pure water at 40 ° C. for 1 hour, the surface resistance value (SR1) was measured, and water resistance was evaluated. Moreover, the coating surface appearance was evaluated. These results are shown in Table 4.

<Carrier tape cover tape>
The conductive packaging materials obtained in Examples 6 and 7 were cut into the carrier tape having a width of 20 mm and joined together to form a cover tape model.

<Electronic parts bag>
[Example 15]
The conductive packaging material obtained in Example 6 was three-side sealed by a heat seal method with the conductive layer facing inward to produce a bag (100 mm × 100 mm). The surface resistance value (SR0) of the bag was measured. The bag was immersed in pure water at 40 ° C. for 1 hour, the surface resistance value (SR1) was measured, and the water resistance was evaluated. Moreover, the coating surface appearance was evaluated. These results are shown in Table 5.

[Example 16]
A bag was produced in the same manner as in Example 15 except that the conductive packaging material obtained in Example 7 was used instead of the conductive packaging material obtained in Example 6. The surface resistance value (SR0) of the bag was measured. The bag was immersed in pure water at 40 ° C. for 1 hour, the surface resistance value (SR1) was measured, and the water resistance was evaluated. Moreover, the coating surface appearance was evaluated. These results are shown in Table 5.

The conductive packaging material of the present invention includes semiconductor devices such as IC, LSI, VLSI, LCD (liquid crystal display), PDP (plasma display), silicon wafer, hard disk, liquid crystal substrate, magnetic device, optical device, magneto-optical device, and these When storing, transporting, and mounting electronic materials such as electronic components that form the electronic material, the electronic materials can be used to protect them from destruction due to static electricity or the like, and adhesion of dust. In addition, the conductive packaging material of the present invention can be used for containers for electronic parts such as carrier tapes, cover tapes, trays, magazines, bulk cases, and OA equipment covers.

Claims (25)

A substrate and a conductive layer;
A conductive packaging material, wherein the conductive layer is a layer containing a conductive polymer (a) and a carbon nanotube (c).   The conductive layer is a layer formed by coating a carbon nanotube-containing composition containing a conductive polymer (a), a solvent (b), and a carbon nanotube (c) on a substrate. The conductive packaging material according to claim 1.   The conductive packaging material according to claim 2, wherein the carbon nanotube-containing composition further contains a polymer compound (d).   The conductive packaging material according to claim 2 or 3, wherein the carbon nanotube-containing composition further contains a basic compound (e).   The conductive packaging material according to any one of claims 2 to 4, wherein the carbon nanotube-containing composition further contains a surfactant (f).   Furthermore, colloidal silica (h) is contained, The electroconductive packaging material as described in any one of Claim 2 thru | or 5 characterized by the above-mentioned.   The conductive packaging material according to any one of claims 2 to 6, wherein the conductive polymer (a) is a water-soluble conductive polymer. The conductive packaging material according to claim 7, wherein the carbon nanotube-containing composition further contains a silane coupling agent (g) represented by the following formula (1).

(In the formula (1), R ⁴² , R ⁴³ and R ⁴⁴ are each independently hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, X is a group selected from the group consisting of an amino group, an acetyl group, a phenyl group, and a halogen group.

1 and m are numbers from 0 to 6, and Y is a group selected from the group consisting of a hydroxyl group, a thiol group, an amino group, an epoxy group, and an epoxycyclohexyl group. )   The conductive packaging material according to claim 7 or 8, wherein the water-soluble conductive polymer has a sulfonic acid group and / or a carboxyl group. The water-soluble conductive polymer having a sulfonic acid group and / or a carboxyl group contains at least one or more repeating units selected from the following formulas (2) to (10) in a total number of repeating units of 20 to 100 in the whole polymer. The conductive packaging material according to claim 9, wherein the conductive packaging material is a water-soluble conductive polymer.

(In the formula (2), R ¹ and R ² are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —OCH ₃ , —CH _{3. , -C 2 H 5, -F,} -Cl, -Br, -I, -N (R 35) 2, -NHCOR 35, -OH, -O -, -SR 35, -OR 35, -OCOR 35, ^{_{-NO 2, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO, and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Alternatively, it is an alkylene, arylene or aralkylene group, and at least one of R ¹ and R ² is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH and —R. ³⁵ is a group selected from the group consisting of COOH.)

(In the formula (3), R ³ and R ⁴ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —OCH ₃ , —CH _{3. , -C 2 H 5, -F,} -Cl, -Br, -I, -N (R 35) 2, -NHCOR 35, -OH, -O -, -SR 35, -OR 35, -OCOR 35, ^{_{-NO 2, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO, and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Or an alkylene, arylene, or aralkylene group, and at least one of R ³ and R ⁴ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH, and —R. ³⁵ is a group selected from the group consisting of COOH.)

(In the formula (4), R ^{5 to} R ⁸ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —OCH ₃ , —CH _{3. , -C 2 H 5, -F,} -Cl, -Br, -I, -N (R 35) 2, -NHCOR 35, -OH, -O -, -SR 35, -OR 35, -OCOR 35, ^{_{-NO 2, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO, and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Alternatively, it is an alkylene, arylene or aralkylene group, and at least one of R ^{5 to} R ⁸ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH and —R. ³⁵ is a group selected from the group consisting of COOH.)

(In the formula (5), R ^{9 to} R ¹³ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —OCH ₃ , —CH _{3. , -C 2 H 5, -F,} -Cl, -Br, -I, -N (R 35) 2, -NHCOR 35, -OH, -O -, -SR 35, -OR 35, -OCOR 35, ^{_{-NO 2, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO, and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Alternatively, it is an alkylene, arylene or aralkylene group, and at least one of R ^{9 to} R ¹³ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH and —R. ³⁵ is a group selected from the group consisting of COOH.)

(In the formula (6), R ¹⁴ is selected from the group consisting of —SO ₃ ⁻ , —SO ₃ H, —R ⁴² SO ₃ ⁻ , —R ⁴² SO ₃ H, —COOH and —R ⁴² COOH, R ⁴² is an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms.)

(In the formula (7), R ^{52 to} R ⁵⁷ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —OCH ₃ , —CH _{3. , -C 2 H 5, -F,} -Cl, -Br, -I, -N (R 35) 2, -NHCOR 35, -OH, -O -, -SR 35, -OR 35, -OCOR 35, ^{_{-NO 2, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO, and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Alternatively, it is an alkylene, arylene or aralkylene group, and at least one of R ^{52 to} R ⁵⁷ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH and —R. ³⁵ is a group selected from the group consisting of COOH, Ht ^{is, NR 82, S, O,} Se and Te A heteroatom group selected from Li Cheng group, R ⁸² represents hydrogen and straight-chain or branched alkyl group having 1 to 24 carbon atoms, or substituted, the unsubstituted aryl group, carbonization of R ⁵² to R ⁵⁷ The hydrogen chains are bonded to each other at any position to form a divalent chain that forms a cyclic structure of at least one or more 3- to 7-membered saturated or unsaturated hydrocarbons together with carbon atoms substituted by such groups. The cyclic bond chain thus formed may contain a carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, imino bond at any position, and n is a heterocycle and a substituent. This represents the number of condensed rings sandwiched between benzene rings having R ^{53 to} R ⁵⁶ , and is an integer of 0 or 1-3.)

(In the formula (8), R ^{58 to} R ⁶⁶ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —OCH ₃ , —CH _{3. , -C 2 H 5, -F,} -Cl, -Br, -I, -N (R 35) 2, -NHCOR 35, -OH, -O -, -SR 35, -OR 35, -OCOR 35, ^{_{-NO 2, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO, and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Alternatively, it is an alkylene, arylene or aralkylene group, and at least one of R ^{58 to} R ⁶⁶ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH and —R. a group selected from the group consisting of ³⁵ COOH, benzene and n having substituents R ⁵⁸ and R ⁵⁹ It represents the number of condensed rings sandwiched between a benzene ring having a substituent R ⁶¹ to R ⁶⁴ with the ring and is an integer of 0 or 1-3.)

(In the formula (9), R ^{67 to} R ⁷⁶ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —OCH ₃ , —CH _{3. , -C 2 H 5, -F,} -Cl, -Br, -I, -N (R 35) 2, -NHCOR 35, -OH, -O -, -SR 35, -OR 35, -OCOR 35, ^{_{-NO 2, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO, and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Alternatively, it is an alkylene, arylene or aralkylene group, and at least one of R ^{67 to} R ⁷⁶ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH and —R. ³⁵ is a group selected from the group consisting of COOH, benzene and n having a substituent R ⁶⁷ to R ⁶⁹ And represents the number of condensed rings sandwiched benzoquinone ring and is an integer of 0 or 1-3.)

(In the formula (10), R ^{77 to} R ⁸¹ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —OCH ₃ , —CH _{3. , -C 2 H 5, -F,} -Cl, -Br, -I, -N (R 35) 2, -NHCOR 35, -OH, -O -, -SR 35, -OR 35, -OCOR 35, ^{_{-NO 2, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO, and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Alternatively, it is an alkylene, arylene or aralkylene group, and at least one of R ^{77 to} R ⁸¹ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH and —R. ³⁵ is a group selected from the group consisting of COOH, X ^a- is chloride, bromide, yo Elementary ion, fluorine ion, nitrate ion, sulfate ion, hydrogen sulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, methanesulfonate ion, p-toluenesulfone At least one anion selected from the group of 1 to 3 anions consisting of an acid ion, a trifluoroacetate ion, and a trifluoromethanesulfonate ion, a represents the ionic valence of X, (It is an integer, p is the doping rate, and its value is 0.001-1.) The water-soluble conductive polymer having a sulfonic acid group and / or a carboxyl group contains 20 to 100% of a repeating unit represented by the following formula (11) in the total number of repeating units of the whole polymer. Item 10. A conductive packaging material according to Item 9.

(In the formula (11), y represents an arbitrary number of 0 <y <1, and R ^{15 to} R ³² are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , _{^{-R 35 SO 3 H, -OCH 3}} , -CH 3, -C 2 H 5, -F, -Cl, -Br, -I, -N (R 35) 2, -NHCOR 35, -OH, -O ^{-, -SR 35, -OR 35,} -OCOR 35, -NO 2, -COOH, -R 35 COOH, -COOR 35, -COR 35, selected from the group consisting of -CHO, and -CN, wherein, R ³⁵ is an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene or aralkylene group, and at least one of R ^{15 to} R ³² is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ^— , -R ³⁵ SO ₃ H, -COOH and -R ³⁵ COOH. The conductive packaging material according to claim 9, wherein the water-soluble conductive polymer having a sulfonic acid group and / or a carboxyl group is represented by the following formula (12).

(In the formula (12), R ³³ is one group selected from the group consisting of a sulfonic acid group, a carboxyl group, and alkali metal salts, ammonium salts and substituted ammonium salts thereof, and R ³⁴ is a methyl group. , Ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, dodecyl group, tetracosyl group, methoxy group, ethoxy group, n-propoxy group A group selected from the group consisting of iso-butoxy group, sec-butoxy group, tert-butoxy group, heptoxy group, hexoxy group, octoxy group, dodecoxy group, tetracosoxy group, fluoro group, chloro group and bromo group X represents an arbitrary number of 0 <X <1, and n represents the degree of polymerization and is 3 or more.) The water-soluble conductive polymer having a sulfonic acid group and / or a carboxyl group is an acidic group-substituted aniline represented by the following formula (13), an alkali metal salt thereof, an ammonium salt and / or a substituted ammonium salt, a basic compound: The conductive packaging material according to claim 9, wherein the conductive packaging material is a water-soluble conductive polymer obtained by polymerization with an oxidizing agent in a solution.

(In the formula (13), R ^{36 to} R ⁴¹ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —OCH ₃ , —CH _{3. , -C 2 H 5, -F,} -Cl, -Br, -I, -N (R 35) 2, -NHCOR 35, -OH, -O -, -SR 35, -OR 35, -OCOR 35, ^{_{-NO 2, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO, and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Alternatively, it is an alkylene, arylene or aralkylene group, and at least one of R ^{36 to} R ⁴¹ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH and —R ^35. A group selected from the group consisting of COOH.)   A water-soluble conductive polymer having a sulfonic acid group and / or a carboxyl group contains an alkoxy group-substituted aminobenzene sulfonic acid, an alkali metal salt, an ammonium salt and / or a substituted ammonium salt thereof in a solution containing a basic compound. The conductive packaging material according to claim 9, wherein the conductive packaging material is a water-soluble conductive polymer obtained by polymerization.   The conductive packaging material according to claim 9, wherein the water-soluble conductive polymer having a sulfonic acid group and / or a carboxyl group is polyethylene dioxythiophene polystyrene sulfate. The conductive packaging material according to any one of claims 1 to 15, wherein a surface resistance value at a temperature of 25 ° C and a relative humidity of 15% is 10 ¹ to 10 ¹² Ω.   The ratio (SR1 / SR0) of the surface resistance value SR1 after immersion in pure water at a temperature of 40 ° C for 1 hour and the surface resistance value SR0 before immersion is 5 or less, characterized in that The conductive packaging material according to any one of the above.   18. The ratio (SR2 / SR0) between the surface resistance value SR2 after stretching the conductive packaging material by 150% and the surface resistance value SR0 before stretching (SR2 / SR0) is 10 or less. The conductive packaging material according to Item.   The conductive packaging material according to any one of claims 1 to 18, wherein the visible light transmittance is 80% or more.   A container for electronic parts, wherein the conductive packaging material according to any one of claims 1 to 19 is processed.   21. The electronic component container according to claim 20, wherein the electronic component container is a tray, an electronic component carrier tape, an electronic component carrier tape cover tape, or an electronic component packaging bag.   21. The ratio (SR1 / SR0) between the surface resistance value SR1 after immersion in pure water at a temperature of 40 ° C. for 1 hour and the surface resistance value SR0 before immersion is 5 or less. 21. A container for electronic parts according to 21.   23. The ratio (SR3 / SR0) between the surface resistance value SR3 of the concave portion after the unevenness processing and the surface resistance value SR0 before the unevenness processing is 10 or less, according to any one of claims 20 to 22, Electronic component container. In the method for producing a conductive packaging material having a base material and a conductive layer,
A conductive layer is formed by coating and drying a carbon nanotube-containing composition containing a conductive polymer (a), a solvent (b), and a carbon nanotube (c) on a substrate. Manufacturing method of conductive packaging material.   The method for producing a conductive packaging material according to claim 24, wherein the composition containing carbon nanotubes before coating is irradiated with ultrasonic waves.