JP2828662B2 - Radical polymerizable composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a radical polymerizable composition comprising a compound having a π-electron conjugate structure, a radical polymerizable compound, and a photolytic oxidizing agent. More specifically, the present invention is useful in the fields of electric and electronic industries because of light irradiation which is useful as an electrode of a display element, an electrochromic display element material, a circuit material of a printed circuit board, an antistatic material by static electricity, and an electromagnetic shielding material. The present invention relates to a radical polymerizable composition that can be converted into a radical polymerizable composition.

[Prior art] Demands for various conductive materials used in the fields of electric and electronic industries are becoming increasingly severe, and conductive materials having special functions such as good workability, long-term stability, and transparency. The emergence of is strongly desired.

In order to satisfy such demands, new conductive polymer compounds have been actively developed in recent years instead of conventional conductive materials such as carbon and metal, and applications using such polymer compounds have been actively performed. Many proposals have been made. Examples of such a polymer compound include:
Heterocyclic polymers such as polythiophene and polypyrrole are mentioned, and as examples of applications, use as electrode materials for secondary batteries or electrochromic materials has been proposed.

However, many of these heterocyclic polymers are insoluble and infusible, and have the drawback that their moldability is poor for realizing specific applications.

As a method for overcoming this drawback, the present inventors have previously proposed a radical polymerizable composition comprising a compound having a π-electron conjugated structure such as polythiophene and polypyrrole and a radical polymerizable compound (Japanese Patent Application Laid-Open No. Sho 64-64). 20202).

However, it was difficult for this radical polymerizable composition to stably maintain a conductive state in air.

[Problems to be Solved by the Invention] An object of the present invention is to provide a radically polymerizable composition that can be formed into an arbitrary shape and that can easily impart extremely stable conductivity in air.

[Means for Solving the Problems] The present invention provides a radically polymerizable composition that can achieve the above object.

That is, the present invention relates to a radical polymerizable composition comprising a compound having a π-electron conjugate structure, a radical polymerizable compound, and a light-separating oxidizing agent.

The compound having a π-electron conjugate structure used in the present invention is a compound represented by the following general formula [I].

[In the formula, Z ₁ and Z ₂ each represent H, or a linear or branched alkyl group or alkoxyl group having 3 to 12 carbon atoms. m is a number from 5 to 5000 indicating the degree of polymerization. Among the compounds having a π-electron conjugated structure represented by the general formula [I], those which are preferably used are radically polymerizable compounds or compounds having a π-electron conjugated structure soluble in an organic solvent. Tianaphthene oligomers,
Examples thereof include polyisothianaphthenes into which various substituents have been introduced. Among these, a particularly preferred compound is poly (5,6-dibutoxyisothianaphthene). It is known that these compounds having a π-electron conjugate structure can be imparted with high conductivity by performing an operation called doping of oxidizing or reducing a part of the compounds (for example, Chemical Special Edition, Vol. 87, “Synthesis”). Metals ”(published by Kagaku Dojin).

As the radical polymerizable compound used in the present invention, various compounds described in “Polymerization reaction course”, Vol. 1, “Radical polymerization (I)”, pp. 5 to 9 can be used, but it is preferable. Are styrene-based compounds such as styrene, divinylbenzene, and p-chloromethylene; acrylate-based compounds such as methyl acrylate, epoxy acrylate and trimethylolpropane triacrylate; methacrylates such as methyl methacrylate and epoxy methacrylate. Reaction compounds of arylidene compounds such as diallylpentaerythritol with other compounds such as polythiol compounds, allyl compounds such as allyl chloride, vinylamide compounds such as N-vinylpyrrolidone, acrylamide, methacrylamide, etc. Acrylamide compounds, imides, lactams, ureas, carbazole compounds such as and the like, preferably may be mentioned styrene, epoxy acrylate or epoxy methacrylate and mixtures thereof. By blending these radically polymerizable compounds, durability is imparted to a cured product obtained from the radically polymerizable composition.

Further, the photolytic oxidizing agent used in the present invention is a compound represented by the following general formula [II] or [III].

[Wherein, Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ , Y ₈ and Y ₉ each represent H, a methyl group, a methoxy group, a hydroxyl group or a methylene group, and MX _n ⁻ Represents an anion composed of a metal and a halogen. Among the photo-decomposable oxidizing agents represented by the general formula [II], diphenyl iodonium salts are preferably used, and among the photo-decomposable oxidizing agents represented by the general formula [III], What is used is a triphenylsulfonium salt, and examples of the anion include BF ₄ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , and SbF ₆ ⁻ .

These photolytic oxidizing agents represented by the general formula [II] or [III] are known to be cleaved by irradiation with ultraviolet rays and dope polyacetylene [TC Clarke, Journal of the・ Chemical Society Chemical Communication (JC
S., Chem. Commun.), 1981, p. 384].

However, this method is a method in which a preformed polyacetylene is immersed in an organic solvent solution of a photolytic oxidizing agent and is irradiated with ultraviolet rays to perform doping, so that uniform doping is not performed and the doping state is stable for a long time. However, there was a drawback that it was not possible to maintain

The present invention is a radical polymerizable composition comprising a compound having a π electron conjugate structure, a radical polymerizable compound, and a photodecomposable oxidizing agent, wherein the compound having a π electron conjugate structure is dissolved in the radical polymerizable compound. Irradiate light,
Doping is caused by a photo-decomposable oxidizing agent at the same time as polymerization, or doping is caused by a photo-decomposable oxidizing agent in a cured product by irradiating light after polymerizing the radical polymerizable composition.

Therefore, the cured product obtained from the radically polymerizable composition of the present invention is uniformly dispersed or dissolved in the photodecomposable oxidizing agent in the radically polymerizable composition, so that the doping is performed uniformly and is stable. The doping state can be maintained for a long time.

The mixing ratio of each component of the radically polymerizable composition of the present invention is not particularly limited, but in order to impart sufficient properties, the content of the compound having a π-electron conjugate structure in the composition is 0.1 to It is desirably 40% by weight, preferably 5 to 30% by weight. When the content of the compound having a π-electron conjugate structure is less than 0.1% by weight, the conductivity of the obtained cured product is insufficient, and when the content is more than 40% by weight, the moldability and The mechanical strength of the cured product is insufficient. The content of the photolytic oxidizing agent in the composition is determined depending on the electric conductivity of the target cured product, but is generally 0.01 to 50% by weight, preferably 1 to 40% by weight. When the content of the photolytic oxidant is less than 0.01% by weight, the conductivity of the obtained cured product is insufficient, and when the content is more than 50% by weight, the dissolution of the photolytic oxidant is Sex matters. The content of the radical polymerizable compound in the composition is 50 to 99.5% by weight, preferably 60 to 90%.
% By weight. When the content of the radically polymerizable compound is less than 50% by weight, the mechanical strength of the cured product is insufficient, and when the content is more than 99.5% by weight, the conductivity of the obtained cured product is insufficient. It is.

The method for preparing the radically polymerizable composition of the present invention is not particularly limited, but it is desirable to disperse or dissolve a compound having a π-electron conjugated structure as uniformly as possible, a radically polymerizable compound and a photolytic oxidizing agent, For this purpose, a method of appropriately adding an organic solvent or mixing by heating is suitably used. Further, the preparation of the radical polymerizable composition is desirably performed under light shielding.

The type of the organic solvent appropriately used is not particularly limited as long as it can disperse or dissolve a compound having a π-electron conjugated structure, a radical polymerizable compound and a photodecomposable oxidizing agent, but preferably benzene, toluene, Examples thereof include aromatic hydrocarbons such as xylene, halogenated hydrocarbons such as chloroform, ether compounds such as tetrahydrofuran, and acetonitrile. The amount of the organic solvent used is appropriately 5 to 10 times (by weight) the amount of the radical polymerizable compound used.

Above, a compound having a π-electron conjugate structure, a radical polymerizable compound obtained by mixing a radical polymerizable compound and a photolytic oxidizing agent, when irradiated with light, doping occurs simultaneously with polymerization, Doping occurs during light irradiation after the production of a cured product. In addition, since the photolytic oxidizing agent is uniformly dissolved and dispersed in the radically polymerizable composition, a high conductive state can be stably obtained. Furthermore, the radical polymerizable composition of the present invention is characterized in that the doping level is determined by the content of the photodecomposable oxidizing agent, and not only can the electric conductivity be easily controlled, but also it has good moldability and photopolymerizability. have.

Various additives can be added to the radically polymerizable composition of the present invention as needed. Examples of additives include:
Examples include a radical polymerization initiator and a radical polymerization initiation auxiliary. Examples of the radical polymerization initiator include carbonyl compounds such as benzophenone and benzoin isopropyl ether, azo compounds such as azobisisobutyronitrile and azodibenzoyl, hydrogen peroxide, benzoyl peroxide, ammonium persulfate, and cumene hydroperoxy. It is desirable to use a peroxide, and N, N-dimethylaminoethanol and dimethylaniline can be suitably used as the radical polymerization initiator.

The radical polymerizable composition of the present invention prepared by the above method is applied to various insulator surfaces such as plastic, ceramic and wood by a general application method such as a bar coating method, a spray method, and a dipping method. And polymerize,
Articles having a cured coating on the surface of these various insulators can be manufactured. In addition, the radical polymerizable composition of the present invention can be cast into various types of molds and polymerized in the mold to produce a molded article.

The method of polymerizing the radical polymerizable composition of the present invention is not particularly limited, and various energy sources such as heat, ultraviolet rays, electron beams, and X-rays can be used. It is suitably used because it has good operability and can be given conductivity at the same time. In addition, after the radical polymerizable composition of the present invention is polymerized by heat, it can be irradiated with light to impart conductivity.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1 Epoxy acrylate resin (manufactured by Showa High Polymer Co., Ltd.)
5 g of poly (5,6-dibutoxyisothianaphthene) having an average degree of polymerization of about 200 was added to a mixed solution of 45 g of lipoxy R-804) and 300 g of tetrahydrofuran, followed by heating and mixing. 7.3 g of diphenyliodonium tetrafluoroborate (Ph ₂ IBF ₄ ) was added and uniformly dispersed to prepare a dark blue uniform radically polymerizable composition.
Then, after applying this composition to a glass plate with a thickness of 2 μm using a bar coater, a high-pressure mercury lamp (output
900W / cm) UV curing in air using one lamp,
A light gray cured coating was obtained. The conductivity of this cured coating is 6 ×
It was 10 ^-3 S / cm. This conductivity did not change even after one month.

Comparative Example 1 Epoxy acrylate resin (manufactured by Showa Polymer Co., Ltd.
5 g of poly (3-dodecyl-2,5-thienylene) having an average degree of polymerization of about 200 was added to a mixed solution of 45 g of lipoxy R-804) and 300 g of tetrahydrofuran, followed by heating and mixing to prepare a homogeneous red solution. Thereafter, the same operation as in Example 1 was performed to obtain a red cured coating film. The conductivity of this cured coating film was 5 × 10 ⁻⁸ S / cm.

When the cured coating film was exposed to I ₂ vapor to perform doping, the cured coating film turned brown. When the conductivity of this cured coating film was measured, the value was 7 S / cm.
This conductivity dropped by four to six orders of magnitude after one week.

Comparative Example 2 Epoxy acrylate resin (manufactured by Showa Polymer Co., Ltd.
5 g of poly (3-dodecyl-2,5-thienylene) having an average degree of polymerization of about 200 was added to a mixed solution of 45 g of lipoxy R-804) and 300 g of tetrahydrofuran, followed by heating and mixing to prepare a homogeneous red solution. Thereafter, the same operation as in Example 1 was performed to obtain a red cured coating film. The conductivity of this cured coating film was 5 × 10 ⁻⁸ S / cm.

The cured coating film was impregnated with a solution of diphenyliodonium tetrafluoroborate in acetonitrile, taken out of the solution, and then subjected to the same ultraviolet irradiation as in Example 1, but the UV-V spectrum did not change and the conductivity did not change. Was.

Comparative Example 3 Epoxy acrylate resin (manufactured by Showa Polymer Co., Ltd.
5 g of poly (3-dodecyl-2,5-thienylene) having an average degree of polymerization of about 200 was added to a mixed solution of 45 g of lipoxy R-804) and 300 g of tetrahydrofuran, followed by heating and mixing to prepare a homogeneous red solution. Thereafter, the same operation as in Example 1 was performed to obtain a red cured coating film. The conductivity of this cured coating film was 5 × 10 ⁻⁸ S / cm.

This cured coating film was impregnated with a solution of diphenyliodonium tetrafluoroborate in acetonitrile, and the same ultraviolet irradiation as in Example 1 was performed in the solution. The cured coating turned blue and the conductivity increased to 5 × 10 ⁻⁴ S / cm, but after one week the conductivity decreased by three to four orders of magnitude.

[Effects of the Invention] The radical polymerization composition of the present invention is excellent in moldability, transparency and mechanical strength, and exhibits extremely stable conductivity in air. Therefore, the radical polymerizable composition of the present invention, in the field of electrical and electronic industry, the electrode of the display element,
It is useful as an electrochromic display element material, a printed circuit board circuit material, an antistatic material, an electromagnetic shielding material, and the like.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-64-20202 (JP, A) JP-A-61-47625 (JP, A) JP-A-59-215303 (JP, A) Pitchumani, et al. , Journal of the Chemical Society, Chemical Communications, 1983 (15) 809-810. Yoshino, et al. , Japanese Journal of Applied Physics, 1985 24 (1) 33-34 (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 65/00 C08G 61/12 C08K 5/00-5/59 CA ( STN) REGISTRY (STN)

Claims (12)

(57) [Claims] 1. A radically polymerizable composition comprising a compound having a π-electron conjugated structure soluble in an organic solvent represented by the following general formula [I], a radically polymerizable compound, and a photolytic oxidizing agent. . [In the formula, Z ₁ and Z ₂ each represent H, or a linear or branched alkyl group or alkoxyl group having 3 to 12 carbon atoms. m is a number from 5 to 5000 indicating the degree of polymerization. ] 2. The radically polymerizable composition according to claim 1, wherein the photolytic oxidizing agent is a compound represented by the following general formula [II] or [III]. [Wherein, Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ , Y ₈ and Y ₉ each represent H, a methyl group, a methoxy group, a hydroxyl group or a methylene group, and MX _n ⁻ Represents an anion composed of a metal and a halogen. ] 3. The radical polymerizable compound is a nucleus-substituted styrene compound, an acrylate compound, a methacrylate compound, a reaction product of an arylidene compound with a polythiol compound, an allyl compound, a vinylamide compound, or acrylamide. The radical polymerizable composition according to claim 1, wherein the radical polymerizable composition is at least one of a compound, an imide, a lactam, and a carbazole compound. 4. The radical polymerizable composition according to claim 1, wherein the radical polymerizable compound is styrene, epoxy acrylate or epoxy methacrylate, or a mixture thereof. 5. A compound having a π-electron conjugated structure of 0.1 to 40.
The radical polymerizable compound according to any one of claims (1) to (4), wherein the amount of the photolytic oxidizing agent is 0.01 to 40% by weight, and the amount of the radical polymerizable compound is 50 to 99.5% by weight. Composition. 6. A compound having a π-electron conjugated structure, a radically polymerizable compound and a photolytic oxidizing agent, comprising an aromatic hydrocarbon,
The method for producing a radically polymerizable composition according to claim 1, further comprising a step of dispersing or dissolving in a halogenated hydrocarbon, an ether compound or acetonitrile. 7. A method for producing a cured film, comprising applying the radically polymerizable composition according to any one of claims (1) to (5) to an insulator surface and polymerizing the same. 8. A method for producing an article in the form of a mold, characterized in that the radical polymerizable composition according to any one of (1) to (5) is cast into a mold and polymerized in the mold. Method. 9. The method according to claim 1, wherein light irradiation is performed.
(5) A method for producing a conductive cured product, which comprises doping the radically polymerizable composition according to any of (5) after or simultaneously with the polymerization. 10. A method for producing a conductive cured product, which comprises irradiating light after polymerizing the radically polymerizable composition according to any one of claims (1) to (5) with heat. 11. A doping method comprising irradiating the radically polymerizable composition according to any one of claims (1) to (5) with light to dope simultaneously with the polymerization. 12. The method according to claim 1, wherein the light irradiation is performed.
(5) A conductive cured product obtained by doping after or simultaneously with the polymerization of the radically polymerizable composition according to any of (5).