JP3121646B2 - Organic electronic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electronic material, and more particularly, to a binder made of a polymer having a high dielectric constant, a crosslinked type and excellent heat resistance, and a binder for an organic dispersion type electroluminescence (EL). The present invention relates to an electronic material useful as a dielectric material for a film capacitor.

[0002]

2. Description of the Related Art An organic electronic material, for example, a binder for EL, has a high dielectric property, invariance of electrical characteristics due to temperature (heat resistance), and a high degree of compatibility with phosphors and electrode surfaces. It is required to have properties such as adhesiveness. On the other hand, among these, as an organic polymer used for a binder for EL, a high dielectric polymer in which a cyano group having a high dipole efficiency, which is particularly effective for increasing the dielectric constant, has been attracting attention and has been brought to the present day. . By the way, for example, polyvinyl alcohol and celluloses
Cyanoethylated products (e.g., cellulose containing a glucose ring, hydroxyethylcellulose) are known.However, since they exhibit thermoplasticity, their dielectric properties are extremely reduced at temperatures exceeding their glass transition point, and they remain in the molecule. The problem of hygroscopicity remains due to the free hydroxyl groups.
Recently, as a polymer having high dielectric properties and having no free hydroxyl group, a polymer obtained by copolymerizing cyanoethyl vinyl ether and cyanoethyl acrylate has been developed [Yoshihiro Taguchi et al.
Vol. 2, No. (1990) "(pages 32 to 35)," High Dielectric Polymer Material "].

[0003]

Means for Solving the Problems The present inventors have intensively studied a new polymer for an organic electronic material which satisfies the conventional required characteristics and can exhibit dielectric properties comparable to those of the developed polymer. By introducing an alkoxysilyl crosslinkable functional group into a polymer comprising a novel cyano group-containing acrylic monomer alone or in combination with a copolymerizable monomer, there is no problem of hygroscopicity,
It has been found that a high-dielectric cross-linkable polymer having excellent heat resistance and solvent resistance with a dielectric constant of 15 to 25 can be obtained,
The present invention has been completed.

That is, the present invention provides a compound represented by the following formula:

Embedded image (Where 1 ≦ nm, n is 2 to 4, m is 1 to 3, R ¹ is H or CH ₃ , and R ² is at least one of an oxygen atom, a phenylene group, a hydrogenated phenylene group and an amino group. A cyano group-containing acrylic monomer represented by the formula:
A polymer obtained from a species and, if necessary, at least one of a comonomer and a chain transfer agent, wherein at least one of the copolymerizable monomer and the chain transfer agent has an alkoxysilyl crosslinkable functional group. It is an object of the present invention to provide an organic electronic material comprising a viscous liquid high dielectric crosslinked polymer.

The cyano group-containing acrylic monomer used in the present invention can be roughly classified into two methods. Hereinafter, the manufacturing method for each will be described.

Part 1: One mole of acrylonitrile is added to one mole of 2-hydroxyethyl (meth) acrylate to form a compound having the formula:

Embedded image To obtain a cyano group-containing acrylic monomer. The addition reaction may be performed using a reaction solvent (for example, benzene, toluene,
(Ethyl acetate, dimethylformamide, acetonitrile)
, A suitable amount of a basic catalyst such as Triton B (trimethylbenzylammonium salt) or a polymerization inhibitor such as hydroquinone is added, and the reaction may be performed at a temperature of 10 to 50 ° C. for 4 to 48 hours. In addition, throughout this specification, "(meta)
“Acrylate” refers to acrylate or methacrylate, “(meth) acrylic acid” refers to acrylic acid or methacrylic acid, and “(meth) acryloxy” refers to acryloxy or methacryloxy.

Part 2: First, the equation:

Embedded image 1 mole of an n-valent polyhydroxyl compound of the formula is reacted with an addition reaction of mmol of acrylonitrile to obtain

Embedded image To obtain a cyanoethyl compound. The addition reaction may be performed using a reaction solvent (for example, toluene, benzene, ethyl acetate, dimethylformamide, acetonitrile) if necessary.
B (trimethylbenzylammonium salt), a basic catalyst such as sodium hydroxide solution and a polymerization inhibitor such as hydroquinone are added in an appropriate amount, and the mixture is heated at a temperature of 20 to 100 ° C and a temperature of 1 to 48 ° C.
It may be performed under the condition of time.

The polyhydroxyl compounds include, for example, ethylene glycol, propylene glycol,
-Methyl-1,3-propanediol, 1,3-butylene glycol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol, bisphenol A,
Examples include hydrogenated bisphenol A, 1,4-dimethylolcyclohexane, glycerin, trimethylolethane, trimethylolpropane, trishydroxymethylaminomethane, and pentaerythritol, and glycerin and pentaerythritol are particularly preferred.

Next, (nm) mole of (meth) acrylic acid is added to the remaining hydroxyl groups of the cyanoethyl compound at 50 to 150 ° C. for 4 to 48 hours in the presence of an acid catalyst. By performing an esterification reaction (dehydration reaction), a cyano group-containing acrylic monomer having no residual hydroxyl group is obtained.

In the present invention, as the copolymerizable monomer which can be used in combination with the cyano group-containing acrylic monomer, if necessary, i) an alkoxysilyl crosslinkable functional group can be introduced into a desired highly dielectric crosslinked polymer. They are broadly classified into copolymerized monomers and ii) other copolymerized monomers. Hereinafter, specific examples in each case are listed.

[0011] The copolymerized monomer formula of i) :

Embedded image (Wherein R ³ is an alkyl group having 1 to 4 carbon atoms, X is a methoxy group or an ethoxy group, and a is 0, 1 or 2)
Vinylalkoxysilanes (e.g., vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinyldimethylmethoxysilane, etc.),
And the formula:

Embedded image (Wherein R ⁴ is H or CH ₃ , R ⁵ is a divalent hydrocarbon group,
R ⁶ is an alkyl group having 1 to 4 carbon atoms, Y is a methoxy group or an ethoxy group, and b is 0, 1 or 2) (meth) acryloxyalkoxysilane [for example, γ- (meth)
Acryloxypropyltrimethoxysilane, γ- (meth)
Acryloxypropylmethyldimethoxysilane, γ-
(Meth) acryloxypropyltriethoxysilane, γ-
(Meth) acryloxypropylmethyldiethoxysilane, etc.).

Ii) Copolymerization monomer acrylic acid ester (for example, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, etc.) ), Methacrylates (e.g., methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, etc.), styrene or derivatives thereof (α-methylstyrene, chloromethylstyrene Etc.),
Fumaric acid diesters (diethyl fumarate, dibutyl fumarate, dipropyl fumarate, etc.), vinyl halides (vinyl chloride, vinylidene chloride, ethylene fluoride, vinylidene fluoride, vinylene fluoride, etc.), vinyl acetate,
Examples thereof include vinyl propionate, vinyl versatic acid (manufactured by Shell Chemical Co., Beova), acrylonitrile, acrylamide, vinylpyridine, vinylpyrrolidone, butadiene and the like.

These copolymer monomers i) and ii) are used to adjust the mechanical strength and various physical properties of the highly dielectric crosslinked polymer or to introduce a crosslinkable functional group, and to have a high dielectric property. May be used in an amount that does not detrimentally affect the total amount of the monomer including the cyano group-containing acrylic monomer in an amount of 50% by weight or less. The copolymerizable monomer of the above-mentioned i) for the purpose of introducing a crosslinkable functional group may be used in an amount of 0.1 to 5% by weight based on all the monomers.

As the chain transfer agent used in the present invention, mercaptans generally used (for example, n-butyl mercaptan, octyl mercaptan, lauryl mercaptan, benzyl mercaptan, cyclohexyl mercaptan, etc.) may be used, but high dielectric constants may be used. In order to introduce an alkoxysilyl crosslinkable functional group into the crosslinked polymer, the above i)
A chain transfer agent having an alkoxysilyl crosslinkable functional group instead of or in combination with the copolymerized monomer of the formula:

Embedded image (Wherein, R ⁷ is a divalent hydrocarbon group, R ⁸ is an alkyl group having 1 to 4 carbon atoms, Z is a methoxy group or an ethoxy group, and
c is 0, 1 or 2) mercaptoalkoxysilane [eg γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-
Mercaptopropylmethyldimethoxysilane, mercaptomethylethyldimethoxysilane, mercaptomethylethyldiethoxysilane, mercaptoethylmethyldimethoxysilane, mercaptoethylmethyldiethoxysilane, mercaptoethylethyldimethoxysilane, mercaptoethylethyldiethoxysilane, mercaptopropylethyldimethoxysilane , Mercaptopropylethyldiethoxysilane, mercaptobutylmethyldimethyl (ethoxy) silane, mercaptobutylethyldimethyl (ethoxy) silane or a disulfide compound thereof [for example, bis
(Trime (d) ethoxysilylmethyl) disulfide, bis
(Trime (d) ethoxysilylethyl) disulfide, bis
(Trime (e) ethoxysilylpropyl) disulfide, bis
(Trime (d) toxoxysilylbutyl) disulfide, bis
(Methyldimethyl (e) toxisilylmethyl) disulfide, bis (methyldim (e) toxisilylethyl) disulfide,
Bis (methyldim (e) toxilylpropyl) disulfide, bis (methyldim (e) toxilylbutyl) disulfide, bis (ethyldim (e) toxilylmethyl) disulfide, bis (ethyldim (e) toxilylethyl) disulfide, bis ( (Ethyl dime (e) toxicsilyl propyl)
Disulfide, bis (ethyldim (e) toxilylbutyl) disulfide, bis (propyldim (e) toxilylmethyl) disulfide, bis (propyldim (e) toxilylethyl) disulfide, bis (propyldim (e) toxilylpropyl) disulfide, Bis (propyldime
(E) ethoxysilyl butyl) disulfide, bis (dimethylme (E) ethoxysilylmethyl) disulfide, bis (dimethylme (E) ethoxysilylethyl) disulfide, bis (dimethylme (E) ethoxysilylpropyl) disulfide, Bis
(Dimethylme (e) toxisilylbutyl) disulfide, bis (diethylme (e) toxisilylmethyl) disulfide,
Bis (diethylme (e) toxisilylethyl) disulfide, bis (diethylme (e) toxisilylpropyl) disulfide, bis (diethylme (e) toxisilylbutyl) disulfide, bis (dipropylme (e) toxisilylmethyl)
Disulfide, bis (dipropylme (e) ethoxysilylethyl) disulfide, bis (dipropylme (e) toxisilylpropyl) disulfide, bis (dipropylme (e) toxisilylbutyl) disulfide, etc.] can be used. In addition, the above “me (ethoxy) ethoxy” refers to methoxy or ethoxy.

The amount of the chain transfer agent used is usually from 0 to 5 based on 100 parts of the cyano group-containing acrylic monomer.
Parts, preferably in the range of 0 to 1 part.

By subjecting the above-mentioned cyano group-containing acrylic monomer and, if necessary, copolymer monomers i) and ii) to radical polymerization in the presence of a chain transfer agent or a polymerization initiator, the desired high dielectric cross-linking type is obtained. Polymers can be produced. 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobisisovaleronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide as a polymerization initiator Known polymerization methods using t-butyropoxide, methyl ethyl ketone peroxide and the like, for example, bulk polymerization, solution polymerization and the like may be used, and a redox catalyst (transition metal salt,
Redox polymerization using a combination of an amine or the like) and a peroxide-based polymerization initiator may be performed.

The resulting highly dielectric crosslinked polymer has an alkoxysilyl crosslinkable functional group introduced by the use of a copolymerization monomer i) and / or a chain transfer agent having an alkoxysilyl crosslinkable functional group. Both the case of using a cyano group-containing acrylic monomer alone and the case of using a copolymerization monomer are polymers exhibiting a viscous liquid, and are usually preferably set to have an average molecular weight of 1,000 to 50,000.

The organic electronic material according to the present invention comprises the above-mentioned highly dielectric cross-linked polymer, and may be added with a usual thermoplastic resin, thermosetting resin, ultraviolet cross-linkable resin, filler, dye or pigment, if necessary. Agents and the like are used in appropriate amounts.

[0019]

The organic electronic material of the present invention having the above constitution has a high dielectric constant of 15 to 25, and is particularly excellent in heat resistance due to moisture crosslinking of alkoxysilyl crosslinking functional groups. Or as a film capacitor dielectric material.

[0020]

Next, the present invention will be described more specifically with reference to examples and comparative examples. Example 1 (1) Production of cyano group-containing acrylic monomer To 136.15 g (1 mol) of pentaerythritol, 188 g of a 4% sodium hydroxide solution was added and stirred in a four-necked flask. Acrylonitrile (164.1 g, 3 mol) is added dropwise thereto, and the addition reaction is completed while controlling the reaction temperature at 40 to 45 ° C. 680 g of acrylic acid and 36.7 parts of p-toluenesulfonic acid were added to the resulting cyanoethyl compound.
g, and 2.7 g of hydroquinone as a polymerization inhibitor. The esterification reaction is carried out under reflux in 1 liter of benzene, and excess acrylic acid is washed away with water to obtain a cyano group-containing acrylic monomer. The cyano group-containing acrylic monomer was subjected to IR analysis (manufactured by JASCO Corporation, I
OH at 3550-3200 cm ^-1 using R-810
Extinction and CN absorption at 2260-2240 cm ^-1 )
And the identification was confirmed by the number of protons by NMR analysis.

(2) Production of high dielectric cross-linked polymer 1 g of 2,2'-azobisisobutyronitrile and γ-mercaptopropyltrimethoxysilane (100 g of cyano group-containing acrylic monomer of (1) above) Co., Ltd., K
BM-803) 0.5 g and γ-methacryloxypropyltrimethoxysilane (KBM-50 manufactured by Shin-Etsu Chemical Co., Ltd.)
3) After adding 1 g, the mixture was adjusted to a 50% acetonitrile solution, and polymerized at 80 ° C. for 2 hours under a nitrogen stream to obtain a highly dielectric crosslinked polymer product. The highly dielectric crosslinked polymer was a viscous substance having a molecular weight of 6000 (in terms of GPC).

(3) Crosslinking reaction After removing acetonitrile and unreacted materials from the highly dielectric crosslinked polymer product of (2), an alkyltin catalyst is used.
0.5% by weight (manufactured by Sankyoki Co., Ltd.) was added, and after heating and defoaming, applied on a 1 mm-thick aluminum plate at 200 μm and humidified at 35 ° C. and 95% RH for 3 days. After performing a crosslinking reaction, it is dried at 80 ° C. under reduced pressure for 5 hours to form a film.

(4) Dielectric properties The film of (3) above was subjected to aluminum deposition as an electrode, and an LCZ meter (manufactured by NF Circuit Block: 2322) was used.
After measuring the capacitance using, the relative dielectric constant was calculated by the following equation. The results are shown in Table 1 below.

(Equation 1)

(5) Heat resistance / solvent resistance Heat resistance was evaluated by a creep test at 80 ° C./100 g.
(75 μm PET film: 2 cm ² wrap area). Solvent resistance is determined by curing a film (2) in various solvents (see Table 1).
00 μm, 4 cm ² ), and the appearance change after 24 hours was examined. Table 1 shows the results.

Example 2 In Example 1 / (2), Example 1 was used as a monomer component.
A high dielectric cross-linked polymer is obtained in the same manner except that 50 g of the cyano group-containing acrylic monomer and 50 g of ethyl acrylate in (1) are used. This highly dielectric crosslinked polymer was subjected to a crosslinking reaction according to the description of Examples 1 / (3) to (5), and then subjected to a dielectric property test and a heat resistance / solvent resistance test. Show.

Example 3 (1) Production of cyano group-containing acrylic monomer In a 300 ml flask, 52.1 g (0.4 mol) of 2-hydroxyethyl methacrylate was added, and 0.58 g of trimethylbenzylammonium salt was added as a catalyst. Then, 21.9 g (0.4 mol) of acrylonitrile and 0.2 g of a polymerization inhibitor hydroquinone were added, and the reaction temperature was raised to 40 ° C.
And stir for 24 hours. Unreacted substances are removed by washing with water to obtain a cyano group-containing acrylic monomer. I
The structure was determined by R analysis (confirmation of OH annihilation and CN absorption), and identification was confirmed by the number of protons by NMR analysis.

(2) Production of high dielectric cross-linked polymer To 100 parts of the cyano group-containing acrylic monomer of (1), 1 part of glycidyl methacrylate was added, and then 2,2'-azobisisobutyi was used as a polymerization initiator. 1 part of lonitrile and 0.5 part of γ-mercaptopropyltrimethoxysilane as a chain transfer agent were added to adjust the solution to a 50% acetonitrile solution, and then 80% in a four-necked flask under a nitrogen stream.
The polymerization reaction is carried out at a temperature of 2 hours. The resulting highly dielectric crosslinked polymer was a viscous material having a molecular weight of 7,000.

(3) Cross-linking reaction After removing the residual solvent of the high dielectric cross-linked polymer of (2), 100 parts of the polymer was used as a cross-linking agent for 4,4 ′.
A 10% acetone solution of diaminodiphenylmethane 20
And cured at 120 ° C. for 2 hours. The thickness of the cured product was adjusted to 200 μ.

Next, according to the description of Examples 1 / (4) and (5), the samples were subjected to dielectric properties and heat / solvent resistance tests. The results are shown in Table 1.

Comparative Example 1 The cyano group-containing acrylic monomer 10 of Example 1 / (1)
To 0 g, 1 g of 2,2′-azobisisobutyronitrile as a polymerization initiator and 0.5 g of lauryl mercaptan as a chain transfer agent were added, and the mixture was adjusted to a 50% acetonitrile solution. Polymerized. The obtained polymer was a viscous substance having a molecular weight of 6,000 (in terms of GPC). Table 1 shows the dielectric properties and heat resistance / solvent resistance results of this polymer.

Comparative Example 2 A viscous polymer having a molecular weight of 7000 was obtained in the same manner as in Comparative Example 1, except that 100 g of the cyano group-containing acrylic monomer of Example 3 / (1) was used. Table 1 shows the results of the solvent resistance.

[0032]

[Table 1]

From the results shown in Table 1, in Examples 1 to 3,
Since it is liquid and then cured after application, a highly dielectric material having excellent film-forming properties can be obtained, and furthermore excellent in heat resistance / solvent resistance, it is useful as a binder for various electronic materials, especially organic dispersion EL. Is recognized.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-200595 (JP, A) JP-A-57-179210 (JP, A) JP-A-59-78221 (JP, A) JP-A-62 119254 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 20/36 C08F 230/08 H01G 4/18 327

Claims (3)

(57) [Claims] 1. The formula: (Wherein 1 ≦ nm, n is 2 to 4 , m is 1 to 3, R ¹ is H or CH ₃ , and R ² is at least one of an oxygen atom, a phenylene group, a hydrogenated phenylene group and an amino group. A cyano group-containing acrylic monomer represented by the formula:
A polymer obtained from a species and, if necessary, at least one of a comonomer and a chain transfer agent, wherein at least one of the copolymerizable monomer and the chain transfer agent has an alkoxysilyl crosslinkable functional group. An organic electrode comprising a viscous liquid highly dielectric cross-linked polymer.
Child material . 2. A copolymerizable monomer having an alkoxysilyl crosslinkable functional group, such as vinylalkoxysilane and
The organic electronic material according to claim 1, wherein at least one kind of (meth) acryloxyalkoxysilane is used. 3. The organic electronic material according to claim 1, wherein mercaptoalkoxysilane is used as a chain transfer agent having an alkoxysilyl crosslinkable functional group.