JPH06263825A - Highly dielectric polymer composition - Google Patents

Abstract

PURPOSE:To obtain a composition comprising a polymer having a high relative permittivity, exceedingly low hygroscopicity, and a low dielectric loss factor by copolymerizing a (meth)acrylic ester monomer containing a cyanoethyl group with a specific monomer to give the polymer. CONSTITUTION:This polymer composition contains a copolymer of a (meth) acrylic ester monomer containing a cyanoethyl group and represented by formula I with at least one monomer represented by formula II. In the formulae, 1<=m<=n-1; (m) is 1-3; R<1> is H or CH3; R<2> is a linear or branched alkyl which may have at least one of O, phenylene, hydrogenated phenylene, and amino; R<3> is H or CH3; R<4> is a single bond, an alkylene, or an ester group; and X is an aromatic hydrocarbon group, an aliphatic hydrocarbon group, an amide group, a cyclic amide group, an N-substituted amide group, or a fluoroalkyl.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high dielectric polymer composition, more specifically, a binder for an organic dispersion type electroluminescence (EL) which is an organic electronic material, a film capacitor dielectric material, a polymer battery, a piezoelectric pyroelectric material. The present invention relates to a composition comprising a polymer having a high relative dielectric constant, an excellent moisture absorption resistance, and a small dielectric loss coefficient.

[0002]

2. Description of the Related Art Binders of organic electronic materials, such as organic dispersion type EL binders, have high dielectric properties, low hygroscopicity for long life, and invariance of electrical characteristic values with temperature. It is required to have characteristics such as (heat resistance) and high adhesiveness with the phosphor and the electrode surface. Under these circumstances, as the organic polymer used for the binder for organic dispersion type EL, a high-dielectric polymer into which a cyano group having a high dipole efficiency is introduced, which is particularly effective for increasing the relative dielectric constant, is attracting attention. Has arrived. By the way, for example, polyvinyl alcohol and celluloses (glucose ring-containing cellulose, hydroxyethyl cellulose, etc.)
Cyanoethylated compounds of are known, but these polymers have a limited cyano group introduction rate due to steric hindrance, etc.,
Free hydroxyl groups (active hydrogen) remain in the molecule, leaving a problem of hygroscopicity. Furthermore, there are limitations in polymer design.
On the other hand, as another requirement, it is important that the high dielectric polymer has a small dielectric loss coefficient (tan δ). When the organic dispersion type EL element has a large dielectric loss coefficient, power loss becomes large, which is not preferable. Of course, the heat generated by the power loss raises the temperature of the organic dispersion type EL element itself. It is possible to accelerate the deterioration of In addition, the dielectric constant of the high dielectric polymer itself generally increases with this temperature rise. It is conjectured that this increase in the dielectric loss coefficient causes a vicious cycle in which the temperature also rises, and ultimately the deterioration of the phosphor rapidly progresses.

[0003]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made earnest studies on a high dielectric polymer having a high relative dielectric constant, no residual free hydroxyl groups, excellent moisture absorption resistance and a small dielectric loss coefficient. As a result, they have found that a copolymer composed of a novel cyanoethyl group-containing (meth) acrylic acid ester monomer and a specific copolymerizable monomer is suitable for the intended polymer, and completed the present invention.

That is, the present invention has the formula:

[Chemical 2] (In the formula, 1 ≦ m ≦ n−1, m is 1 to 3, R ¹ is H or C
H ₃ and R ² are a linear or branched alkylene group which may have at least one of an oxygen atom, a phenylene group, a hydrogenated phenylene group and an amino group). An acid ester monomer (hereinafter, referred to as cyanoethyl monomer) and a copolymer of copolymerized monomers (hereinafter, referred to as cyanoethyl copolymer), wherein the copolymerized monomer has the formula: (In the formula, R ³ is H or CH ₃ , R ⁴ is a single bond or an alkylene group or an ester group, and X is an aromatic hydrocarbon group, an alicyclic hydrocarbon group, an amide group, a cyclic amide group, N-
The present invention provides a high dielectric polymer composition characterized by being at least one kind of a monomer represented by a substituted amide group or a fluorinated alkyl group.

Throughout the specification, "(meth) acrylic" means acrylic or methacrylic, and "(meth) acrylate" means acrylate or methacrylate.

Cyanoethyl monomer [I] used in the present invention
Can be manufactured according to the following procedure. That is, first, the formula:

[Chemical 3] 1 mol of n-valent polyhydroxyl compound [II] of the present invention is subjected to a Michael addition reaction with 1 mol of acrylonitrile in the presence of an acid or alkali catalyst at a temperature of 20 to 100 ° C. for 1 to 48 hours to obtain a compound represented by the formula:

[Chemical 4] To obtain the cyanoethyl compound [III]. Here, the relationship between n and m is set so that 1 ≦ m ≦ n−1, and the obtained cyanoethyl compound [III] has (n−m) in the molecule.
Individual, ie one or more hydroxyl groups remain.

Examples of the polyhydroxyl compound [II] include ethylene glycol, propylene glycol, 2-methyl-1,3-propanediol, 1,3-butylene glycol, 1,6-hexanediol, neopentyl glycol and diethylene glycol. , Dipropylene glycol, triethylene glycol, bisphenol A, hydrogenated bisphenol A, 1,4-dimethylolcyclohexane, glycerin, trimethylolethane, trimethylolpropane, trishydroxymethylaminomethane, pentaerythritol and the like. Glycerin and pentaerythritol are preferred.

Next, with respect to the residual hydroxyl groups of the cyanoethyl compound [III], (n-m) mol of (meth) acrylic acid is added in the presence of an acid catalyst, usually at 50 to 150 ° C. and 4 to
By carrying out an esterification reaction (dehydration reaction) under the condition of 48 hours, a cyanoethyl monomer [I] having no residual hydroxyl group can be obtained.

Copolymerizable monomer used in the present invention
[IV] contributes to the reduction of the dielectric loss coefficient, and particularly polar groups,
A monomer having few polar bonds and small hydrophilicity is preferable. Specifically, aromatic vinyl compounds [eg, styrene, vinyltoluene, vinylnaphthalene, vinyl (alkyl) phenols, etc.], alicyclic or aromatic hydrocarbon-based (meth) acrylates [eg, dicyclopentenyl]
(Meth) acrylate, tricyclodecanyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, etc.],
Fluoroalkyl (meth) acrylate [eg 2,2,
2-trifluoroethyl methacrylate, 2,2,3,3
-Tetrafluoropropyl methacrylate, 2- (perfluoro-3-methylbutyl) ethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 1,1,1,3,3,3 3-hexafluoropropyl (meth) acrylate, etc.], (meth) acrylamide, aliphatic to alicyclic or aromatic hydrocarbon-based N-substituted (meth) acrylamide [eg N-dimethylacrylamide, N-dibutylacrylamide, N] -Diphenylacrylamide and the like] and N-vinylpyrrolidone, and one or a mixture of two or more thereof can be preferably used. The amount used is usually 50% (% by weight, the same applies hereinafter) or less, preferably 1 to 20% of the total amount of the monomers. If the amount used exceeds 50%, the relative dielectric constant of the cyanoethyl copolymer tends to be lowered.

The cyanoethyl copolymer in the present invention is a cyanoethyl monomer [I] and a copolymerized monomer.
[IV] can be produced by a usual polymerization method, for example, by subjecting it to bulk polymerization, solution polymerization, photopolymerization, etc. in the presence of a polymerization initiator and, if necessary, a chain transfer agent.

Examples of the above-mentioned polymerization initiator include peroxides (ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester, peroxydicarbonate, etc.) and azo-based initiators. 2,2'-azobis (4
-Methoxy-2,4-dimethylvaleronitrile), 2,2 '
-Azobis (2-cyclopropylpropionitrile),
2,2'-azobis (2,4-dimethylvaleronitrile),
2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano- 1-methylethyl) azo] formamide, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile and the like]. The amount used is usually 0.1 to 100 parts of cyanoethyl monomer [I] (parts by weight, the same applies hereinafter).
It may be selected in the range of 5 parts, preferably 0.1 to 1 part. If the amount used is unnecessarily large, the molecular weight of the cyanoethyl copolymer will decrease or it will remain as unreacted impurities, which will adversely affect the electrical properties.

Examples of the chain transfer agent include mercaptans which are generally used (for example, n-butyl mercaptan,
Aliphatic, aromatic, and alicyclic compounds such as octyl mercaptan, lauryl mercaptan, benzyl mercaptan, and cyclohexyl mercaptan). The amount used is usually 5 parts or less, preferably 1 part or less, based on 100 parts of the cyanoethyl monomer [I]. Also in this case, if the amount used is more than necessary, the same problems as those of the polymerization initiator tend to occur.

The high dielectric polymer composition according to the present invention is
A system in which an appropriate amount of the above-mentioned cyanoethyl copolymer and, if necessary, a resin such as an ordinary UV-curable resin composition, a thermosetting resin composition, a thermoplastic resin composition, a filler, a dye / pigment, and its commonly used additives are blended Composed of.

[0014]

The composition of the present invention having the above constitution is a polyhydroxyl compound in a cyanoethyl copolymer.
Depending on the type of [II] (increasing n), the introduction ratio of the cyano group can be increased, and generally has a relative dielectric constant of> 15 and T
By adjusting g and reducing the number of residual hydroxyl groups, it is possible to increase the degree of freedom in polymer design and improve the electrical properties, and also have a low dielectric loss coefficient (for example, 0.02).
~ 0.01) It can be a high dielectric material. Applications include insulating layers for organic dispersed EL devices, binders for light emitting layers and film capacitor dielectric materials, polymer batteries,
Application to piezoelectric pyroelectric materials can be mentioned.

[0015]

EXAMPLES The present invention will be described in detail with reference to Examples and Comparative Examples. Examples 1 to 11 (1) Production of cyanoethyl monomer To 136.15 g (1 mol) of pentaerythritol, 188 g of 4% sodium hydroxide solution was added and stirred in a four-necked flask. 164.1 g (3 mol) of acrylonitrile was added dropwise thereto, and the Michael addition reaction was completed while controlling the reaction temperature at 40 to 45 ° C. 680 g of acrylic acid and 36.7 p-toluenesulfonic acid were added to the obtained cyanoethyl compound.
g, and then 2.7 g of hydroquinone as a polymerization inhibitor are added, an esterification reaction is carried out in 1 liter of benzene under reflux, and then excess acrylic acid is washed off with water to obtain a cyanoethyl monomer. Regarding the cyanoethyl monomer, I
R analysis (manufactured by JASCO Corporation, IR-810, 35
OH disappearance at 50-3200 cm ^-1 and 2260-
Identification was confirmed by structure determination by CN absorption at 2240 cm ⁻¹ ) and number of protons by NMR analysis.

(2) Preparation of cyanoethyl copolymer In a four-necked flask, 0.1 g (0.0006 mol) of 2,2'-azobisisobutyronitrile and 0.1 of lauryl mercaptan were introduced.
1 g (0.0005 mol), N-dimethylformamide 10
0 g, the above-mentioned cyanoethyl monomer (1) and various copolymerizable monomers were charged in the composition (g) shown in Table 1 below, and the mixture was stirred under nitrogen gas at 60 ° C. for 3 hours for polymerization. Next, 300 g of methanol is added to precipitate the polymer component, and the mixture is washed several times with a mixed solution of methanol / water (50/50, weight ratio). Then, the solvent is dried under reduced pressure to obtain a cyanoethyl copolymer. The relative permittivity and the dielectric loss were measured at a predetermined temperature using an LCZ meter, and the results are also shown in Table 1.

[0017]

[Table 1]

Comparative Example 1 In a four-necked flask, 100 g of the same cyanoethyl monomer as in the Example, 0.1 g of 2,2'-azobisisobutyronitrile
(0.0006 mol), 0.1 g of lauryl mercaptan (0.1
0005 mol) and N-dimethylformamide 100 g
Is charged, and the mixture is stirred and polymerized at 60 ° C. for 3 hours under nitrogen gas. Next, 300 g of methanol is added to precipitate the polymer component, and the mixture is washed several times with a mixed solution of methanol / water (50/50, weight ratio). Then, the solvent is dried under reduced pressure to obtain a cyanoethyl homopolymer. The polymer had a relative permittivity of 17.5 and a dielectric loss of 0.028 at 20 ° C., and a relative permittivity of 21.0 and a dielectric loss of 0.18 at 60 ° C.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08F 220/34 MMT 7242-4J C08L 33/14 LHT 7921-4J

Claims (2)

[Claims] 1. The formula: (In the formula, 1 ≦ m ≦ n−1, m is 1 to 3, R ¹ is H or C
H ₃ and R ² are a linear or branched alkylene group which may have at least one of an oxygen atom, a phenylene group, a hydrogenated phenylene group and an amino group). A copolymer of an acid ester monomer and a copolymerization monomer, wherein the copolymerization monomer has the formula: (In the formula, R ³ is H or CH ₃ , R ⁴ is a single bond or an alkylene group or an ester group, and X is an aromatic hydrocarbon group, an alicyclic hydrocarbon group, an amide group, a cyclic amide group, N-
A high dielectric polymer composition comprising at least one monomer represented by a substituted amide group or a fluorinated alkyl group. 2. The copolymerization monomer is an aromatic vinyl compound, an alicyclic or aromatic hydrocarbon (meth) acrylate,
Fluoroalkyl (meth) acrylate, (meth) acrylamide, aliphatic to alicyclic or aromatic hydrocarbon N
The high dielectric polymer composition according to claim 1, which is selected from the group of -substituted (meth) acrylamide and N-vinylpyrrolidone and used in an amount of 50% by weight or less based on the total amount of monomers.