JP5740893B2 - Hard coat composition, hard coat film and display device - Google Patents

Description

The present invention relates to a hard coat composition having antistatic properties, a hard coat film and a display device using the hard coat composition.

Various optical films (antireflection film, antifouling film, etc.) and optical filters typified by flat panel display applications are often provided with a hard coat layer or antistatic layer to prevent scratches and dust adhesion. . High transparency is required for the hard coat layer and the antistatic layer used in such optical applications. The antistatic layer is required to have a surface resistance of about 10 ⁶ to 10 ¹² Ω. Furthermore, in such applications, stable antistatic properties are important, and there is a demand for a material that does not increase in resistance value and decrease in antistatic performance over time.
In response to such demands, conventionally, as an antistatic paint having hard coat properties, fine particles of transparent inorganic conductive oxides such as ITO (tin oxide doped indium oxide) and ATO (tin oxide antimony oxide), Hard coat resin compositions dispersed in various curable resins have been used.

As a method for forming a conductive film as an antistatic property, a method in which particles of In ₂ O ₃ or SnO ₂ are dispersed in an organic solvent is also known (see, for example, Patent Document 1). Therefore, although the conductive film can be formed at low cost, the resistance value is easily affected by the dispersibility of the inorganic conductive oxide, and the antistatic property is unstable. In addition, the transparent conductive film produced by printing, coating and firing the ITO powder described above, the volatile components and pyrolysis components escape from the film during drying and firing, so that voids remain after removal. Since it becomes a porous film and the bond between the substrate and the ITO powder and the ITO powder is weak, there is a drawback that the film lacks the strength and the adhesion is poor. Furthermore, since the intrinsic refractive index of an inorganic conductive oxide is greatly different from that of an organic resin, when it is added in a large amount, haze increases and transparency is impaired.

Further, as the antistatic resin composition, an antistatic resin composition in which a conductive polymer is dissolved or dispersed in a solvent and a hard coat component is mixed can be considered. However, conductive polymers are usually insoluble and infusible, and are poorly workable, so they do not dissolve and disperse uniformly in the resin composition, and even when formed into a coating film, they are inferior in transparency, film strength, and adhesion. There was a trend.

In order to solve such a problem, a conductive polymer that can be dissolved in a solvent by introducing a lipophilic substituent into the structure of the conductive polymer has been disclosed (see, for example, Patent Document 2).
In addition, a soluble conductive polymer including a solubilized polymer component having an anionic group and / or an electron-withdrawing group in the molecule and a conductive polymer component has been proposed (see, for example, Patent Document 3).

JP-A-4-26768 Japanese Patent No. 3024867 Japanese Patent No. 4350597

However, since the conductive polymer described in Patent Document 2 contains a bulky alkyl chain that does not contribute to conductivity, the conductive polymer is soluble in a solvent and can be mixed into a hard coat resin. Although possible, there is a problem that a well-balanced composition having excellent conductivity and excellent storage stability cannot be prepared.

Moreover, in the soluble conductive polymer described in Patent Document 3, in order to stably dissolve this soluble conductive polymer in a solvent, the ratio of the soluble conductive polymer must be increased. The compatibility with a hard-coat component fell, and the problem that electroconductivity fell will generate | occur | produce.

That is, in the hard coat composition containing the current conductive polymer and the hard coat component, excellent conductivity (antistatic property) is maintained, and the compatibility between the conductive polymer and the hard coat component is maintained. It has been difficult to simultaneously ensure that it has a high hardness when it is ensured, further preserves storage stability, and forms a hard coat layer.

An object of this invention is to provide the composition for hard-coats which was excellent in antistatic property and storage stability, was highly transparent, and was excellent in adhesiveness with a base material. Furthermore, it aims at providing the hard coat film and display device using this.

As a result of intensive studies to solve the above problems, the present inventors have found that a hard coat composition containing a specific heterocyclic ring-containing aromatic polymer that is a conductive polymer, a curable resin, and a crosslinking agent. In addition to satisfying the required properties (hardness, scratch resistance, transparency, haze, etc.) required for the hard coat agent, the composition for hard coat is excellent in antistatic property and storage stability, and the hard coat film and The present invention was completed by finding out that it can be suitably used for a display device.

That is, the present invention
(A) Heterocycle-containing aromatic polymer MN (1) having a heterocycle-containing aromatic compound represented by the following general formula (1) as a monomer
(In the formula, M represents a substituted or unsubstituted thiophene ring group, and N represents a substituted or unsubstituted pyrrole ring group. The ring represented by M and the ring represented by N are directly bonded to each other. ),
(B) a curable resin, and
(C) It is related with the composition for hard-coats which consists of a resin composition containing a crosslinking agent and has antistatic property.

In the hard coat composition of the present invention, the heterocycle-containing aromatic compound is preferably a heterocycle-containing aromatic compound represented by the following general formula (2 ′),

(In the formula, R ³ and R ⁴ each independently represent a hydrogen atom or an organic group, but at least one represents an organic group. When both R ³ and R ⁴ represent an organic group, these May be bonded to each other to form a ring structure.)
More preferably, it is at least one of the heterocyclic ring-containing aromatic compounds represented by the following structural formulas (2-1) to (2-10).

In the hard coat composition of the present invention, the curable resin preferably contains a polyfunctional acrylate or polyfunctional methacrylate, or contains a silicon-containing organic-inorganic hybrid resin.

The composition for hard coat of the present invention preferably contains an organic solvent.

The hard coat film of the present invention comprises an antistatic hard coat layer formed using the hard coat composition of the present invention.
Moreover, the display device of the present invention has the hard coat film of the present invention.

The composition for hard coat of the present invention contains a specific heterocyclic ring-containing aromatic polymer having a coupling body in which a thiophene ring group and a pyrrole ring group are directly bonded as a conductive polymer. Since this heterocyclic ring-containing aromatic polymer is excellent in solvent solubility and extremely excellent in compatibility with the curable resin, a coating film (hard coat layer) is formed using the hard coat composition of the present invention. Thereby, the hard-coat layer excellent in adhesiveness with a base material and film | membrane intensity | strength can be formed. In addition, since it is highly compatible with various curable resins, it is uniformly dispersed, so that functions can be achieved with a small addition amount, and transparency is improved.
In addition, since the above heterocycle-containing aromatic polymer is excellent in compatibility with various curable resins, it has a high degree of freedom in selecting a curable resin and can be used in combination with an optimal curable resin according to required characteristics. .
The hard coat composition of the present invention is stably stored for a long period of time without causing precipitation or gelation of constituent components over a long period of time due to the characteristics of the heterocyclic ring-containing aromatic polymer described above. be able to.
In addition, since the hard coat composition of the present invention contains a crosslinking agent, the network structure of the curable resin can be made dense and the crosslinking density can be increased. As a result, the hardness of the hard coat layer can be increased. Can be increased.
Moreover, the composition for hard-coats of this invention can be used conveniently for preparation of a hard-coat film, or manufacture of a display device using this hard-coat film.

It is sectional drawing which shows the hard coat film of this invention typically.

First, the hard coat composition of the present invention will be described.
The composition for hard coat of the present invention is:
(A) a heterocycle-containing aromatic polymer having the heterocycle-containing aromatic compound represented by the general formula (1) as a monomer,
(B) a curable resin, and
(C) It consists of a resin composition containing a crosslinking agent and has antistatic properties.
Hereinafter, each component which comprises the composition for hard-coats of this invention is demonstrated in order.

(A) Heterocycle-containing aromatic polymer The heterocycle-containing aromatic polymer contains a heterocycle-containing aromatic compound represented by the following general formula (1) as a monomer.
MN ... (1)
(In the formula, M represents a substituted or unsubstituted thiophene ring group, and N represents a substituted or unsubstituted pyrrole ring group. The ring represented by M and the ring represented by N are directly bonded to each other. Yes.)

Here, the thiophene ring group means a 2-thienyl group, and may have a substituent on a carbon atom.
The pyrrole ring group means a 2-pyrrolyl group, and may have a substituent on a carbon atom or a nitrogen atom.

Examples of the substituted thiophene ring group represented by M in the general formula (1) include the following structures.

(In each formula, n represents an integer of 1 to 10.)

Examples of the substituted pyrrole ring group represented by N in the general formula (1) include the following structures.

(In each formula, n represents an integer of 1 to 10.)

(In each formula, n represents an integer of 1 to 10, and R represents an aromatic group which may have a substituent or an alkyl group having 1 to 10 carbon atoms.)

Examples of the substituent of the thiophene ring group include an organic group described later, and an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 5 carbon atoms is preferable.
Examples of the substituent of the pyrrole ring group include an organic group described later, and the substituent on the carbon atom is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. As the substituent on the nitrogen atom, an alkyl group having 1 to 10 carbon atoms or an optionally substituted phenyl group is preferable.
Here, a functional group such as a halogen element, a carboxylic acid group, or a sulfonic acid group may be bonded to the alkyl group or alkoxy group that is a substituent of the thiophene ring group or the pyrrole ring group.

In the heterocyclic ring-containing aromatic compound represented by the general formula (1) (hereinafter also referred to as the heterocyclic ring-containing aromatic compound (1)), the thiophene ring and the pyrrole ring are connected via an atom not included in the ring structure. Are not directly bonded, but are directly bonded by a bond between atoms contained in both rings.
As the heterocyclic ring-containing aromatic compound (1), the total number of substituents bonded to the 3-position or 4-position of the thiophene ring group or the pyrrole ring group is from the viewpoint of solvent solubility, heat resistance, and weather resistance. Two or more compounds are preferred. In addition, in order to avoid steric hindrance when the total number of substituents bonded to the 3-position or 4-position is 4 (that is, when the substituents are bonded to all the 3-position and 4-position). In addition, in at least one of M and N, the 3-position substituent and 4-position substituent are preferably bonded to form a ring structure.

In the heterocycle-containing aromatic compound (1), at least one carbon atom on the thiophene ring represented by M is unsubstituted and at least one carbon atom on the pyrrole ring represented by N Is unsubstituted. When such a heterocyclic ring-containing aromatic compound (1) is oxidatively polymerized as a monomer, a coupling reaction proceeds between unsubstituted carbon atoms, so that the repeating unit is -M as a heterocyclic ring-containing aromatic polymer. A linear polymer represented by -N- is obtained.
It is preferable that the thiophene ring and the pyrrole ring represented by M and N are bonded to each other between one of the 2-position carbon atoms and the other 2-position carbon atom is unsubstituted.

As said heterocyclic ring-containing aromatic compound, the heterocyclic ring-containing aromatic compound represented by either the following general formula (2) or (3) is preferable.
When oxidative polymerization is performed using these heterocyclic ring-containing aromatic compounds as monomers, the oxidative polymerization is performed at the 2-position unsubstituted carbon atom on the thiophene ring or the 2-position unsubstituted carbon atom on the pyrrole ring. proceed.

In the heterocyclic ring-containing aromatic compound represented by the following general formula (2), M in the general formula (1) is a thiophene ring group that may have a substituent at the 3-position and / or 4-position, and N is It is a pyrrole ring group that may have a substituent at the 3-position and / or 4-position.

In general formula (2), R ¹ and R ² each independently represent a hydrogen atom or an organic group, but at least one of them represents an organic group, and R ³ and R ⁴ each independently represent It represents a hydrogen atom or an organic group (case i), or R ¹ and R ² both represent a hydrogen atom, and R ³ and R ⁴ each independently represent an organic group (case ii).
Here, when both R ¹ and R ² represent an organic group, they may be bonded to each other to form a ring structure, and when both R ³ and R ⁴ represent an organic group, They may combine with each other to form a ring structure. Examples of such a ring structure include a ring structure formed by an ethylenedioxy group.

The heterocyclic ring-containing aromatic compound represented by the general formula (2) is a compound in which, in case i, R ¹ and R ² each independently represent an organic group, and these are bonded to each other to form a ring structure, In case ii, a compound in which R ³ and R ⁴ each independently represents an organic group and these are bonded to each other to form a ring structure is preferable. In case i, R ¹ and R ² are each independently an organic group. And a compound in which they are bonded to each other to form a ring structure is more preferable.

More preferably, in case i, a heterocyclic ring-containing aromatic compound represented by the following general formula (2 ′) in which R ¹ and R ² are bonded to each other to represent an ethylenedioxy group.

Particularly preferably, in order to achieve both high conductivity and stability, the compound has a small band gap and a high oxidation potential, and is a compound represented by the following structural formulas (2-1) to (2-10). is there.
The heterocyclic ring-containing aromatic polymer having these compounds as monomers is extremely excellent in compatibility with a curable resin (hard coat component) described later and solvent solubility, and the heterocyclic ring-containing aromatic polymer has a band. This is because excellent conductivity can be imparted to the hard coat composition of the present invention due to the small gap and high oxidation potential.

In the heterocyclic ring-containing aromatic compound represented by the following general formula (3), M in the general formula (1) is a thiophene ring group that may have a substituent at the 3-position and / or 4-position, and N is It is an N-substituted pyrrole ring group which may have a substituent at the 3-position and / or the 4-position.

In general formula (3), R ⁵ and R ⁶ each independently represent a hydrogen atom or an organic group, but at least one of them represents an organic group, and R ⁷ and R ⁸ are each independently It represents a hydrogen atom or an organic group (case i), or R ⁵ and R ⁶ both represent a hydrogen atom, and R ⁷ and R ⁸ each independently represent an organic group (case ii).
Here, when both R ⁵ and R ⁶ represent an organic group, they may combine with each other to form a ring structure, and when both R ⁷ and R ⁸ represent an organic group, They may combine with each other to form a ring structure. Examples of such a ring structure include a ring structure formed by an ethylenedioxy group. Further, in the general formula (3), Rn ¹ represents an organic group.

In the case i, the heterocyclic ring-containing aromatic compound represented by the general formula (3) is a compound in which R ⁵ and R ⁶ each independently represent an organic group, and these are bonded to each other to form a ring structure, In case ii, a compound in which R ⁷ and R ⁸ each independently represents an organic group and these are bonded to each other to form a ring structure is preferred. In case i, R ⁵ and R ⁶ are each independently an organic group. And a compound in which they are bonded to each other to form a ring structure is more preferable.

More preferably, in case i, a heterocyclic ring-containing aromatic compound represented by the following general formula (3 ′) in which R ⁵ and R ⁶ are bonded to each other to represent an ethylenedioxy group.

In particular, in the general formula (3 ′), a compound represented by the following general formula (3 ″) in which R ⁷ and R ⁸ represent a hydrogen atom and Rn ¹ represents a phenyl group which may have a substituent is preferable. .

In the general formulas (2), (3), and (3 ″), examples of the organic group represented by each of R ^{1 to} R ⁸ , Rn ¹ , and Rx include, for example, linear or branched having 1 to 10 carbon atoms Or a cyclic alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a s-butyl group, a t-butyl group, a hexyl group, a cyclohexyl group, etc.), a straight chain having 1 to 10 carbon atoms Branched or cyclic alkenyl groups (for example, ethylene group, propylene group, butane-1,2-diyl group, cyclohexenyl group, etc.), alkoxy groups having 1 to 5 carbon atoms (for example, methoxy group, ethoxy group, iso Propoxy group etc.), optionally substituted phenyl group (eg phenyl group, tolyl group, dimethylphenyl group, biphenyl group, cyclohexylphenyl group etc.), aralkyl group For example, a benzyl group, phenethyl group, etc.), an alkoxycarbonyl group (for example, methoxycarbonyl group) and the like.
Furthermore, for example, functional groups such as carboxyl group, amino group, nitro group, cyano group, sulfonic acid group and hydroxyl group, and halogen elements such as fluorine, chlorine, bromine and iodine are bonded to these organic groups. Also good.
R ^{1 to} R ⁸ may be a carboxyl group, an amino group, a nitro group, a cyano group, a sulfonic acid group, a hydroxyl group, a halogen element, or the like.
The above organic groups are independently selected.

The organic group represented by R ^{1 to} R ⁸ is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and the organic group represented by Rn ¹ is an alkyl group having 1 to 10 carbon atoms, Alternatively, a phenyl group is preferable, and a phenyl group is particularly preferable.

Adjacent R ^{1 to} R ⁸ (R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁷ and R ⁸ ) are both organic groups, and they are bonded to each other to form a ring structure In this case, the ring structure is not particularly limited, but an alicyclic structure having 2 to 10 carbon atoms is preferable.
The alicyclic structure may contain an oxygen atom, a silicon atom, a sulfur atom, a nitrogen atom and the like, and among them, a ring structure having an alkylenedioxy group containing an oxygen atom is particularly preferable.
Furthermore, the alicyclic structure may have aromaticity. In this case, M and N of the heterocyclic ring-containing aromatic compound (1) have a condensed ring structure (for example, isothianaphthene). Means.

Next, the manufacturing method of the said heterocyclic containing aromatic compound (1) is demonstrated.
The heterocycle-containing aromatic compound (1) can be produced by coupling two types of heteroaromatic compounds in the presence of a hypervalent iodine reactant. Such a coupling reaction proceeds efficiently at a ratio of 1: 1 in the presence of a hypervalent iodine reactant. As the hypervalent iodine reactant, the same ones as described below can be used.

In the above coupling reaction, the amount of the hypervalent iodine reactant used is not particularly limited, and is preferably 0.1 to 4 mol, more preferably 0.2 to 3 mol, per 1 mol of one raw material. Used in a proportion, more preferably in a proportion of 0.3 to 2 mol.

In the above coupling reaction, a substituted or unsubstituted thiophene compound MH and a substituted or unsubstituted pyrrole compound NH are used as raw materials. Here, M and N are the same as described above. These compounds may be appropriately selected in order to obtain a desired product.

The above coupling reaction is usually carried out in the presence of a solvent.
The solvent may be any solvent that dissolves or disperses the raw material, the heterocycle-containing aromatic compound (1), and the hypervalent iodine reactant. Examples of such a solvent include water, methanol, and ethanol. Alcohols such as 2-propanol, 1-propanol and n-butanol; ethylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol; ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol Glycol ethers such as diethyl ether and diethylene glycol dimethyl ether; ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether Glycol ether acetates such as acetate and diethylene glycol monobutyl ether acetate; Propylene glycols such as propylene glycol, dipropylene glycol and tripropylene glycol; Propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono Propylene glycol ethers such as ethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene Propylene glycol ether acetates such as glycol monomethyl ether acetate and dipropylene glycol monoethyl ether acetate; N-methylformamide, N, N-dimethylformamide, N-methylpyrrolidone, dimethylacetamide, dimethylsulfoxide, acetone, acetonitrile, toluene, xylene (O-, m-, or p-xylene), benzene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, diethyl ether, diisopropyl ether, methyl-t-butyl ether, hexane, heptane, chloromethane (methyl chloride), Organic solvents such as dichloromethane (methylene chloride), trichloromethane (chloroform), tetrachloromethane (carbon tetrachloride), water and their organic Examples thereof include a mixed solvent (hydrous organic solvent) with a solvent. These may be used alone or in combination of two or more.

Additives may be appropriately added to the coupling reaction system. By using the hypervalent iodine reactant and the additive in combination, the yield of the heterocyclic ring-containing aromatic compound can be improved, and the amount of the hypervalent iodine reactant can be reduced.
Examples of the additive include bromotrimethylsilane, chlorotrimethylsilane, trimethylsilyl triflate, boron trifluoride, trifluoroacetic acid, hydrochloric acid, sulfuric acid, and the like. Among these, bromotrimethylsilane is preferable. These may be used alone or in combination.
The amount of the additive used is preferably 0.1 to 4 mol, more preferably 0.2 to 3 mol, and still more preferably 0.5 to 1 mol per 1 mol of the heterocyclic ring-containing aromatic compound. The ratio is 2 moles.

Further, a fluorinated alcohol may be added to the coupling reaction system. By using a hypervalent iodine reactant and a fluoroalcohol in combination, the yield of the heterocyclic ring-containing aromatic compound can be improved, and the amount of the hypervalent iodine reactant can be reduced.
Examples of the fluorinated alcohol include 1,1,1,3,3,3-hexafluoro-2-propanol, trifluoroethanol, hexafluoroethanol, and the like. Among these, 1,1,1 3,3,3-hexafluoro-2-propanol is preferred.
Although the usage-amount of the said fluorine-type alcohol is not specified in particular, 1-80 weight part is preferable with respect to 100 weight part of solvents to be used, and 10-40 weight part is especially preferable.

The above coupling reaction is usually performed by mixing each raw material, a hypervalent iodine reactant, a solvent, other reagents and the like at a temperature range of −50 ° C. to 100 ° C. for 10 minutes to 48 hours, The heterocycle-containing aromatic compound can be produced.
The coupling reaction is preferably performed at a temperature range of 0 to 50 ° C for 30 minutes to 8 hours, and more preferably at a temperature range of 10 to 40 ° C for 1 to 4 hours. At this time, the order of the reagents to be added does not matter.

Next, a method for producing a heterocyclic ring-containing aromatic polymer using the heterocyclic ring-containing aromatic compound (1) as a monomer will be described.
In the production of the heterocyclic ring-containing aromatic polymer, the monomer (heterocyclic ring-containing aromatic compound (1)) is oxidatively polymerized by a chemical polymerization method using various oxidizing agents.
Since the chemical polymerization method is simple and capable of mass production, it is a method suitable for an industrial production method as compared with the conventional electrolytic polymerization method.

Although it does not specifically limit as an oxidizing agent used for the said chemical polymerization method, For example, the oxidizing agent etc. which use a sulfonic acid compound as an anion and make an expensive number of transition metals into a cation are mentioned. Examples of the expensive transition metal ions constituting this oxidant include Cu ²⁺ , Fe ³⁺ , Al ³⁺ , Ce ⁴⁺ , W ⁶⁺ , Mo ⁶⁺ , Cr ⁶⁺ , Mn ⁷⁺ and Sn ⁴⁺ . Of these, Fe ³⁺ and Cu ²⁺ are preferred.
Specific examples of the oxidizing agent having a transition metal as a cation include FeCl ₃ , Fe (ClO ₄ ) ₃ , K ₂ CrO ₇ , alkali perborate, potassium permanganate, copper tetrafluoroborate and the like. It is done.
Examples of the oxidizing agent other than the oxidizing agent having a transition metal as a cation include alkali persulfate, ammonium persulfate, and H ₂ O ₂ . Furthermore, hypervalent compounds represented by hypervalent iodine reactants can be mentioned.

In a particularly preferred embodiment, the oxidizing agent is a hypervalent iodine reactant.
A hypervalent iodine reactant refers to a reactant containing an iodine atom in a trivalent or pentavalent hypervalent state. Since the hypervalent iodine reactant has the property of returning to a more stable octet state (monovalent iodine), a heavy metal oxidizing agent such as lead (IV), thallium (III), mercury (II), etc. And similar reactivity. Furthermore, the hypervalent iodine reactant is less toxic than such a heavy metal oxidant, has excellent safety, and is suitable for an industrial production method.

The hypervalent iodine reactant is not particularly limited, and examples of the trivalent hypervalent iodine reactant include phenyliodine bis (trifluoroacetate) or (bis (trifluoroacetoxy) iodobenzene (hereinafter referred to as “bivalent trivalent iodine”). , PIFA)), phenyliodine diacetate (iodosobenzene diacetate (hereinafter sometimes referred to as PIDA)), hydroxy (tosyloxy) iodobenzene, iodosylbenzene, and the like. The structural formulas of these reactants are shown below.

Examples of the pentavalent hypervalent iodine reactant include Dess-Martin periodinane (DMP), o-iodoxybenzoic acid (IBX), and the like. The structural formulas of these reactants are shown below.

Among these, a trivalent hypervalent iodine reactant is preferable, and PIFA is more preferable because it is stable and easy to handle and has a sufficiently high oxidizing ability.

In addition, among the hypervalent iodine reactants, it is preferable to select a hypervalent iodine reactant having an adamantane structure and a hypervalent iodine reactant having a tetraphenylmethane structure because they can be recovered and reused. More specifically, 1,3,5,7-tetrakis- (4- (diacetoxyiodo) phenyl) adamantane, 1,3,5,7-tetrakis-((4- (hydroxy) tosyloxyiodo) phenyl ) A hypervalent iodine reactant having a trivalent adamantane structure such as adamantane, 1,3,5,7-tetrakis- (4-bis (trifluoroacetoxyiodo) phenyl) adamantane, or tetrakis-4- (di Hypervalent iodine reactants having a trivalent tetraphenylmethane structure such as acetoxyiodo) phenylmethane and tetrakis-4-bis (trifluoroacetoxyiodo) phenylmethane are stable and easy to handle and have a sufficiently high oxidizing ability Furthermore, it is more preferable because it has high fat solubility and can be recovered and reused.
When a pentavalent hypervalent iodine reactant is used, desmartin periodinane (DMP) is preferred.

As such a hypervalent iodine reactant, one obtained by synthesis may be used, or a commercially available product may be used. For example, PIFA can be obtained by adding trifluoroacetic acid to PIDA and reacting, so that PIFA is precipitated as a reaction product (see J. Chem. Soc. Perkin Trans. 1, 1985, 757). ). PIDA is obtained by oxidizing iodobenzene with sodium peroxoborate (tetrahydrate) (NaBO ₃ .4H ₂ O) in acetic acid (Tetrahedron, 1989, 45, 3299 and Chem. Rev., 1996, 96, 1123). In addition, PIDA is obtained from iodobenzene using m-chloroperbenzoic acid (mCPBA) as an oxidizing agent (see Angew. Chem. Int. Ed., 2004, 43, 3595). 1,3,5,7-tetrakis- (4- (diacetoxyiodo) phenyl) adamantane, 1,3,5,7-tetrakis-((4- (hydroxy) tosyloxyiodo) phenyl) adamantane, 1,3 , 5,7-tetrakis- (4-bis (trifluoroacetoxyiodo) phenyl) adamantane, tetrakis-4- (diacetoxyiodo) phenylmethane, tetrakis-4-bis (trifluoroacetoxyiodo) phenylmethane, for example It can be synthesized by the method described in Kaikai 2005-220122.

Although the usage-amount of the said oxidizing agent is not specifically limited, The range of 1-5 mol per 1 mol of said monomers is preferable, More preferably, it is the range of 2-4 mol. In particular, when a hypervalent iodine reactant is used as the oxidizing agent, it is preferably used in a proportion of 1 to 4 mol, more preferably 1.5 to 4 mol, more preferably 1 mol of the monomer. Used in a proportion of 2 to 2.5 mol.
When the amount of the hypervalent iodine reactant is small, the oxidative polymerization reaction may be difficult to proceed. On the other hand, if the amount of the hypervalent iodine reactant is too large, excessive oxidation may occur and a product that is completely insoluble in the solvent may be obtained, and the yield of the desired polymer may be reduced.

In the method for producing a heterocyclic ring-containing aromatic polymer, a hypervalent iodine reactant and a metal-free oxidizing agent may be used in combination. The combined use of a hypervalent iodine reactant and an oxidizing agent that does not contain a metal can reduce the amount of hypervalent iodine reactant used. Examples of the metal-free oxidizing agent include peroxodisulfuric acid, ammonium peroxodisulfate, hydrogen peroxide, metachloroperbenzoic acid, and the like.

As described above, when the hypervalent iodine reactant and the metal-free oxidizing agent are used in combination, the hypervalent iodine reactant acts as an oxidation catalyst, and preferably with respect to 1 mol of the monomer. It is used in a proportion of 0.001 to 0.3 mol, more preferably 0.01 to 0.1 mol. On the other hand, the metal-free oxidizing agent is preferably used in a proportion of 1 to 4 molar equivalents, more preferably 1.5 to 2.5 molar equivalents, relative to 1 mol of the monomer.

Moreover, when using together the oxidizing agent which does not contain a metal, and a hypervalent iodine reactant, when there is too little quantity of a hypervalent iodine reactant, a polymerization reaction may not fully advance. On the other hand, even if the amount of the hypervalent iodine reactant is too large, the degree of polymerization does not exceed a certain degree of polymerization, and the hypervalent iodine reactant may be wasted.

In the case where a hypervalent iodine reactant and an oxidizing agent not containing a metal are used in combination, a precursor of the hypervalent iodine reactant may be used when starting the polymerization reaction. Specifically, for example, 1,3,5,7-tetrakis- (4-iodophenyl) adamantane, which is a precursor of 1,3,5,7-tetrakis- (4- (diacetoxyiodo) phenyl) adamantane A hypervalent iodine reagent may be generated in the reaction system by adding a catalytic amount and a stoichiometric amount of metachloroperbenzoic acid.

In the method for producing a heterocyclic ring-containing aromatic polymer, the heterocyclic ring-containing aromatic polymer may be doped with a dopant. By doping with a dopant, higher conductivity can be imparted to the resulting heterocyclic ring-containing aromatic polymer. The dopant may be charged as a raw material before the polymerization reaction, may be added during the polymerization reaction, or may be added to the heterocyclic ring-containing aromatic polymer obtained after the polymerization reaction.

Is not particularly restricted but includes dopants _{such, Cl 2, Br 2, I} 2, halogen such as _ICl; PF 5, BF _3, Lewis acids such as trimethylsilyl _{trifluoromethanesulfonate; HF, HCl, HNO 3,} H 2 SO Protic acids such as ₄ ; organic acids such as p-toluenesulfonic acid and polystyrenesulfonic acid.

The dopant used for the purpose of imparting conductivity is preferably used in a proportion of 0.05 to 6 mol, more preferably in a proportion of 0.2 to 4 mol, relative to 1 mol of the monomer.
When the amount of the dopant is less than 0.05 mol, sufficient conductivity may not be imparted to the heterocyclic ring-containing aromatic polymer. On the other hand, when the amount of the dopant is more than 6 moles, all the dopant added to the heterocyclic ring-containing aromatic polymer is not doped, and an effect proportional to the added amount cannot be expected. Also, excess dopant is wasted.

The Lewis acid not only functions as a dopant but also has an effect of promoting an oxidative polymerization reaction. When a Lewis acid is used for the purpose of promoting the oxidative polymerization reaction, trimethylsilyl trifluoromethanesulfonate is particularly preferably used.

The oxidative polymerization reaction is usually carried out in the presence of a solvent.
The solvent may be any solvent that dissolves or disperses the monomer, oxidizing agent, and dopant. Examples of such a solvent include water, methanol, ethanol, 2-propanol, 1-propanol, alcohols such as n-butanol; ethylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol; glycol ethers such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether and diethylene glycol dimethyl ether Class: Ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol Glycol ether acetates such as coal monobutyl ether acetate; propylene glycols such as propylene glycol, dipropylene glycol and tripropylene glycol; propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether , Propylene glycol ethers such as propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether Propylene glycol ether acetates such as diacetate and dipropylene glycol monoethyl ether acetate; N-methylformamide, N, N-dimethylformamide, N-methylpyrrolidone, dimethylacetamide, dimethylsulfoxide, acetone, acetonitrile, toluene, xylene (o -, M-, or p-xylene), benzene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, diethyl ether, diisopropyl ether, methyl-t-butyl ether, hexane, heptane, chloromethane (methyl chloride), dichloromethane ( Organic solvents such as methylene chloride), trichloromethane (chloroform), tetrachloromethane (carbon tetrachloride), mixed solvents of water and these organic solvents (hydrous organic solutions) Medium) and the like. These may be used alone or in combination of two or more.

The temperature of the oxidative polymerization reaction is preferably -100 ° C to 100 ° C. In either case of using an organic solvent as the solvent and water, the temperature is more preferably 0 ° C to 40 ° C. When the reaction temperature is lower than −100 ° C., the reaction rate becomes slow, or depending on the solvent, the yield of the heterocyclic ring-containing aromatic polymer may be lowered. On the other hand, when the reaction temperature is higher than 100 ° C., side reaction or excessive oxidation occurs, and the yield of the heterocyclic ring-containing aromatic polymer may be reduced.

The reaction time of the oxidative polymerization reaction is not particularly limited. When a Lewis acid is used to promote the oxidative polymerization reaction, about 12 hours are preferable, and when a Lewis acid is not used, about 20 hours are preferable.

The thus obtained heterocyclic ring-containing aromatic polymer may be subjected to a purification treatment.
Although it does not specifically limit as a purification method (purification process), For example, after reaction, a solvent is filtered with a glass filter and methanol, ethanol, 2-propanol, n-hexane, diethyl ether, acetonitrile, acetic acid is obtained. Examples include a method of washing with ethyl, toluene, and the like. Other purification methods include purification by Soxhlet extraction and the like.

In such a method for producing a heterocyclic ring-containing aromatic polymer, after washing, the obtained heterocyclic ring-containing aromatic polymer is dried by a usual means as necessary (drying step).
Here, the drying method can be appropriately determined depending on the degree of polymerization, the substituent, and the dopant contained. For example, drying under reduced pressure (about 0.5 mmHg) at room temperature (about 25 ° C.), heating air blowing under normal pressure ( About 60 ° C.) and the like. The drying temperature is preferably 100 ° C. or lower, and if it exceeds 200 ° C., the risk of decomposition of the heterocyclic ring-containing aromatic polymer increases.

In the above oxidative polymerization, when a hypervalent iodine reactant having an adamantane structure and a tetraphenylmethane structure is used, it is desirable to recover by the following method. For example, the solution after the reaction is concentrated under reduced pressure and methanol is added to the residue (polymer, adamantane or tetraphenylmethane structure hypervalent iodine reactant, metal-free oxidant, unreacted monomer). By mixing and filtering using a glass filter, the metal-free oxidizing agent and unreacted monomer can be removed as a methanol solution. The polymer remaining as a residue and the adamantane structure or tetraphenylmethane structure hypervalent iodine reactant are mixed with diethyl ether and filtered using a glass filter, whereby the residue polymer and the adamantane structure of the diethyl ether solution are mixed. And a hypervalent iodine reactant having a tetraphenylmethane structure. By concentrating the diethyl ether, the hypervalent iodine reactant having an adamantane structure and a tetraphenylmethane structure can be recovered. The recovery method of the hypervalent iodine reactant having an adamantane structure and a tetraphenylmethane structure is not limited to the above example, but the polymer, the hypervalent iodine reactant having the adamantane structure or the tetraphenylmethane structure, and the oxidizing agent not containing a metal. Each component can be separated by selecting an appropriate solvent using the difference in solubility between the unreacted monomer and the solvent species.

(B) Curable resin In the hard coat composition of the present invention, the curable resin is a component capable of imparting hardness to the cured product of the hard coat composition by curing, heat, light, Cured by electron beam.
In the present specification, the curable resin is also referred to as a hard coat component.

Examples of the curable resin (hard coat component) include cyclic ether resins such as (meth) acrylic resins (polyfunctional acrylates), polyester acrylates, epoxy resins, oxetane resins, polyacrylic, polyurethane, polyimide, polyamide, polyamideimide. , Polyimide silicone, melamine resin, silicon-containing organic-inorganic hybrid resin, and the like. These may be used alone or in combination of two or more.

The hard coat component preferably includes a (meth) acrylic resin, a cyclic ether resin, a melamine resin, and a silicon-containing organic-inorganic hybrid resin, and includes a polyfunctional acrylate or polyfunctional methacrylate, or silicon. More preferably, it contains an organic-inorganic hybrid resin.
This is because (meth) acrylic resins and cyclic ether resins can easily construct a network with a high cross-linking density, provide high hardness, and have high adhesion to the substrate.
Moreover, the melamine resin is a thermosetting resin made of a polycondensate of melamine and formaldehyde, and it is easy to construct a high-density network.

The organic-inorganic hybrid resin containing silicon can be obtained by hydrolyzing a trifunctional silane such as methyltrimethoxysilane, epoxypropyltrimethoxysilane, methyltriethoxysilane, or methyltrichlorosilane (RSiO _{1. 5} ) A network-type polymer having an _n structure (so-called silsesquioxane) or a polyhedral cluster having a structure such as a cage type, a ladder type, or a random type is known. The organic-inorganic hybrid resin containing silicon can be modified with a functional group such as an epoxy group or an acrylate group, and can be imparted with characteristics such as thermosetting property and UV curable property.
These organic-inorganic hybrid resins are not only hydrolyzed / condensed polymers of trifunctional silanes, but also bifunctional silanes such as diphenyldimethoxysilane and dimethyldimethoxysilane, tetraethoxysilane, methyltrimethoxyethoxysilane and the like 4 It may be a copolymer with a functional silane or the like.

Further, the hard coat component may contain a curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier and the like, if necessary.

The hard coat component preferably contains a photocurable compound and / or a thermosetting compound.
Here, the photo-curable compound is one that crosslinks and cures when irradiated with ultraviolet light. Specifically, it is a polyfunctional (trifunctional or higher) acrylate resin, bifunctional or higher polybutadiene acrylate, silicon. Examples include acrylates, aminoplast resin acrylates, and organic-inorganic hybrid resins.
Examples of the thermosetting compound include melamine resin, polyurethane resin, epoxy resin, alkyd resin, unsaturated polyester resin, and silicon resin.
The hard coat component may contain a resin that is cured by an electron beam.

Examples of the polyfunctional acrylate resin include epoxy acrylate resin, urethane (meth) acrylate resin, bifunctional or higher polyester acrylate, polyether acrylate, carboxyl-modified reactive polyacrylate, and the like.

Examples of the urethane (meth) acrylate resin include compounds obtained by reacting a hydroxy group-containing (meth) acrylate with a polyisocyanate. Examples of the hydroxy group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, pentaerythritol triacrylate, Examples include dipentaerythritol pentaacrylate and trimethylolpropane diacrylate. These hydroxy group-containing (meth) acrylates may be used alone or in combination of two or more.

The polyisocyanate may be any of aliphatic, aromatic and alicyclic polyisocyanates, such as methylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone. Examples include diisocyanate, xylene diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, phenylene diisocyanate, and methylene bisphenyl diisocyanate. These polyisocyanates may be used alone or in combination of two or more. Of these polyisocyanates, those that are non-yellowing urethanes are preferred.

The combination of the hydroxy group-containing (meth) acrylate and the polyisocyanate is not particularly limited. For example, a combination of 2-hydroxyethyl acrylate and isophorone diisocyanate, and 2-hydroxyethyl acrylate and 2,2,4-trimethyl. A combination with hexamethylene diisocyanate is preferred.

As a method for producing the urethane (meth) acrylate resin, for example, the molar ratio of the hydroxy group in the hydroxy group-containing (meth) acrylate and the isocyanate group in the polyisocyanate (hydroxy group: isocyanate group) is 1: Hydroxy group-containing (meth) acrylate and polyisocyanate are placed in a reaction vessel so as to be 0.8 to 1: 1, and a catalytic amount of an organic tin compound such as di-n-butyltin dilaurate is added, and polymerization such as hydrokinos is prohibited. A method of adding an agent and heating and stirring at a reaction temperature of 30 to 120 ° C., preferably 50 to 90 ° C., may be mentioned. Here, the reaction temperature is preferably raised stepwise. In the reaction product, an oligomerized urethane (meth) acrylate may be contained.

Various commercial products may be used as the urethane (meth) acrylate resin. As a commercial item of urethane (meth) acrylate resin, for example, Shimitsu series (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), New Frontier R-1000 Series (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), UA-306H ( And Kyoeisha Chemical Co., Ltd.) and UF-8001 (manufactured by Kyoeisha Chemical Co., Ltd.).

Examples other than the above acrylate resins include monofunctional or polyfunctional monomers such as styrene, methylstyrene, N-vinylpyrrolidone, or monomers such as bisphenol type epoxy compounds, novolac type epoxy compounds, aromatic vinyl ethers, aliphatic vinyl ethers, etc. Examples include compounds having a cationic polymerizable functional group.

Examples of the photocurable compound include cyclic ether bond-containing oligomers such as epoxy oligomers such as bisphenol type epoxy resins and novolac type epoxy compounds, and vinyl ether type oligomers such as fatty acid vinyl ethers and aromatic vinyl ethers. It is done.

Examples of thermosetting compounds include, for example, alkoxy groups, hydroxyl groups, carboxyl groups, amino groups, epoxy groups, isocyanate groups, aziridine groups, oxazoline groups, aldehyde groups, carbonyl groups, hydrazine groups, vinyl groups, cyano groups. And monomers or oligomers having a thermosetting group such as a group, a methylol group or an active methylene group. In addition, the thermosetting group has a blocking agent bonded to a reactive functional group such as a block isocyanate group, and when heated, the decomposition reaction of the blocking agent proceeds to cause polymerization and crosslinkability. May be a functional group.
In addition, as a thermosetting resin monomer, an organometallic compound such as an organosilicon compound (silicon alkoxide or silane coupling agent), an organotitanium compound (titanate coupling agent), or an organoaluminum compound that is usually used as a coupling agent. Can also be used.
Examples of the organosilicon compound include bifunctional silanes such as diphenyldimethoxysilane and dimethyldimethoxysilane, trifunctional silanes such as methyltrimethoxysilane, epoxypropyltrimethoxysilane, methyltriethoxysilane, and methyltrichlorosilane, and tetraethoxy. Examples thereof include tetrafunctional silanes such as silane and methyltrimethoxyethoxysilane. Since the organosilicon compound having these reactive groups easily cures and bonds strongly with other monomers and oligomers, the strength of the resulting hard coat layer is improved.
Examples of the organic titanium compound include tetramethoxy titanium and tetraethoxy titanium.

The mixing amount of the heterocycle-containing aromatic polymer and the hard coat component is appropriately selected depending on the required antistatic properties, the hardness of the cured product (hard coat layer), etc., but the heterocycle-containing aromatic polymer: the hard coat component = 0.001: 99.999 to 99.9: 0.1 (mass ratio), preferably 5:95 to 95: 5.

(C) Crosslinking agent Although it does not specifically limit as said crosslinking agent, For example, a low molecular acrylate, a low molecular epoxy resin, isocyanate etc. can be used. Specifically, bifunctional low-molecular acrylates such as ethylene oxide-modified bisphenol diacrylate, ethylene oxide-modified isocyanuric acid diacrylate, tripropylene glycol diacrylate, pentaerythritol diacrylate monostearate, pentaerythritol triacrylate, trimethylolpropane triacrylate , Trifunctional low molecular acrylates such as propylene oxide modified trimethylolpropane triacrylate, ethylene oxide modified isocyanuric acid triacrylate, propylene oxide modified trimethylolpropane triacrylate, ethylene oxide modified trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, dipenta Erythritol hexaacrylate, Tetramethylolpropane tetraacrylate, pentaerythritol tetraacrylate and other low-functional acrylates such as 3,4-epoxycyclohexenylmethyl-3′-4′-epoxycyclohexenecarboxylate, vinylcyclohexene monooxide-1,2- Alicyclic epoxy such as epoxy-4-vinylcyclohexane, acrylate having an epoxy group such as 3,4-epoxycyclohexylmethyl methacrylate, 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, Polyfunctional aliphatic epoxy compounds such as cyclohexanedimethanol diglycidyl ether, trimethylolpropane polyglycidyl ether, diethylene glycol diglycidyl ether, 4,4 ′ Diphenylmethane diisocyanate, tolylene diisocyanate, 1,3-phenylene bismethylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, isophorone diisocyanate, 1,6-diisocyanate hexane, polymethylene polyphenyl isocyanate, trimethylolpropane modified tolylene diene Isocyanates such as isocyanate, trimethylolpropane-modified hexamethylene diisocyanate, trimethylolpropane-modified isophorone diisocyanate, and the like.
The compounding quantity of the said crosslinking agent is 1-100 weight part with respect to the said curable resin (B), Preferably, it is 10-70 weight part. If the amount is too small, the hardness does not increase when the hard coat layer is formed, and if the amount is too large, the film becomes too brittle.

In the composition for hard coat of the present invention, the combination using the cross-linking agent and a polyfunctional acrylate or organic / inorganic hybrid resin as a hard coat component is an excellent combination particularly for maintaining high hardness. In particular, urethane acrylate and epoxy acrylate are preferable as the polyfunctional acrylate, and curable silsesquioxane is preferable as the organic-inorganic hybrid resin.

In addition to (A) a heterocyclic ring-containing aromatic polymer, (B) a curable resin (hard coat component), and (C) a cross-linking agent, the hard coat composition of the present invention can include (D ) A binder resin, (E) fine particles, (F) a polymerization initiator, (G) an additive, (H) a solvent and the like may be contained.
Hereinafter, the components (D) to (H) will be described.

(D) Binder resin Examples of the binder resin include polyester, poly (meth) acrylate, polyurethane, polyvinyl acetate, polyvinylidene chloride, polyamide, polyimide, and styrene, vinylidene chloride, vinyl chloride, and alkyl (meth) acrylate. And a copolymer composed of two or more monomers selected from the group consisting of:
The content of the binder resin is preferably 10 to 5000 parts by weight with respect to 100 parts by weight of the solid content of the heterocyclic ring-containing aromatic polymer (A). More preferably, it is 30 to 2000 parts by weight. When the content exceeds 5000 parts by weight, transparency and conductivity may be deteriorated. On the other hand, when the amount is less than 10 parts by weight, the curability is lowered, and sufficient scratch resistance and solvent resistance may be difficult to be imparted to the conductive film.

(E) Fine particles The fine particles contribute to improvement of the slipperiness of the coating film when the coating film is formed using the hard coat composition.
The fine particles preferably have a primary particle size of 100 nm or less, more preferably less than 50 nm, in order not to lower the transparency of the coating film. When the particle diameter exceeds 100 nm, light scattering occurs, and transparency may decrease due to a decrease in transmittance.

Examples of the fine particles include fine particles composed of metal oxides such as antimony oxide, indium tin mixed oxide and antimony tin mixed oxide, silica, etc. Among these, the primary particle diameter is from the viewpoint of transparency and hardness. Silica fine particles having a size of 100 nm or less are preferred.

The content of the fine particles is preferably blended so as to occupy a ratio of 0.5 to 200 parts by weight with respect to 100 parts by weight of the total amount of the heterocyclic ring-containing aromatic polymer, the curable resin, and the crosslinking agent. . More preferably, it is 1-50 weight part.

(F) Polymerization initiator Examples of the polymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butylacetophenone. Acetophenones; benzophenones such as benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone; benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzyldimethyl ketal, thio Xanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, etc. Sulfur compounds; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone; organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, cumene peroxide And thiol compounds such as 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, and the like.
These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

It is preferable that content of the said polymerization initiator is 0.1-50 weight part with respect to 100 weight part of curable resin (B). More preferably, it is 0.1 to 10 parts by weight.

Furthermore, a compound which does not act as a photopolymerization initiator itself but can increase the ability of the photopolymerization initiator by using it in combination with the above compound can also be added. Examples of such compounds include tertiary amines such as triethanolamine which are effective when used in combination with benzophenone.

(G) Additive As the additive, for example, when forming a coating film using the hard coat composition, it is intended to improve the adhesion with the substrate or to improve the durability of the coating film. Examples thereof include a silane coupling agent and a leveling agent and a surfactant for improving coating properties.
Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) methyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) methyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, 3 -(Meth) acryloxytrialkoxysilane such as methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p- Styryl trimethoxysilane, and the like. These may be used alone or in combination of two or more.
When the silane coupling agent is blended, the blending amount is preferably 0.2 to 10 parts by weight with respect to 100 parts by weight of the total amount of the heterocyclic ring-containing aromatic polymer, the curable resin, and the crosslinking agent. And more preferably 0.5 to 5 parts by weight.

Examples of the surfactant include, for example, nonionic surfactants such as polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, sorbitan fatty acid ester, fatty acid alkylolamide; fluoroalkylcarboxylic acid, perfluoroalkylbenzenesulfone Examples thereof include fluorine-based surfactants such as acid, perfluoroalkyl quaternary ammonium, and perfluoroalkyl polyoxyethylene ethanol.
When the surfactant is blended, the blending amount is preferably 0.1 to 60 parts by weight with respect to 100 parts by weight of the total amount of the heterocyclic ring-containing aromatic polymer, the curable resin, and the crosslinking agent. 2 to 20 parts by weight is more preferable.

(H) Solvent solvent may not be used. Examples of the solvent include water and alcohols such as methanol, ethanol, 2-propanol, 1-propanol, and n-butanol; ethylene glycol, diethylene glycol, and triethylene glycol. Ethylene glycols such as tetraethylene glycol; glycol ethers such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether; ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol Glycol ether acetate such as monobutyl ether acetate Propylene glycols such as propylene glycol, dipropylene glycol, tripropylene glycol; propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol Propylene glycol ethers such as dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate Any propylene glycol ether acetates; N-methylformamide, N, N-dimethylformamide, N-methylpyrrolidone, dimethylacetamide, dimethylsulfoxide, acetone, acetonitrile, toluene, xylene (o-, m-, or p-xylene), Benzene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, diethyl ether, diisopropyl ether, methyl-t-butyl ether, hexane, heptane, chloromethane (methyl chloride), dichloromethane (methylene chloride), trichloromethane (chloroform), tetra Examples thereof include organic solvents such as chloromethane (carbon tetrachloride), mixed solvents of water and these organic solvents (hydrous organic solvents), and the like.
These may be used alone or in combination of two or more.
The hard coat composition of the present invention preferably contains an organic solvent. The reason is that it has high hardness, high adhesion to the substrate, and is suitable for forming a uniform hard coat layer.

The blending amount of the solvent is preferably 100 to 5000 parts by weight and more preferably 500 to 3000 parts by weight with respect to 100 parts by weight of the heterocyclic ring-containing aromatic polymer.

The composition for hard coat of this invention which consists of such a structure can be manufactured by mixing each component with a mixer, for example.
At this time, the method of adding each component is not particularly limited. For example, all components may be added simultaneously.

Next, the hard coat film of the present invention will be described with reference to the drawings.
The hard coat film of the present invention comprises an antistatic hard coat layer formed using the hard coat composition described above.

FIG. 1 is a cross-sectional view schematically showing a hard coat film of the present invention.
As shown in FIG. 1, the hard coat film 1 includes a film base 10 and a hard coat layer 20 formed on the film base 10.
In FIG. 1, the hard coat layer 20 is formed only on one side of the film substrate 10, but the hard coat film of the present invention may have a hard coat layer formed on both sides of the film substrate.

Here, examples of the film substrate 10 include films made of polyethylene terephthalate, polyimide, polyether sulfone, polyether ether ketone, polycarbonate, polypropylene, polyamide, acrylamide, cellulose propionate, and the like.
Moreover, it is preferable that the film base material 10 is subjected to etching treatment or undercoating treatment such as sputtering, corona discharge, flame, ultraviolet ray irradiation, electron beam irradiation, chemical conversion, oxidation, etc., as necessary. If such a treatment is applied to the surface, the adhesion to the hard coat layer 20 can be further improved.
Furthermore, the surface of the film substrate 10 may be dust-removed and cleaned by solvent cleaning, ultrasonic cleaning, or the like as necessary before providing the hard coat layer 20.

The hard coat layer 20 is a layer formed by applying a hard coat composition of the present invention and drying it, followed by curing treatment.
Here, the coating of the hard coat composition can be performed by a conventionally known method, such as a spin coat method, a dip method, a spray method, a slide coat method, a bar coat method, a roll coater method, a meniscus coater method, It can be performed by a method such as a flexographic printing method, a screen printing method, or a pea coater method.
Examples of the drying method include reduced-pressure drying or heat drying, and a combination of these drying methods. Specifically, for example, when the hard coat composition contains a ketone solvent as a solvent, it is room temperature to 80 ° C, preferably 40 ° C to 60 ° C, preferably 20 seconds to 3 minutes, preferably May be performed in a time of about 30 seconds to 1 minute.

Moreover, the said hardening process hardens the coating film dried by light irradiation, for example with respect to the coating film which apply | coated and dried the composition for hard-coats, when the said composition for hard-coats is a photocurable type | mold. By doing. For the light irradiation, ultraviolet rays, visible light, electron beams, ionizing radiation, etc. are mainly used. In the case of ultraviolet curing, ultraviolet rays emitted from light such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp are used. Here, the irradiation amount of the energy ray source is about 50 to 5000 mJ / cm ² as an integrated exposure amount at an ultraviolet wavelength of 365 nm.
When the hard coat composition is a thermosetting type, it is cured by heating to form a hard coat layer, which is usually treated at a temperature of 40 ° C to 150 ° C. Moreover, you may react by leaving it to stand for 24 hours or more at room temperature (25 degreeC).
Further, depending on the composition of the hard coat composition, photocuring and thermosetting may be used in combination.

Next, the display device of the present invention will be described.
The display device of the present invention has the hard coat film of the present invention.

The display device of the present invention is a liquid crystal display, plasma display, organic EL display, electronic paper or the like, and includes the hard coat film of the present invention as an optical film such as an antireflection film or a polarizing plate.

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

(Production Example 1)
In a 200 mL beaker, 120 g of toluene, 8.0 g of methanol, 13.91 g of iron (III) p-toluenesulfonate (40% butanol solution), 1.3 g (3.3 mmol) of the above structural formula (2- The heterocycle-containing aromatic compound represented by 3) (hereinafter also referred to as heterocycle-containing aromatic compound (2-3)) was added.
Thereafter, the mixture was stirred for 2 hours in an ice bath (internal temperature of 5 to 7 ° C.), and disappearance of the heterocyclic ring-containing aromatic compound (2-3) was confirmed by HPLC. Thereby, 110 g (solid content 1.5%) of a p-toluenesulfonic acid-doped heterocyclic ring-containing aromatic compound (2-3) polymer toluene dispersion was obtained.

This heterocyclic ring-containing aromatic compound (2-3) polymer toluene dispersion does not dissolve in the GPC eluent, and the GPC measurement shows that the heterocyclic ring-containing aromatic compound (2-3) polymer toluene dispersion itself It was difficult to measure the molecular weight. However, in the polymerization reaction, the heterocycle-containing aromatic compound (2- 3) is completely disappeared and the test results of the hard coat composition shown below show that the heterocycle-containing aromatic compound (2- 3) From the result that the polymer toluene dispersion showed conductivity, it is clear that the heterocyclic ring-containing aromatic compound (2-3) polymer toluene dispersion was produced.

(Production Example 2)
In a 200 mL beaker, 100 g MEK, 8.0 g methanol, 10.0 g iron (III) sulfate (1% aqueous solution), 10.0 g ammonium persulfate (10% water-methanol aqueous solution), 5.0 g di-acid. Sodium ethylhexyl sulfosuccinate, 1.3 g (3.3 mmol) of the heterocycle-containing aromatic compound (2-3) was added.
Then, it stirred at room temperature (internal temperature 20-25 degreeC) for 6 hours, and the loss | disappearance of the heterocyclic ring-containing aromatic compound (2-3) was confirmed by HPLC. Thereby, 120 g (solid content: 1.5%) of a DEHS-doped heterocycle-containing aromatic compound (2-3) polymer MEK dispersion was obtained.

The heterocyclic ring-containing aromatic compound (2-3) polymer MEK dispersion does not dissolve in the GPC eluent, and the GPC measurement shows that the heterocyclic ring-containing aromatic compound (2-3) polymer MEK dispersion itself It was difficult to measure the molecular weight. However, in the polymerization reaction, the heterocycle-containing aromatic compound (2- 3) is completely disappeared and the test results of the hard coat composition shown below show that the heterocycle-containing aromatic compound (2- 3) From the result that the polymer MEK dispersion shows conductivity, it is clear that the heterocyclic ring-containing aromatic compound (2-3) polymer MEK dispersion is produced.

(Production Example 3)
In a 200 mL beaker, 100 g ethylene dichloride, 10.0 g methanol, 12.0 g iron (III) p-toluenesulfonate (40% butanol solution), 5.0 g sodium diethylhexylsulfosuccinate, 1.3 g ( 4.7 mmol) of the heterocyclic ring-containing aromatic compound represented by the structural formula (2-1) (hereinafter also referred to as a heterocyclic ring-containing aromatic compound (2-1)) was added.
Then, it stirred at room temperature (internal temperature 20-25 degreeC) for 24 hours, and the loss | disappearance of the heterocyclic ring-containing aromatic compound (2-1) was confirmed by HPLC. As a result, 120 g (solid content: 1.4%) of a DEHS-doped heterocycle-containing aromatic compound (2-1) polymer EDC dispersion was obtained.

This heterocyclic ring-containing aromatic compound (2-1) polymer EDC dispersion does not dissolve in the GPC eluent, and the GPC measurement shows that the heterocyclic ring-containing aromatic compound (2-1) polymer EDC dispersion itself It was difficult to measure the molecular weight. However, in the above polymerization reaction, the heterocycle-containing aromatic compound (2-1) is completely disappeared and the test results of the hard coat composition shown below show that the heterocycle-containing aromatic compound (2- 1) From the result that the polymer EDC dispersion shows conductivity, it is clear that the heterocyclic ring-containing aromatic compound (2-1) polymer EDC dispersion is produced.

(Production Example 4)
In a 200 mL beaker, 120 g of toluene, 10.0 g of methanol, 12.0 g of iron (III) p-toluenesulfonate (40% butanol solution), 12.0 g of polyvinylsulfonic acid, 1.3 g (3.0 mmol) ) Of the heterocycle-containing aromatic compound represented by the above structural formula (2-5) (hereinafter also referred to as heterocycle-containing aromatic compound (2-5)).
Then, it stirred at room temperature (internal temperature 20-25 degreeC) for 6 hours, and the loss | disappearance of the heterocyclic ring-containing aromatic compound (2-5) was confirmed by HPLC. As a result, 125 g (solid content 1.6%) of a PVS-doped heterocyclic ring-containing aromatic compound (2-5) polymer toluene dispersion was obtained.

The heterocyclic ring-containing aromatic compound (2-5) polymer toluene dispersion does not dissolve in the GPC eluent, and the GPC measurement shows that the heterocyclic ring-containing aromatic compound (2-5) polymer toluene dispersion itself. It was difficult to measure the molecular weight. However, in the above polymerization reaction, the heterocycle-containing aromatic compound (2-5) has completely disappeared and the test results of the hard coat composition shown below show that the heterocycle-containing aromatic compound (2- 5) From the result that the polymer toluene dispersion shows conductivity, it is clear that the heterocyclic ring-containing aromatic compound (2-5) polymer toluene dispersion is produced.

(Production Example 5)
In a 200 mL beaker, 120 g MEK, 8.0 g methanol, 13.91 g iron (III) sulfate (1% aqueous solution), 20.00 g ammonium persulfate (10% water-methanol aqueous solution), 2.06 g p -Toluenesulfonic acid, 1.3 g (2.6 mmol) of a heterocyclic ring-containing aromatic compound represented by the above structural formula (2-8) (hereinafter also referred to as a heterocyclic ring-containing aromatic compound (2-8)). added.
Then, it stirred at room temperature (internal temperature 20-25 degreeC) for 6 hours, and the loss | disappearance of the heterocyclic ring-containing aromatic compound (2-8) was confirmed by HPLC. This obtained 110 g (solid content 1.5%) of p-toluenesulfonic acid doped heterocycle-containing aromatic compound (2-8) polymer MEK dispersion.

This heterocyclic ring-containing aromatic compound (2-8) polymer MEK dispersion does not dissolve in the GPC eluent, and the GPC measurement shows that the heterocyclic ring-containing aromatic compound (2-8) polymer MEK dispersion itself It was difficult to measure the molecular weight. However, in the above polymerization reaction, the heterocycle-containing aromatic compound (2-8) has completely disappeared and the test results of the hard coat composition shown below show that the heterocycle-containing aromatic compound (2- 8) From the result that the polymer MEK dispersion showed conductivity, it is clear that the heterocycle-containing aromatic compound (2-8) polymer MEK dispersion was produced.

(Comparative Production Example 1)
In a 2000 mL three-necked flask, 1.53 g (10.9 mmol) of 3,4-ethylenedioxythiophene (EDOT), 410 g of ion-exchanged water, 253 g of 12.8 mass% polystyrene sulfonic acid aqueous solution, 16.5 g (0 .41 mmol) of 1% aqueous iron (III) sulfate solution was added. Next, 11.8 g (5.7 mmol) of 10.9 mass% peroxodisulfuric acid aqueous solution was added. Thereafter, the mixture was stirred at room temperature (about 25 ° C.) for 24 hours, disappearance of EDOT was confirmed by HPLC, and 650 g of a polystyrenesulfonic acid-doped poly (3,4-ethylenedioxythiophene) (PEDOT) aqueous dispersion ( Solid content 1.3%).

About this PEDOT aqueous dispersion, since polystyrene sulfonic acid is used as a dopant, it was difficult to measure the molecular weight of PEDOT itself by GPC measurement. However, in the above polymerization reaction, PEDOT was generated because EDOT had completely disappeared and the test results of the conductive resin composition shown below showed that the water dispersion showed conductivity. Obviously.

Table 1 below shows the formulations of Production Examples 1 to 5 and Comparative Production Example 1.

Abbreviations in Table 1 are as follows.
TOL: Toluene MEK: Methyl ethyl ketone EDC: Ethylene dichloride PTS-Fe: p-Toluenesulfonic acid iron Fe ₂ SO ₄ / APS: Iron (III) sulfate / ammonium persulfate PTS: p-toluenesulfonic acid DEHS: diethylhexyl sodium sulfosuccinate PVS : Polyvinylsulfonic acid

Next, hard coat compositions were produced by the following methods (Examples 1 to 5 and Comparative Example 1). Table 2 shows the composition of hard coat compositions produced in Examples and Comparative Examples.

Example 1
Heterocycle-containing aromatic compound (2-3) polymer obtained in Production Example 1 1.4 g of toluene dispersion, 0.03 g of UV curable urethane acrylate (manufactured by Nippon Synthetic Chemical Co., Ltd., UV-7600B), dipentaerythritol hexa A hard coat composition is prepared by mixing 0.02 g of acrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA), 0.003 g of acetophenone photopolymerization initiator (manufactured by Ciba Specialty Chemicals, Irgacure 127) and 2.0 g of methyl ethyl ketone. Manufactured.

(Example 2)
1.4 g of heterocyclic ring-containing aromatic compound (2-3) polymer MEK dispersion obtained in Production Example 2, 0.05 g of thermosetting silsesquioxane (SQ-1) synthesized by the following method, alicyclic ring A hard coat composition was prepared by mixing 0.02 g of an epoxy resin (manufactured by Daicel Chemical Industries, Celoxide 2021-P) and 0.003 g of a thermal cationic curing catalyst (SI-60L, manufactured by Sanshin Chemical Industry Co., Ltd.). .

(Synthesis of SQ-1)
A reactor equipped with a stirrer and a thermometer was charged with 150 g of methyl isobutylene ketone (MIBK), 4.8 g of a 20% aqueous solution of tetramethylammonium hydroxide (1.1 mmol of tetramethylammonium hydroxide), and 13.5 g of distilled water. Thereafter, 107.4 g (541.0 mmol) of phenyltrimethoxysilane and 42.6 g (180.0 mmol) of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane were gradually added at 50 to 55 ° C. for 3 hours. The mixture was left stirring. After completion of the reaction, 150 g of MIBK was added to the system, and further washed with 60 g of distilled water until the pH of the aqueous layer became neutral. Next, after washing twice with 80 g of distilled water, MIBK was distilled off under reduced pressure to obtain the target compound (SQ-1). Mw was 4800. SQ-1 was a silsesquioxane derivative mainly composed of a ladder-type or random-type structure having a dispersity Mw / Mn = 1.5 and a residual silanol peak in the vicinity of 3500 cm ⁻¹ by IR measurement.

(Example 3)
Heterocycle-containing aromatic compound (2-1) polymer EDC dispersion obtained in Production Example 3 1.4 g, UV-7600B (UV curable urethane acrylate) 0.05 g, 1,6-hexanediol diacrylate (Daicel) Cytec Co., Ltd., HDDA) 0.025 g, allyl methacrylate (Shin Nakamura Chemical Co., Ltd., S-1800M) 0.06 g, alkylphenone photopolymerization initiator (Ciba Specialty Chemicals Co., Ltd., Irgacure 184) 0.003 g Then, 2.0 g of toluene was mixed to produce a hard coat composition.

Example 4
Heterocycle-containing aromatic compound (2-5) polymer obtained in Production Example 4 1.4 g of toluene dispersion, polyester acrylate (Miramer PS420, manufactured by Toyo Chemicals Co., Ltd.) 0.05 g, trimethylolpropane triacrylate (Toagosei Co., Ltd.) Manufactured by Aronics M-309), 0.03 g of Irgacure 184 (photopolymerization initiator), 0.01 g of ethyl vinyl ether, and 2.0 g of methyl ethyl ketone were mixed to prepare a hard coat composition.

(Example 5)
1.4 g of the heterocyclic ring-containing aromatic compound (2-8) polymer MEK dispersion obtained in Production Example 5, 0.05 g of UV curable silsesquioxane (SQ-2) synthesized by the following method, KAYARAD DPHA (dipentaerythritol hexaacrylate) 0.02 g, silane coupling agent (Momentive Performance Materials Japan GK, SILQUEST A187 SILANE) 0.02 g, azobisisobutyronitrile 0.005 g, toluene 4. 0g was mixed and the composition for hard-coats was manufactured.

(Synthesis of SQ-2)
A reaction vessel equipped with a stirrer and a thermometer was charged with 150 g of MIBK, 4.8 g of a 20% aqueous solution of tetramethylammonium hydroxide (1.1 mmol of tetramethylammonium hydroxide), and 13.5 g of distilled water, and then phenyltrimethoxy 107.4 g (541.0 mmol) of silane and 42.6 g (180.0 mmol) of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane were gradually added at 50 to 55 ° C., and the mixture was allowed to stand for 3 hours. After completion of the reaction, 150 g of MIBK was added to the system, and further washed with 60 g of distilled water until the pH of the aqueous layer became neutral. Next, after washing twice with 80 g of distilled water, MIBK was distilled off under reduced pressure to obtain the target compound (SQ-2). Mw was 4800. SQ-2 was a silsesquioxane derivative mainly composed of a ladder type or random type structure having a dispersity Mw / Mn = 1.5 and a peak of residual silanol near 3500 cm ⁻¹ by IR measurement.

(Comparative Example 1)
10.0 g of PEDOT aqueous dispersion obtained in Comparative Production Example 1, 0.10 g of water-soluble aliphatic urethane acrylate (manufactured by Daicel Cytec Co., Ltd., EBECRYL 2000), 0.10 g of KAYARAD DPHA (dipentaerythritol hexaacrylate), polydimethylsiloxane A hard coat composition was prepared by mixing 0.05 g of a system surface conditioner (BYKUV3500, manufactured by BYK Japan, Inc.), 0.01 g of Irgacure 184 (photopolymerization initiator), 10 g of ethanol, and 2.0 g of water.

The following evaluation was performed about the composition for hard-coats manufactured by the Example and the comparative example.
That is, the hard coat composition was applied onto a blue plate glass substrate with a wire bar, dried and cured by exposure to a high-pressure mercury lamp to form an antistatic hard coat layer having a thickness of 5 μm.
And about this hard-coat layer, the surface resistivity (SR), the total light transmittance (Tt), the haze value, adhesiveness (cross-cut test), pencil hardness, and scratch resistance were measured by the following method. The results are shown in Table 3.

Surface resistance (SR)
According to JIS K6911, it measured using Mitsubishi Chemical Corporation make Hirestar UP (MCP-HT450).

Total light transmittance (Tt) / haze value Measured according to JIS K 7150 using a haze computer HGM-2B manufactured by Suga Test Instruments Co., Ltd.

Adhesion (cross cut test)
It was carried out in accordance with a grid peel test of JIS K 5400.

Pencil hardness was measured according to the test method of JIS K 5400. The pencil hardness was defined as the highest hardness at which the coating film was not scratched when a load of 9.8 N was applied using a pencil hardness tester.

After the surface friction test (load 1 kgf, stroke width 30 mm, 10 reciprocations) with scratch resistance # 0000 steel wool, the presence or absence of scratches was visually observed and evaluated according to the following criteria.
○: 0 scratches ×: 1 or more scratches

Further, the storage stability of the hard coat composition was evaluated by the following method. The results are shown in Table 3.
Here, storage stability was evaluated using the rate of increase in surface resistivity (SR) before and after the passage of a certain time and the liquid appearance as indicators.
That is, using the hard coat composition immediately after preparation, a hard coat layer was formed by the above-described method, and the surface resistivity (SR) measured at that time was used as the initial surface resistivity. After storing in a dark place at 40 ° C. for 1 week, a hard coat layer was formed by the same method, and the measured surface resistivity (SR) was defined as the surface resistivity after the test, and the surface resistivity after the test was defined as the initial surface resistance. The rate of increase in surface resistivity (SR) was calculated by dividing by the rate.

Moreover, after leaving the composition for hard-coats used for the measurement of the surface resistivity after a test for 1 hour, the liquid was visually observed and evaluated in three stages of 1 to 3 according to the following criteria.
3: No precipitate is observed.
2: A slight precipitate is observed.
1: A large amount of precipitate is observed.

From the above results, the coating film formed using the hard coat compositions of Examples 1 to 5 is Comparative Example 1 containing another conductive polymer (poly (3,4-ethylenedioxythiophene)). As compared with the coating film formed using the hard coat composition, it was revealed that the film was excellent in adhesion to the substrate, pencil hardness and scratch resistance, and also in storage stability.
And this reason is considered that the composition for hard coats of this invention is because the conductive polymer (heterocyclic ring-containing aromatic polymer) is excellent in solvent solubility and compatibility with hard coat components. It was.

The hard coat composition of the present invention can be suitably used as a hard coat agent having antistatic properties, and a hard coat film having antistatic properties is obtained by using the hard coat composition of the present invention. be able to. Moreover, the hard coat film of this invention can be used conveniently as an optical film of various display devices. The hard coat film having antistatic properties obtained with the hard coat composition of the present invention has excellent antistatic properties, high transparency, and good hardness, especially plastic optical parts, optical disks, touch panels, flat panels. It is a hard coat film suitable for fields that do not like dust, require hardness and transparency, such as displays, mobile phones, and film liquid crystal elements. Furthermore, the present invention can be applied to other fields such as semiconductor wafer storage containers, optical disks, magnetic tapes, other electronic / electrical members, and clean room members for semiconductor production sites.

1 Hard Coat Film 10 Film Base 20 Hard Coat Layer

Claims (5)

(A) Heterocyclic ring-containing aromatic polymer having a heterocyclic ring-containing aromatic compound represented by the following general formula ( 2 ' ) as a monomer

(In the formula, R ³ and R ⁴ each independently represent a hydrogen atom or an organic group, but at least one represents an organic group. When both R ³ and R ⁴ represent an organic group, these May be bonded to each other to form a ring structure.)
(B) a curable resin containing an organic-inorganic hybrid resin containing polyfunctional acrylate, polyfunctional methacrylate, or silicon , and
(C) A hard coat composition comprising a resin composition containing a crosslinking agent and having antistatic properties. 2. The hard coat according to claim 1, wherein the heterocycle-containing aromatic compound is at least one of heterocycle-containing aromatic compounds represented by the following structural formulas (2-1) to (2-10). Composition.

The composition for hard-coats of Claim 1 or 2 containing an organic solvent. Hard coat film, characterized in that it comprises the antistatic hard coat layer formed by using the hard coat composition according to any one of claims 1-3. A display device comprising the hard coat film according to claim 4 .

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