JPH05230442A - Antistatic material - Google Patents

Abstract

PURPOSE:To provide an antistatic material excellent in all of properties such as light transmission (transparency), surface hardness, scratch resistance and heat resistance. CONSTITUTION:The title material is prepared by applying a curing composition consisting mainly of fine conductive particles such as fine indium oxide particles or fine tin oxide particles or conductive fine particles prepared by surface- coating fine particles with the conductive fine particles and a curable phosphazene compound to a substrate and curing the applied composition to form a cured resin layer on its surface.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic material, and more particularly to an antistatic material having excellent properties such as translucency (transparency), surface hardness, scratch resistance and heat resistance.

[0002]

2. Description of the Related Art Various members subjected to antistatic treatment are widely used in various fields including electric and electronic devices. These members are required to have antistatic properties, and there are various substances having antistatic properties used in this application.
Those having transparency are particularly preferred. Conventionally, a technique of vapor-depositing indium oxide or tin oxide is well known as a device having such transparency and antistatic property. However, although these compounds are excellent in performance, there is a problem in that it takes time to evacuate during vapor deposition and productivity becomes low. Further, there is a problem that the material of the substrate is restricted because the substrate is exposed to high temperature, and the vapor deposition film obtained is easily damaged. Further, a binder having excellent transparency such as an acrylic resin or a polyester resin is mixed and dispersed with conductive fine particles, a surfactant or the like, which is applied to a base material and cured, which is used. However, this product has no problem in productivity, but has a problem that it has low surface hardness and is easily scratched.

[0003]

Therefore, in view of the above situation, the present inventor has conducted earnest studies to solve the problems. As a result, it is possible to solve the above-mentioned problems by combining specific conductive fine particles and a curable phosphazene compound as a binder resin thereof, and providing a cured resin surface layer made of a curable composition containing this as a main component. Found. The present invention has been completed based on such findings. That is, the present invention comprises, as a main component, (A) conductive fine particles of indium oxide-based fine particles or tin oxide-based fine particles, or conductive fine particles whose surfaces are coated with these and (B) curable phosphazene compound. The present invention provides an antistatic material obtained by applying and curing a curable composition as described above to form a cured resin surface layer.

First, as the base material constituting the antistatic material of the present invention, various synthetic resins, metals, papers, which are widely used in various fields including electric and electronic devices,
Wood, ceramics and the like, which may be in the form of sheet, film, plate or the like. Specifically, for example, a thermoplastic resin among synthetic resins is a base material using polyethylene, polypropylene, polycarbonate, acrylic resin, methacrylic resin, polyvinyl chloride, polyester resin, polyamide resin, or the like. Further, it is a substrate using an unsaturated polyester resin, a phenol resin or the like as the thermosetting resin.

Next, on each of the various substrates, (A) conductive fine particles of indium oxide type fine particles or tin oxide type fine particles, or conductive fine particles whose surfaces are coated with these, and (B) curable phosphazene compound. The antistatic material of the present invention can be obtained by applying and curing a curable composition containing as a main component to form a cured resin surface layer. The conductive fine particles of the component (A) used for providing the cured resin surface layer are indium oxide fine particles, tin oxide fine particles, or a fine particle coated with these, and have a specific resistance value of 10 ⁷ Ωcm or less. Here, as the indium oxide-based conductive fine particles, Sn-doped In ₂ O ₃ is preferable. Further, as the tin oxide-based conductive fine particles,
Examples thereof include Sb-doped SnO ₂ and P-doped SnO ₂ .
As the conductive fine particles whose surfaces are coated with these indium oxide-based fine particles or tin oxide-based fine particles, for example, BaSO coated with Sb-doped SnO ₂ is used.
Suitable examples include BaSO ₄ coated with ₄ and Sn-doped In ₂ O ₃ . The inorganic fine particles used for the conductive fine particles include, for example, BaSO ₄ , Mg.
SO ₄ , SiO ₂ or the like can be used. The primary particle diameter of these conductive fine particles is not particularly limited, but is preferably 20 μm or less in view of the characteristics of the cured resin surface layer. However, considering the haze of the obtained antistatic material, it is particularly preferable that the thickness be 1 μm or less.

On the other hand, as the curable phosphazene compound of the component (B) which serves as a binder for the conductive fine particles when the cured resin surface layer is provided, for example, the general formula (I) is used.

[0007]

[Chemical 1]

(In the formula, A represents a polymerization-curable group, B represents a non-polymerization-curable group, and a and b are 0 <a and 0 ≦ b.
And a real number that satisfies a + b = 2. ) And a phosphazene compound having a repeating unit represented by), and there are various compounds depending on the type of each substituent. In the formula, A
Represents a polymerization-curable group, and the polymerization-curable group means a functional group that is cured by reaction with irradiation of ultraviolet rays, visible rays or electron beams, use of a chemical curing agent or heating, and is usually It is a group having a reactive double bond. There are various groups having this reactive double bond. For example,
Functional groups including acryloyl group, methacryloyl group, vinyl group or allyl group are mentioned. The functional group containing an acryloyl group or a functional group containing a methacryloyl group is an acryloyloxy group or a methacryloyloxy group,
Furthermore, the general formula (II)

[0009]

[Chemical 2]

[In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkylene group having 1 to 12 carbon atoms (preferably 1 to 5) (including a branched alkylene group). ] Is represented.

Specific examples of the group represented by the general formula (II) include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 6-hydroxy-3-methylhexyl methacrylate, 5-hydroxyhexyl methacrylate, 3-hydroxy-2-t-butylpropyl methacrylate, 3-hydroxy-2,2-dimethylhexyl Removal of hydrogen atom from hydroxyl groups in methacrylates such as methacrylate, 3-hydroxy-2-methyl-2-ethylpropyl methacrylate and 12-hydroxydodecyl methacrylate. Residues, and 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 6-hydroxy -3-Methylhexyl acrylate, 5-hydroxyhexyl acrylate, 3-hydroxy-2-t-butylpropyl acrylate, 3-hydroxy-2,2-dimethylhexyl acrylate, 3-hydroxy-2-methyl-2-
Examples thereof include a residue obtained by removing a hydrogen atom from a hydroxyl group in acrylates such as ethylpropyl acrylate and 12-hydroxydodecyl acrylate. Particularly preferred groups are 2-hydroxyethyl methacrylate residue and 2-hydroxyethyl acrylate residue.
Further, the functional group containing an acryloyl group or a methacryloyl group can be a compound represented by the general formula (I
II)

[0012]

[Chemical 3]

(Wherein R ¹ and R ² are the same as above), that is, a residue obtained by removing a hydrogen atom from a hydroxyl group of hydroxyalkyl-substituted (meth) acrylamide, and further a general formula ( IV)

[0014]

[Chemical 4]

A functional group represented by the formula (wherein R ¹ is the same as the above), that is, a residue obtained by removing one hydrogen atom from the amino group of acrylamide or methacrylamide is exemplified. Furthermore, as the functional group containing an allyl group, in addition to the allyl group itself, for example, an allyloxy group (CH
₂ = CH-CH ₂ O-) it is not limited to this allyloxy group, broadly, the general formula (V) ~ (VII)

[0016]

[Chemical 5]

(Wherein R ¹ , R ³ and R ⁴ are the same as defined above), that is, a residue obtained by removing a hydrogen atom from a hydroxyl group of an allyl compound having one hydroxyl group. You can Specific examples of the functional groups represented by the general formulas (V) to (VII) include:

[0018]

[Chemical 6]

There is a residue obtained by removing a hydrogen atom from a hydroxyl group in an allyl compound such as. On the other hand, B in the general formula (I) is
As described above, the general formulas (VIII), (IX)

[0020]

[Chemical 7]

(In the formula, M is an oxygen atom, a sulfur atom or
Represents a mino group, R^FiveIs an alkyl group having 1 to 18 carbon atoms
Or represents a halogenated alkyl group having 1 to 18 carbon atoms. Well
R ⁶~ R^TenAre independently hydrogen atom and halogen atom
Child, alkyl group having 1 to 4 carbon atoms or ha having 1 to 4 carbon atoms
A rogenated alkyl group is shown. ) Represents a group represented by. one
Specific examples of general formula (VIII) include methoxy group and ethoxy group.
Group, propoxy group, butoxy group, pentyloxy group,
Xyloxy group, heptyloxy group, octyloxy group
Alkoxy groups such as, halogen (eg fluorine, chlorine,
A similar alkoxy group substituted with bromine, etc., methyl
O group, ethylthio group, propylthio group, butylthio group,
Pentylthio group, heptylthio group, octylthio group, etc.
Alkylthio group, halogen (eg fluorine, chlorine, odor
A similar alkylthio group substituted with
Mino group, ethylimino group, propylimino group, butyrui
Mino group, pentylimino group, hexyluimino group, hepti
Alkylimino such as ruimino group and octylimino group
Substitute with groups or halogens (eg fluorine, chlorine, bromine, etc.)
The similar alkylimino group etc.
It The group of formula (IX) is specifically a phenoxy group or a thiol group.
Phenyl group, halogenated phenoxy group (2, 4, 6-to
Libromophenoxy group, 4-bromophenoxy group, 2-
Chlorophenoxy group, 2,4-dichlorophenoxy group
And halogenated thiophenyl group (4-chlorophene)
Nylthio group) or aniline and halogenated
Aniline (2-chloroaniline, 2,4-dichloroani
Amino of phosphorus, 2,4,6-tribromoaniline, etc.
Examples include residues in which hydrogen atoms have been removed from groups.
Wear.

Regarding a and b in the above-mentioned general formula (I), 0 <a ≦ 2, 0 ≦ b <2, and a + b =
It may be any real number that satisfies 2, but preferably 0.6 ≦ a ≦
2,0 ≦ b ≦ 1.4. It should be noted that the substituent A is, when the phosphazene compound of the general formula (I) is polymerized (cured),
The substituent B is a group exhibiting a curing action, and the substituent B is a group exhibiting the action of adjusting the physical properties of the polymer and the polymerization performance. However, since those with a = 0 have no curability, such phosphazene compounds are excluded from the scope of the present invention. However, a = 2, b = 0,
That is,

[0023]

[Chemical 8]

The phosphazene compound having a repeating unit represented by the formula (A is the same as above) can be used as a raw material of the curable composition of the present invention, and the present invention is more advantageous in terms of curability. Can be effective. The curable phosphazene compound used in the present invention is preferably a curable phosphazene compound having a repeating unit represented by the above general formula (I), and its degree of polymerization is 3 or more, preferably 3 to 10000.
The range is more preferably 3 to 18, and most preferably 3 or 4 or a mixture thereof. In addition, there are those in which the repeating units of the general formula (I) are linked (polymerized) in a chain shape, but preferably they are linked (polymerized) in a cyclic form.
It was done. Specific examples of such a curable phosphazene compound are as follows.

[0025]

[Chemical 9]

Such a curable phosphazene compound is
It can be manufactured by various methods and is not particularly limited. For example, when it is desired to introduce a group represented by the general formula (II) as the substituent A, a hydroxyalkyl (meth) acrylate corresponding to the general formula (II), that is, a general formula

[0027]

[Chemical 10]

(In the formula, R ¹ and R ² are the same as above.)
When a hydroxyalkyl (meth) acrylate represented by the formula (1) is used and a group represented by the general formula (III) is desired to be introduced as the substituent A, the corresponding general formula

[0029]

[Chemical 11]

(In the formula, R ¹ and R ² are the same as above.)
When using a hydroxyalkyl (meth) acrylamide represented by the formula (1) and introducing a group represented by the general formula (IV) as the substituent A, the corresponding general formula

[0031]

[Chemical 12]

(In the formula, R ¹ is the same as above), or when it is desired to introduce the groups represented by the general formulas (V) to (VIII) as the substituent A, The corresponding general formula

[0033]

[Chemical 13]

(In the formula, R ¹ , R ³ and R ⁴ are the same as above.) Allyl alcohol, allylphenol, allyl ester of hydroxybenzoic acid or its derivative is used. On the other hand, in the group represented by the general formula (VIII) introduced as the substituent B, when M is an oxygen atom, an alkanol represented by R ⁵ OH (wherein R ⁵ is the same as the above),
Using halogenated alkanol or its derivative, M
Is a sulfur atom, an alkylmercaptan represented by R ⁵ SH (wherein R ⁵ is the same as above), a halogenated alkylmercaptan or a derivative thereof is used, and when M is an imido group, R ⁵ NH ₂ R ⁵ is the same as the above), and an alkylamine, a halogenated alkylamine or a derivative thereof is used. In the group represented by the general formula (IX) introduced as the substituent B, when M is an oxygen atom, the general formula

[0035]

[Chemical 14]

(Wherein R ^{6 to} R ¹⁰ are the same as above), and when M is a sulfur atom, a general formula is used.

[0037]

[Chemical 15]

(Wherein R ^{6 to} R ¹⁰ are the same as above), and when M is an imide group, a general formula is used.

[0039]

[Chemical 16]

(In the formula, R ^{6 to} R ¹⁰ are the same as above.) An aniline or a derivative thereof is used. The compound forming the substituent A and the compound forming the substituent B are mixed with chlorophosphazene [a cyclic compound represented by the formula (NPCl ₂ ) _n or a compound represented by the formula Cl ₄ P. (NPCl ₂ ) _n-1.
The desired phosphazene compound of the general formula (I) can be obtained by reacting with a chain compound represented by PCl ₃ (n is an integer of 3 or more, preferably 3-18). When the compound forming the substituent B is an alcohol, a mercaptan, a phenol or a thiophenol, an alcoholate, a phenolate or a mercaptide is previously reacted with an alkali metal such as sodium metal or potassium metal. , It may be stored as thiophenolates. Further, in the reaction of the compound forming each of the substituents A and B with chlorophosphazene, it is preferable to use a dehydrohalogenating agent such as a tertiary amine. Examples of the tertiary amine include trimethylamine, triethylamine, triisopropylamine, tri-n-propylamine, tri-n-butylamine, pyridine, and the like. Of these, pyridine is preferable. Furthermore, this reaction is usually performed in an organic solvent. The organic solvent used is benzene, toluene,
Examples thereof include xylene, chloroform, cyclohexane, methylene chloride, tetrahydrofuran, 1,4-dioxane. These can be used alone or in combination. In the curable phosphazene compound obtained by the above reaction, it is preferable that all the chlorine atoms of chlorophosphazene which is a raw material are substituted with the above-mentioned substituents, but some chlorine may remain.

The antistatic material of the present invention is mainly composed of the conductive fine particles of the component (A) and the curable phosphazene compound of the component (B), and, if necessary, the curable phosphazene of the component (B). A curable composition is prepared by blending a monomer copolymerizable with the compound (monomer for copolymerization) or an additive such as an emulsifier, a suspension stabilizer, a polymerization initiator, an ultraviolet absorber and a lubricant. The curable composition can be obtained by applying the curable composition onto the substrate and polymerizing and curing the curable phosphazene compound as the component (B) to form a cured resin surface layer. Here, the mixing ratio of the conductive fine particles of the component (A) in this curable composition is 30 to 300 parts by weight based on the characteristics of the cured resin surface layer, relative to 100 parts by weight of the curable phosphazene compound of the component (B). , Preferably 60 to 250 parts by weight.

Various kinds of monofunctional monomers and / or polyfunctional monomers copolymerizable with the curable phosphazene compound as the component (B) can be used. That is, as the monomer (copolymerization monomer) copolymerizable with the curable phosphazene compound, a silicone-modified curable compound, a polymerizable prepolymer, and further an acryloyl group, a methacryloyl group, a vinyl group or an allyl group can be used. Examples thereof include compounds having a reactive double bond such as a polymerizable monomer. Here, the silicone-modified curable compound is not particularly limited as long as it is a compound having a silicone (silane) group and preferably a (meth) acrylate group in one molecule. Specific examples of the silicone-modified curable compound include silicone-modified urethane acrylate, (meth) acryloxysilane compound, and (meth) acrylate-modified polysiloxane. Examples of the (meth) acryloxysilane compound include γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropylmethyldimethoxysilane. As the (meth) acrylate-modified polysiloxane, there is a compound containing a silicone (silane) group and a (meth) acrylate group in one molecule.

Specific examples of the polymerizable monomer having an acryloyl group, a methacryloyl group and the like include methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and 2-hydroxy. Monofunctional groups such as propyl (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (Meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate , Bifunctional functional groups such as hydroxybivalic acid ester neopentyl glycol di (meth) acrylate, trifunctional functional groups such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate Mention may be made of polyfunctional compounds having groups or more.

On the other hand, as the polymerizable prepolymer, for example, polyester (meth) acrylate, polyurethane (meth) acrylate, epoxy (meth) acrylate, polyether (meth) acrylate, melamine (meth) acrylate, oligo (meth) acrylate. , Alkyd (meth) acrylates, polyol (meth) acrylates, silicon (meth) acrylates, and other prepolymers having at least one (meth) acryloyl group. A particularly preferred prepolymer is polyester,
Epoxy and polyurethane (meth) acrylates. As the polyester (meth) acrylate,
For example, ethylene glycol, 1,4-butadiol,
Polyhydric alcohols such as 1,6-hexanediol, diethylene glycol trimethylolpropane, dipropylene glycol, polyethylene glycol, polypropylene glycol, pentaerythritol, dipentaerythritol and phthalic acid, adipic acid, maleic acid, trimellitic acid, itaconic acid Polyesters obtained from a polybasic acid such as succinic acid, terephthalic acid, and alkenylsuccinic acid, and then (meth) acrylated one are listed. Examples of the above (meth) acrylated ones include adipic acid / 1,6-hexanediol / (meth) acrylic acid type, phthalic anhydride / propylene oxide / (meth) acrylic acid type, trimellitic acid / diethylene glycol /
Acrylic acid-based polyester (meth) acrylates may be mentioned. Epoxy (meth) acrylate is obtained by esterifying an epoxy group of an epoxy resin with (meth) acrylic acid to make a functional group a (meth) acryloyl group. An example of this is bisphenol A-
Epoxy (meth) acrylates such as epichlorohydrin type epoxy resin / (meth) acrylic acid type, phenol novolac-epichlorohydrin type epoxy resin / (meth) acrylic acid type, alicyclic epoxy resin / (meth) acrylic acid type and the like can be mentioned. The polyurethane (meth) acrylate can be obtained, for example, by reacting an isocyanate compound such as tolylene diisocyanate with a (meth) acrylate having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate. In this case, the central part of the molecule often has a polyester structure, and is often (meth) acrylated by disposing isocyanate groups at both ends. Examples of urethane compounds include oil-modified polyurethane resin systems, moisture-curable polyurethane resin systems, block-type polyurethane resin systems, and catalyst-curable polyurethane resin systems. Examples of the epoxy compound include those obtained by adding an appropriate curing agent to epoxy resin, those obtained by esterification by the reaction of epoxy resin and fatty acid, and those obtained by using epoxy resin and alkyd resin together. Examples of the silicone compound include an initial condensate obtained by mixing a small amount of dimethyldichlorosilane and diethyldichlorosilane with monomethyl or monoethyltrichlorosilane and reacting them. The obtained initial condensate is usually dissolved in a suitable solvent and, if necessary, a curing accelerator such as a soluble fatty acid salt or zinc octinate is added before use.

A normal temperature curing method can be used to coat and cure this curable composition on a substrate. However, considering the characteristics of the cured resin surface layer to be obtained, a heat curing method and an active energy ray are used. It is preferable to use a method of curing by irradiating with (visible light, ultraviolet ray, electron beam, X-ray, γ-ray, etc.). Therefore, in preparing this curable composition, the preparation method is changed depending on the curing method at the time of polymerization or copolymerization of the curable phosphazene compound as the component (B). That is, when a heat curing method is used in carrying out the above-mentioned polymerization or copolymerization, it is preferable to use a peroxide compound or an azo compound as a polymerization initiator, if necessary, alone or in combination. Examples of the peroxide-based compound include benzoyl peroxide; p-chlorobenzoyl peroxide; 2,4-dichlorobenzoyl peroxide; t-butyl hydroperoxide; di-t-butyl peroxide; Examples include mill peroxide, t-butyl peroxyacetate and t-butyl peroxybenzoate. Other peroxides (persulfate, redox type) can also be used. Examples of the persulfate include ammonium persulfate and potassium persulfate, and for the redox type, hydrogen peroxide-metal salt. , Organic peroxide-metal salt, organic peroxide-aliphatic or alicyclic polyamine compound, organic peroxide-dimethylaniline, potassium dichromate-metal oxide, etc.
Examples of the azo compound include aromatic diazoamino compounds, aromatic diazothioethers, aromatic diazooxy compounds, and aliphatic diazo compounds. In the heat curing method, it may be completely cured at 100 ° C. or higher, though it depends on the conditions such as the coating amount and the coating speed of the curable composition.

On the other hand, when carrying out the above-mentioned polymerization or copolymerization,
When utilizing a curing method using active energy rays such as ultraviolet rays, electron rays or visible rays, it is preferable to use a polymerization initiator (photosensitizer), if necessary. As the polymerization initiator, various kinds can be used. Specifically, for example, 1-hydroxycyclohexyl phenyl ketone, dibenzoyl, benzoyl, benzoin methyl ether, benzoin ethyl ether, p-
Chlorobenzophenone, p-methoxybenzophenone,
Examples thereof include benzoyl peroxide, di-t-butyl peroxide and camphorquinone. These reaction initiators can be used alone or in combination. The compounding amount of these reaction initiators is usually 0.05 with respect to 100 parts by weight of the curable phosphazene compound.
It is used in the range of 10 to 10 parts by weight. In this curing method using active energy rays, for example, in the case of ultraviolet rays, the ultraviolet rays having a wavelength in the range of 200 to 550 nm are
Irradiation may be performed for 2 seconds or more, preferably for 3 to 300 seconds.
Here, the integrated light quantity of the irradiation light rays is usually 500 to 5,000.
It is mJ / cm ² . Here, the amount of the polymerization initiator used is
Usually, based on 100 parts by weight of the curable phosphazene compound,
It is selected in the range of 0.1 to 10 parts by weight.

When the curable composition is applied onto the substrate, it can be diluted with an organic solvent and used for its workability and control of the film thickness of the cured resin surface layer.
Here, as the organic solvent, for example, ketones such as methyl ethyl ketone and methyl ime butyl ketone, alcohols such as 2-propanol and 1-butanol, cellosolves, acetic acid esters, ethers, aromatic hydrocarbons, etc. Or, it can be used by appropriately mixing them. Further, the curable composition may be blended with other various additives as long as the purpose is not impaired. Here, examples of other additives include ordinary curing agents, polymerization inhibitors, color formers, antioxidants, ultraviolet absorbers and lubricants. The lubricant may be liquid or grease-like, and silicone-based, fluorine-based, and other synthetic lubricants may be used.

An example of the component composition of the curable composition prepared by providing the cured resin surface layer is as follows. (A) 100 parts by weight of curable phosphazene compound (b) 0 to 300 parts by weight of monofunctional monomer and / or polyfunctional monomer copolymerizable with curable phosphazene compound (c) Organic solvent (d) Photoreaction initiator or thermal polymerization initiator 0.05 to 5 parts by weight [relative to 100 parts by weight of (a) and (b)] (e) Conductive fine particles 30 to 300 parts by weight [(a) and ( (b) to 100 parts by weight in total] (f) Other additives The curable resin having such a composition is sufficiently stirred and dispersed by a dispersing / stirring machine generally used for dispersing the pigment. And prepared. As the dispersing / stirring machine used for preparing the curable composition, various kinds can be used. Specific examples include a sand mill, a roll mill, a ball mill, an ultrasonic disperser, and a microfluidizer disperser. The organic solvent is not necessarily used, but in terms of workability and thickness control of the cured resin surface layer after curing as described above, the weight concentration of the mixture of (a) and (b) is preferably 0.5-6
It may be dissolved in an organic solvent so that the concentration becomes 0%.

The antistatic material of the present invention comprises the curable composition thus prepared on a substrate, and a coater (for example, spin coater,
After coating with a gravure coater, roll coater, blade coater, doctor coater, spray coater, curtain flow coater, etc., remove the solvent if necessary. Then, it is cured by the above-mentioned curing method,
It can be obtained by forming a cured resin surface layer. Thus, the thickness of the cured resin surface layer formed on the substrate is 1 μm or more, preferably 5 to 100 μm, and an antistatic material having excellent properties such as transparency, scratch resistance, and heat resistance is obtained. You can

[0050]

EXAMPLES Next, the present invention will be described in more detail based on production examples and examples, but the present invention is not limited thereto. Production Example 1 Production of curable phosphazene compound (A) In a 2 liter flask equipped with a thermometer, a stirrer, a dropping funnel and a condenser, hexachlorocyclotriphosphazene [cyclic compound of formula (NPCl ₂ ) ₃ ] 8
6.8 g was dissolved in 338 g of dehydrated benzene. To this benzene solution, 310 g of pyridine and 0.29 g of hydroquinone were added and stirred. Next, 200 ml of 2-hydroxyethyl methacrylate was dissolved in 237 ml of benzene, and this solution was dropped into the above flask and reacted at 60 ° C. for 30 hours. After the reaction, the pyridine hydrochloride was removed by filtration. The filtrate was washed with water, then dried using Glauber's salt, the solvent was removed by vacuum distillation, and the viscous 1,1,3,3,5,5-hexa (methacryloylethylenedioxy) cyclotriphosphazene [ 200 g of curable phosphazene compound (A) was obtained.

Production Example 2 Production of Curable Phosphazene Compound (B) 300 ml of tetrahydrofuran and 25.5 g of sodium metal were placed in a 2 liter flask equipped with a thermometer, a stirrer, a dropping funnel and a condenser. 104.3 g (1.11 mol) of phenol was added dropwise to the mixture, and after completion of the addition, the mixture was refluxed for 3 hours to obtain a phenolate. Then, a solution prepared by dissolving 193 g (0.555 mol) of hexachlorocyclotriphosphazene in 400 ml of benzene was added dropwise to the above reaction solution, and the reaction was allowed to proceed for 4 hours under reflux. Then, the temperature of the reaction solution was cooled to room temperature, 352 g (4.45 mol) of pyridine was added, and 381 g (2.45 mol) of 2-hydroxyethyl methacrylate was gradually added dropwise from the dropping funnel. Furthermore, the mixture was heated to 60 ° C. in a hot water bath, reacted for 20 hours while stirring, the precipitated crystals and catalyst were filtered off, the solvent in the obtained filtrate was removed by distillation under reduced pressure, and the residue was sufficiently dried. To obtain 452 g of a yellow liquid [curable phosphazene compound (B)].

Example 1 Curable composition blend Curable phosphazene compound (A) 25 g Sb-doped SnO ₂ 25 g [T-1, manufactured by Mitsubishi Materials Corp., primary particle size 0.02 μm] Methyl isobutyl ketone 36 g Butyl cellosolve 3 g Isopropanol 40 g Cellosolve acetate 36 g The component composition having the above composition was mixed and treated in a 200 W ultrasonic cleaning tank for 15 minutes, and then treated using a microfil diser as a disperser and sufficiently dispersed. 2-Methyl- [4- (methylthio) phenyl] -2 was added to this dispersion.
-Morifolino-1-propanone (1.25 g) was added and dissolved to prepare a curable composition (a). This curable composition (a) was applied to a transparent polycarbonate plate having a thickness of 3 mm using a spin coater, the solvent was evaporated at 80 ° C. for 10 minutes, and then 500 mJ / cm ² ultraviolet rays were irradiated with a high pressure mercury lamp. Then, a polycarbonate plate of the present invention having a cured resin surface layer of 2 μm was obtained.

Example 2 A cured resin surface layer was prepared in the same manner as in Example 1 except that the curable phosphazene compound (B) was used in place of the curable phosphazene compound (A). A polycarbonate plate having The evaluation results are shown in Table 1. Example 3 In Example 1, Sn was used instead of Sb-doped SnS _2.
The same procedure was performed as in Example 1 except that doped In ₂ O ₃ was used. The evaluation results are shown in Table 1. Example 4 Curable composition blended Sb-doped SnO ₂ coated BaSO ₄ 25 g [Mitsui Metals Co., Ltd. Pastran IV, primary particle size 0.5 μm] Methyl isobutyl ketone 36 g Butyl cellosolve 3 g Butanol 35 g Isopropanol 40 g Cellosolve acetate 36 g Nonionic system Surfactant 0.5 g The component composition having the above composition was mixed and treated in a 600 W ultrasonic cleaning bath for 30 minutes. Curable phosphazene compound (A) 12.5 g dipentaerythritol hexaacrylate 12.5 g [Arakawa Chemical Co., Ltd. beam set 700] 1-hydroxycyclohexyl phenyl ketone 1.2 g was added and dissolved in this liquid. As a result, a curable composition (b) was prepared by treating with a microfil diser and sufficiently dispersing. It carried out like Example 1 except having changed curable composition (a) of Example 1 into curable composition (b).

Example 5 Curable composition blending Sb-doped SnO ₃ 20 g [T-1, manufactured by Mitsubishi Materials Corporation, primary particle size 0.02 μm] Toluene 160 g Nonionic surfactant 0.5 g Component composition consisting of the above blending Were mixed and treated with a microfil diser as a disperser to sufficiently disperse. Curable phosphazene compound (A) 7g Dipentaerythritol hexaacrylate 7g [Kayarad DPHA manufactured by Nippon Kayaku Co., Ltd.] 2,2-bis (4-acryloxydiethoxyphenyl) propane 6g [Nippon Kayaku Co., Ltd.] ) Kayarad R-551] 2-methyl [4- (methylthio) phenyl] -2-morpholino-1-propane 1 g p-Dimethylaminobenzoic acid ethyl ester 0.6 g was added and dissolved, and a microfil dye was used as a disperser. A curable composition (c) was prepared by treating and sufficiently dispersing it using a mill. This curable composition (c) was applied to a 100 μm-thick transparent polyethylene terephthalate film using a gravure coater, the solvent was evaporated with hot air at 80 ° C. for 20 seconds, and then 500 mJ / cm ² ultraviolet rays were applied using a high pressure mercury lamp. To obtain a polyethylene terephthalate film of the present invention having a cured resin surface layer of 2 μm.

Comparative Example 1 Curable composition blend Curable phosphazene compound (A) 25 g Dipentaerythritol hexaacrylate 25 g [Beamset 700 manufactured by Arakawa Chemical Co., Ltd.] Nonionic surfactant 1 g [Nippon Oil & Fat Co., Ltd. Elegan S-100] Methyl isobutyl ketone 36 g Butyl cellosolve 3 g Butanol 35 g Isopropanol 40 g Cellosolve acetate 36 g The component composition having the above composition was mixed, and the mixture was treated using a microfil diser as a disperser and sufficiently dispersed. The same procedure as in Example 1 was carried out except that this dispersion liquid was used. Comparative Example 2 The procedure of Example 1 was repeated, except that P3055 (UV curable type) manufactured by Catalyst Kasei Co., Ltd. was used as a commercially available transparent conductive powder-dispersed curable composition.

Each of the antistatic materials obtained in Examples and Comparative Examples was tested for steel wool resistance, abrasion resistance, adhesion and the like as physical property evaluation. The evaluation results are shown in Table 1. The test methods are as follows. 1. Total light transmittance Based on JIS K-7105. 2. Haze Based on JIS K-7105. 3. Adhesion The cross-cut (1 mm width, 100 sections) cellophane tape peeling method was used to evaluate the number of unpeeled parts. Example 0/100: All peeling, 100/100: No peeling 4. Abrasion resistance According to Taber abrasion test method. Abrasion wheel CS-10 load 500 g Evaluation was made by the haze difference (ΔH) before and after the test. 5. Steel wool resistance Steel wool test method was followed. Steel wool # 0000 load 500 g / cm ² 100 times reciprocation It was evaluated by the presence or absence of scratches before and after the test. 6. Surface resistivity Based on JIS K-6911.

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[Table 1]

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[Table 2]

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INDUSTRIAL APPLICABILITY As described above, the antistatic material using the fine particles and the curable phosphazene compound, which are based on the indium oxide or tin oxide of the present invention and are subjected to the conductivity imparting treatment, has high hardness and transparency. It also has excellent properties such as scratch resistance and heat resistance, as well as excellent antistatic properties. Therefore, the antistatic material of the present invention is effectively used as a member for electric / electronic devices and the like.

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[Procedure amendment]

[Submission date] February 12, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0047

[Correction method] Change

[Correction content]

When the curable composition is applied onto the substrate, it can be diluted with an organic solvent and used for its workability and control of the film thickness of the cured resin surface layer.
Here, as the organic solvent, for example, ketones such as methyl ethyl ketone and methyl ime butyl ketone, alcohols such as 2-propanol and 1-butanol, cellosolves, acetic acid esters, ethers, aromatic hydrocarbons, etc. Or, it can be used by appropriately mixing them. Further, the curable composition may be blended with other various additives as long as the purpose is not impaired. Here, other additives include ordinary curing agents, polymerization inhibitors, color formers, antioxidants, ultraviolet absorbers, lubricants, surface modifiers,
Examples include a dispersant.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0049

[Correction method] Change

[Correction content]

The antistatic material of the present invention comprises the curable composition thus prepared on a substrate, and a coater (for example, spin coater,
After coating with a gravure coater, roll coater, blade coater, doctor coater, spray coater, curtain flow coater, etc., remove the solvent if necessary. Then, it is cured by the above-mentioned curing method,
It can be obtained by forming a cured resin surface layer. Thus, the thickness of the cured resin surface layer formed on the substrate is 1 μm or more, preferably 2 to 100 μm, and an antistatic material having excellent properties such as transparency, scratch resistance, and heat resistance is obtained. You can

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0053

[Correction method] Change

[Correction content]

Example 2 A cured resin surface layer was prepared in the same manner as in Example 1 except that the curable phosphazene compound (B) was used instead of the curable phosphazene compound (A). A polycarbonate plate having The evaluation results are shown in Table 1. Example 3 In Example 1, Sn was used instead of Sb-doped SnO _2.
Same as Example 1 except that doped In ₂ O ₃ was used. The evaluation results are shown in Table 1. Example 4 Curable composition blended Sb-doped SnO ₂ coated BaSO ₄ 25 g [Mitsui Kinzoku Co., Ltd. Pastran IV, primary particle size 0.5 μm] Methyl isobutyl ketone 36 g Butyl cellosolve 3 g Butanol 35 g Isopropanol 40 g Cellosolve acetate 36 g Nonionic system Surfactant 0.5 g The component composition having the above composition was mixed and treated in a 600 W ultrasonic cleaning bath for 30 minutes. Curable phosphazene compound (A) 12.5 g dipentaerythritol hexaacrylate 12.5 g [Arakawa Chemical Co., Ltd. beam set 700] 1-hydroxycyclohexyl phenyl ketone 1.2 g was added to this liquid and dissolved to obtain a disperser. As a result, a curable composition (b) was prepared by treating with a microfil diser and sufficiently dispersing. It carried out like Example 1 except having changed curable composition (a) of Example 1 into curable composition (b).

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0057

[Correction method] Change

[Correction content]

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[Table 1]

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location H01B 1/00 D 7244-5G // C08L 43:02 7921-4J

Claims (3)

[Claims] 1. A main component comprising (A) conductive fine particles of indium oxide-based fine particles or tin oxide-based fine particles, conductive fine particles coated with the surface of the fine particles, and (B) curable phosphazene compound on a substrate. An antistatic material obtained by applying and curing a curable composition to form a cured resin surface layer. 2. The antistatic material according to claim 1, wherein the conductive particles of the component (A) have a primary particle diameter of 20 μm or less. 3. The antistatic material according to claim 1, wherein the content of the conductive fine particles as the component (A) is 30 to 300 parts by weight based on 100 parts by weight of the curable phosphazene compound as the component (B).