KR100512687B1 - Uv curing type composition having high conductivity and superior anti-scratching - Google Patents

Abstract

The present invention relates to a composition for forming sheets having conductivity and scratch resistance, comprising a polythiophene conductive polymer, a UV-oligomer or / and a monomer, an organic solvent, a photoinitiator, and a scratch additive. 4 to 5.9% by weight of a polythiophene-based conductive polymer, 7 to 9.9% by weight of UV-oligomer or / and monomer, 82 to 89% by weight of solvent, 0.4 to 0.8% by weight of photoinitiator and 0.03 to 0.05% by weight of scratch resistant additive The present invention relates to a composition for molding sheets having electroconductivity and scratch resistance.

Description

UV curing type composition having high conductivity and superior anti-scratching

The present invention relates to a UV-curable composition having high conductivity, high transparency and excellent scratch resistance when coated on a transparent plastic polymer material. More specifically, a small amount of UV-oligomer or / and monomer, organic solvent, and scratch resistant additives are added to the polythiophene-based conductive polymer solution, so that visible light transmittance is 96%. It is related with the ultraviolet curable composition which has the high electrical conductivity whose surface resistance is 10 ⁷ ohms / square or less, and was excellent in scratch resistance.

Recently, as the conductive coating material of the CRT glass surface using a conductive polymer has been attracting attention, polyethylene dioxythiophene (PEDT), which is a polythiophene-based conductive polymer, is described, as described in US Pat. It is from the beginning of attention.

This conductive polymer has a property of exhibiting excellent transparency compared with other conductive polymers such as polyaniline and polypyrrole, as well as polythiophene. The PEDT has excellent properties in terms of processability as it can prepare a water dispersible coating solution using a high molecular acid salt (for example, polystyrene sulfonate) as a doping material. In addition, due to the characteristics of the water dispersion, it is also excellent in compatibility with organic solvents can be used as a coating material for a variety of applications, such as CRT glass, plastic film surface. In addition, since an ether or an alcohol is used as the organic solvent, it is very advantageous from an environmental point of view.

A representative example of such a water-dispersible PEDT is BAYTRON PH of Bayer Co., Ltd., which is currently being sold.

However, even though the PEDT conductive polymer is excellent in transparency, it is difficult to achieve a surface resistance of 10 ⁷ Ω / □ or less by coating with a low concentration of PEDT in order to maintain high transparency of 96%.

In addition, silicon oil or mineral oil is used as a scratch-resistant agent to reinforce the film hardness, but when it is used, the conductivity decreases, making it impossible to manufacture a conductive film of 10 ⁷ Ω / □ or less, which requires low conductivity. It is a situation that is used only as a low level antistatic coating material.

Due to these shortcomings, a technique having a high transmissivity of 96% or more and having a commercially available surface resistance of less than 10 ⁷ Ω / □ as an electromagnetic wave shielding material or a high performance antistatic coating agent has not been possible with conventional techniques. .

The present invention provides a composition for producing a PEDT conductive polymer thin film having excellent scratch resistance having a high conductivity of 10 ⁷ Ω / □ or less when the plastic film is coated and having a high transparency of 96% or more. To develop.

Still another object of the present invention is to determine a composition component of the composition that satisfies the target physical properties and to provide a composition component expressing physical properties reproducibly and its composition ratio. By reducing the content of binder solids, visible light transmittance of 96% or more, high concentration of PEDT conductive polymer, small amount of ethoxylated silicon, oligomer and monomer have high conductivity of 10 ⁷ Ω / □ or less. By adding a small amount of ethoxylated silicon, the scratch resistance was further increased to complete the present invention.

Another object of the present invention is to provide a conventional sheet molding such as a film, panel, sheet using the composition.

The present invention provides 4 to 5.9 wt% of polythiophene conductive polymer aqueous solution, 7 to 9.9 wt% of UV-oligomer or monomer, 82 to 88 wt% of solvent, 0.4 to 0.8 wt% of photoinitiator, and 0.02 to 0.05 wt% of scratch resistance additive. An ultraviolet curable composition having conductivity and scratch resistance, characterized in that the surface resistance is 10 ⁷ Ω / □ or less, transmittance of 96% or more, pencil hardness of 4H or more when the coating film is prepared from this solution do.

The composition of the present invention is polymethyl methacrylate, polycarbonate, polyethylene terephthalate, amorphous polyethylene terephthalate, polyether sulfone, polyvinyl chloride, MS resin (copolymer of MMA and SM), triacetate cellulose It is coated and used on a transparent film or sheet made of plastic such as a bath.

When the solution composition according to the present invention is coated on a transparent substrate such as glass or resin film, the conductivity is 1 × 10 ⁶ to 9 × 10 ⁶ Ω / □ or less, transmittance of 96% or more, hardness of 4H or more, high conductivity and high transparency A hard coat film of is obtained.

An example of the conductive polymer in the present invention is Bayer's PEDT (trade name: Baitron P.H.), which is doped with polystyrenesulfonate (PSS) and exhibits a property of being well soluble in water. The safety is very good. PEDT also has a 1.3% PEDT and PSS solids concentration to maintain optimum dispersibility in water. The PEDT can be easily coated by diluting with such a solvent because it is well mixed with water, alcohol or a solvent having a high dielectric constant, and shows excellent transparency compared with other conductive polymers such as polyaniline and polypyrrole even when the coating film is formed. .

PEDT conductive polymer solution usage and suitably 4 to 5.9% by weight, 4% less than when an organic solvent is further added, and raised when the amount of meona monomer be fixed amount of the conductive polymer for conducting implemented so low sheet resistance 10 ⁷ Ω It is difficult to realize high conductivity of / □ or less, and when it is added in excess of 5.9% by weight, the transmittance due to the increase of the conductive high molecular weight with colorability decreases to 96% or less, which is not preferable.

As the organic solvent of the PEDT conductive polymer of the present invention, n-propyl alcohol, methyl cellosolve (MCS), propylene glycol methyl ether (PM), diacetone alcohol (DAA) are used alone or Although mixed with each other, most preferably, methyl cellosolve (MCS) or propylene glycol methyl ether (PM), which is an ether solvent having a methyl group as an organic solvent, is the most preferable to realize the maximum conductivity of the PEDT conductive polymer. Solvent.

In the present invention, methanol, ethanol, butyl acetate (BA), ethyl acetate (EA), isopropanol (IPA) and ethyl cellosolve (EC), which are common solvents used in UV curable resin compositions, are It is not good because it has a very bad effect on conductivity.

The amount of the organic solvent is suitably 82 to 88% by weight, but less than 82% by weight increases the composition of the coating liquid, that is, the amount of the conductive polymer and the oligomer and monomer, so that the visible light transmittance is deteriorated or high resistance is formed. If the content exceeds 88% by weight, the visible light transmittance is extremely improved, but scratch resistance does not meet the criteria of the present invention.

The UV-oligomer used in the present invention uses a urethane-based (meth) acryl oligomer, wherein the molecular weight is less than 2400. It is not good that 2400 or more becomes solubility and dispersibility bad. The urethane-based (meth) acrylic oligomer is a condensate of ordinary isocyanates and diols, and any one can be used as long as the molecular weight is 2400 or less. Among the urethane-based (meth) acryl oligomers having a molecular weight of 2400 or less, dipentaerythritolpentaacrylate (DPPA) represented by the following formula (3) and an isocyanate trimer represented by the formula (2) (general name: H-MDI, manufacturer: Nippon POLYURETHANES, product name: CORONATE) Compound (U-DPPA), which is an oligomer synthesized by reacting HX), shows more excellent physical properties. In addition, when a mixture of monomers such as DPHA (dipentaerithritolhexaacrylate) and U-DPPA is used, it shows a remarkable effect of lowering the resistance value to the order of 0.5 and has very good results.

As the monomer used in the present invention, mono- and bi-functional or higher polyfunctional acrylic monomers and mixtures thereof are used. As polyfunctionality, polyol pentaerythritol, an acrylic monomer of dipentaerythritol, for example, dipentaerythritol hexaacrylate (DPHA), or a hydroxyalkyl acrylate, for example, 2-hydroxyethyl As monofunctional monomers, such as methacrylate (2-hydroxymethacrylate: HEMA), for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylate (Meth) acrylic acid C _1-20 alkyl esters such as octyl (meth) acrylate and 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylate, benzyl (meth) acrylate (Meth) acrylic acid hydroxy C _2-4 alkyl esters such as 2-hydroxyethyl acrylate and 2-hydroxypropyl (meth) acrylate can be used, and these copolymerizable monomers can be used alone or in combination thereof. Can be used.

The amount of UV-oligomer or / and monomer used is 7 to 9.9% by weight. If it is less than 7% by weight, there is a disadvantage in that surface scratches occur due to the hardness, and in the case of 9.9% by weight or more, the surface resistance is 10 ⁷ Ω / □ or more. There is a drawback to increasing.

Photoinitiator of the present invention alpha-hydroxycyclohexylphenylmethanone (photoinitiator of Ciba Geigy: iRgAcure # 184), 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl It is preferable to use propanone, hydroxydimethylacetophenone, benzophenone, or the like, and when cured with iRgAcure # 184, the resistance value can be lowered by 0.5 orders than other initiators.

The use amount of the photoinitiator is preferably 0.4 to 0.8% by weight. If the content is less than 0.4% by weight, the photopolymerization is slow. If the content is 0.8% or more, the reaction rate is high but the surface properties are deteriorated.

The scratch additive of the present invention uses ethoxylated silicon (trade name: SiLWET, company name: GE SiLiCONES), which does not inhibit the conductive implementation of the conductive polymer. In addition, a minimum amount of silicone additive should be added to maintain the surface resistance at an appropriate level (10 ⁶ Ω / □). When using a silicone oil or fruit oil, which is commonly used as a scratch-resistant additive, the surface resistance value is lowered so that the target value cannot be obtained. Therefore, the ethoxylated silicon compound of the present invention should be used. There is no deterioration and it shows a very good effect compared to other scratch resistant additives.

The use amount of the scratch resistant additive is preferably 0.02 to 0.05% by weight. If it is 0.02 wt% or less, scratch resistance is inferior, and if it is 0.05 wt% or more, there is a problem that conductivity is degraded.

The method for preparing a polythiophene conductive polymer solution composition having high conductivity and high transparency according to the present invention is firstly added with an aqueous solution of PEDT conductive polymer in a mixing vessel, and vigorously stirred, followed by organic solvent, UV-oligomer or / and A monomer, a photoinitiator, and a scratch-resistant additive are added and uniformly mixed for about 2 to 4 hours. The prepared composition is made of polymethyl methacrylate, polycarbonate, polyethylene terephthalate, amorphous polyethylene terephthalate, polyether sulfone, polyvinyl chloride. Pour the mixed solution composition of the present invention onto a transparent film made of plastic, such as Ride and MS resin, and apply it uniformly by bar coating, spin coating, flow coating, or dip coating, and then move about 60 to 90 ° C. Keep the chain dry area for 1 to 5 minutes to allow water and solvents in the coating And completely evaporated. Then, the ultraviolet light amount of 400 ~ 1050 mJ / cm ² is irradiated to the acrylic sheet to prepare a transparent high conductivity polymer film.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, and the following Examples are provided to illustrate the present invention and are not necessarily limited to the following Examples. In the following,% is% by weight unless otherwise indicated.

EXAMPLE

For the evaluation of the physical properties of the coating film is as follows. The mixed solution prepared in the Examples was flow coated on a dry acrylic sheet surface washed with alcohol, and then cured by irradiation with UV LAMP (1000 mJ / cm ² ) in a completely dried state in an oven at 70 ° C. for 3 minutes. I was. The thickness of the dried coating film is all 10 micrometers or less.

The physical property evaluation of the highly conductive acrylic sheet produced above was performed as follows.

Conductivity was measured by surface resistance by the test method of ASTM D257 using an ohmmeter group MONROE ELECTRONICS MODEL 292.

Visible light transmittance was measured by the test method of ASTM D1003 using an uv-visible light spectrophotometer.

Hardness was measured by the method of ASTM D3502 with a pencil hardness tester.

The scratch resistance was reciprocated 100 times with a load of 1 Kg / cm ^{2, and} the scratch resistance was measured by the test method of STEEL WOOL # 0000. Scratch is indicated on a 5-point scale. The case where no scratches occurred at all was 5 and the case where excessive scratches occurred was 1, and a comparative evaluation was made on a 5-point scale.

The adhesive strength was measured by measuring the adhesive strength by the method of ASTM D3359.

The composition and physical property evaluation results of Examples 1 to 4 and Comparative Example 1 to Comparative Example 5, which are polymer solution compositions deviating from the composition of the present invention, are shown in Tables 1 and 2, respectively, according to the present invention. It was.

* 1: Scratch-resistant additive: ethoxylated silicone (trade name: SILWET, company name: GE SILICONES)

* 2: Photo Initiator: Igacure # 184

* 3: U-DPPA: Manufacturer: NEW NAKAMURA (JAPAN), Product Name: Oligo U-15HA

As shown in Table 1, 5.9 wt% of the PEDT aqueous solution (hereinafter referred to as "PEDT aqueous solution") of 1.3% by weight in the composition used in Examples 1 to 4 and Comparative Examples 1 to 3 of the present invention, IRgACURE # 184 0.75% by weight as a photoinitiator, 0.02% by weight of ethoxylated silicon as a scratch-resistant additive in common, the component or content of the UV-curable oligomer is included in the composition range of the conductive polymer according to the present invention described above. In the case of the organic solvent In Examples 1 to 4, MCS (methyl cellosolve), PM, n-propyl alcohol, and DAA were used alone or in combination as preferred organic solvents used in the present invention. In 3, the comparison of physical properties was carried out using a mixture of EC and IPA. Comparative Example 4 and Comparative Example 5 is a composition that does not contain a scratch-resistant additive, out of the range of the composition according to the present invention. The physical property test results of the coating film prepared in Examples 1 to 4 and Comparative Examples 1 to 5 are shown in Table 2 below.

As shown in Table 2, Comparative Examples 1 to 3 using EC and iPA mixed solvents commonly used as organic solvents are used alone or in combination of MCS, PM, n-propyl alcohol, DAA (diacetone ethanol) In the case of Comparative Example 4 or Comparative Example 5, which is a polymer composition which exhibits a much higher resistance value than Examples 1 to 4, and does not contain a scratch resistant additive and has a composition deviating from the composition of the present invention, the conductivity drops sharply or the pencil hardness and scratch resistance It can be seen that the properties and transparency is significantly lower compared to the compositions of Examples 1 to 4 of the composition of the present invention. Particularly, in Comparative Example 4, 20 wt% of DPPA and U-DPPA were used as oligomers in excess of the composition content of the present invention, and 15 wt% of the conductive polymer was significantly higher than the composition content of the present invention. It is much lower than Examples 1-4, which is the composition of the invention.

Accordingly, Examples 1 to 4 of the conductive polymer solution composition according to the present invention maintain surface transmittance of 9 × 10 ⁶ Ω / □ while maintaining transmittance of 96% or higher, hardness of 4H or higher, and excellent scratch resistance. It was confirmed to have a high degree of low appearing below. On the other hand, Comparative Example 1 to Comparative Example 5, which is a polymer solution composition deviating from the composition of the present invention, can be confirmed that at least one of conductivity, permeability, and scratch resistance deviates from the object of the present invention, which is very inferior to the physical properties of the present invention in overall physical properties. Was in.

The conductive cured composition according to the present invention has high hardness and high scratch resistance having high hardness and surface resistance of 10 ⁷ Ω / □ or less by using the composition according to the present invention such as DHPA and U-DPPA oligomer and conductive polymer. It also has the advantage, and also reduces the amount of binder solids used to reduce the conductive high molecular weight has the advantage of implementing the visible light transmittance.

Claims (14)

4 to 5.9 wt% of polythiophene conductive polymer solution having 1.3 wt% solids, 7 to 9.9 wt% of UV-oligomer, 82 to 88 wt% of organic solvent, 0.4 to 0.8 wt% of photoinitiator and 0.02 to 0.05 scratch resistance additive A composition consisting of weight percent The organic solvent is at least one selected from n-propyl alcohol, methyl cellosolve, propylene glycol methyl ether or di-acetone alcohol, The photoinitiator is selected from alpha-hydroxycyclohexylphenylmethanone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl propanone, hydroxydimethylacetophenone or benzophenone benzoin Any one or more, The scratch resistant additive is ethoxylated silicon, The coating film prepared by using the composition has a hardness of 4H or more, 10 ⁷ Ω / □ or less surface resistance and 96% or more visible light transmittance, UV curable composition having a scratch resistance. The method of claim 1, The UV-oligomer is a UV-curable composition having a conductive and scratch resistance, characterized in that it further comprises an ultraviolet curing monomer. The method of claim 2, The UV-oligomer is a UV-curable composition having a conductive and scratch resistance, characterized in that the UV-oligomer selected from U-DPPA, a urethane-based (meth) acryl oligomer having an average molecular weight of 2400 or less, or a mixture of U-DPPA and DPHA. . The method of claim 3, wherein The UV-curable composition having a conductive and scratch resistance, characterized in that the UV- oligomer is a mixture of U-DPPA and DPHA. delete delete The method of claim 1,      The photoinitiator is an ultraviolet-curable composition having conductivity and scratch resistance, characterized in that alpha-hydroxycyclohexylphenylmethanone. The method of claim 1, A polythiophene-based polymer is an ultraviolet curable composition having conductivity and scratch resistance, characterized in that polystyrenesulfonate (PSS) is used as a dopant. A sheet molding having an antistatic property and a scratch resistance produced using the ultraviolet curable composition of any one of claims 1 to 8. delete delete 4 to 5.9 wt% of polythiophene-based conductive polymer aqueous solution having a solid content doped with polystyrenesulfonate of 1.3 wt%, 7 to 9.9 wt% of a mixture of U-DPPA and DPHA, 82 to 88 wt% of organic solvent, alpha as photoinitiator 0.4 to 0.8 wt% of hydroxycyclohexylphenylmethanone and 0.02 to 0.05 wt% of ethoxylated silicone as a scratch-resistant additive, and the coating film prepared using the composition has a hardness of 4H or more and 10 ⁷ Ω / □ or less. An ultraviolet curable composition having conductivity and scratch resistance, characterized by having a surface resistance of and a visible light transmittance of 96% or more. The method of claim 12, The organic solvent is a UV-curable composition having conductivity and scratch resistance, characterized in that at least one solvent selected from normal-propyl alcohol, methyl cellosolve, propylene glycol methyl ether, di- acetone alcohol. An antistatic and scratch resistant sheet molded article prepared using the ultraviolet curable composition of claim 12.