KR20200006342A - Heat-curing composition having a flame retardant property and an antistatic property, method of coating using the same, and coating substrate comprising the same - Google Patents

Abstract

The present invention relates to a thermosetting composition having flame retardancy and antistatic properties, to a coating method using the same, and to a coating substrate comprising the same. The thermosetting composition comprises: a binder containing an aqueous thermosetting inorganic material; a flame retardant; and an antistatic agent.

Description

Heat-curing composition having a flame retardant property and an antistatic property, method of coating using the same, and coating substrate comprising the same}

The present invention relates to a thermosetting composition having both flame retardancy and antistatic properties. Specifically, it is an environmentally-friendly aqueous coating composition for the purpose of using an aqueous inorganic compound as a binder and implementing antistatic performance using PEDOT-PSS and simultaneously implementing flame retardancy.

In general, the antistatic coating composition used is a heat drying method by dispersing a conductive material in a solvent such as water and alcohol, and using a water-dispersed polyurethane or acrylic emulsion as a binder to realize surface resistance. Are manufactured. Alternatively, the organic solvent, which is a volatile organic compound, is diluted with UV-curable oligomers or monomers to be UV-curable, and the surface resistance is coated on plastic substrates such as PET, PC, PMMA, and PVC in the range of E6 to E9 to realize charging performance. Doing. However, the heat drying type antistatic composition using polyurethane or acrylic emulsion as a binder has a disadvantage in that its use is limited because its surface state is weak enough to be scratched by nails and its chemical resistance is weak. In addition, the UV-curable antistatic composition is made of most resins susceptible to fire, such as acrylic, epoxy, urethane acrylate-based fire vulnerability of the plastic sheet turns out to be a disadvantage. In addition, due to the use of organic solvents, environmental problems are being raised, the choice of a coating agent that can satisfy all of the flame retardancy and charging properties, and also environmental problems is very narrow.

Accordingly, the present invention develops a new aqueous eco-friendly coating agent with flame retardancy added to the existing antistatic coating composition and coating on the film of PC, PMMA Sheet and PET, OPP, PI, etc. The aim is to develop a coating that meets all its protective properties and is also environmentally safe.

The present invention improves the disadvantages of UV-curable antistatic coating compositions using heat-drying antistatic coating compositions that are poor in flame retardancy, surface hardness, and chemical resistance, and organic solvents of volatile organic compounds and organic resins such as monomers and oligomers that are susceptible to heat. An environmentally friendly coating composition is provided.

The thermosetting composition having the flame retardant and antistatic properties of the present invention includes a binder containing an aqueous thermosetting inorganic material; Flame retardant; And antistatic agents.

The heat-curable inorganic material of the present invention, a modified silicate system, silica acrylic organic-inorganic hybrid system, colloidal silica-based, composite resin or colloidal silica containing nano-silica particles modified by a silicon compound treated silica compound; Inorganic systems including alumina or zirconia; And it is characterized in that it comprises any one selected from the group consisting of organic, inorganic hybrid.

The content of the binder of the present invention is characterized in that 1 to 30 parts by weight.

The flame retardant of the present invention is an aqueous phosphorus-based flame retardant, characterized in that it comprises at least one selected from the group consisting of Ammonium phospate, Guanidine poluphospate and cyclophospate.

The phosphorus-based flame retardant of the present invention is characterized in that it comprises 1 to 40 parts by weight.

The antistatic agent of the present invention is a polyaniline, polypyrrole, poly (3,4-ethylenedioxythiophene) -polystyrene sulfonic acid (PEDOT-PSS) of the conductive polymer, ATO, ITO, ZnO inorganic oxides, CNT, graphene It is characterized in that it comprises at least one selected from the group consisting of CNT-based, quaternary ammonium salt, ionic antistatic agent of the cation / anionic surfactant.

The antistatic agent of the present invention is characterized in that it comprises 1 to 30 parts by weight.

The thermosetting composition of the present invention may further comprise a silane, an aqueous solvent and a surface control agent.

0.1 to 3 parts by weight of the silane of the present invention, 30 to 60 parts by weight of the aqueous solvent and 0.1 to 3 parts by weight of the surface modifier.

The coating method of the present invention is characterized by coating the thermosetting composition at a curing temperature of 80 ° C to 250 ° C and a curing time within 60 minutes.

Coating base material of the present invention, the base material; And a coating layer coated with the thermosetting composition on at least one side of the substrate, wherein the substrate is any one selected from the group consisting of sheets and films of plastic materials such as PC, PMMA, PVC, PET, PI, and OPP. Characterized in that it comprises a.

The thermosetting coating composition according to the present invention is applicable to heat-sensitive plastic products such as sheets such as PC, PMMA, PCTG or films such as PET, PE, PI, and PP. It can be applied to glass, metal, etc., which are difficult to attach, so it can be applied to all materials as antistatic flame retardant coating.

1 is a coated substrate coated with a heat curable composition according to the present invention.

Hereinafter, various embodiments of the present disclosure will be described with reference to the accompanying drawings. The examples and terms used herein are not intended to limit the techniques described in this document to specific embodiments, but should be understood to include various modifications, equivalents, and / or alternatives to the examples.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

The thermosetting composition having the flame retardant and antistatic properties of the present invention may include a binder, a flame retardant, and an antistatic agent.

The binder may comprise an aqueous heat curable inorganic material. For example, the thermosetting inorganic material may include a silica compound treated by modifying a modified silicate system, a silica acrylic organic-inorganic hybrid system, a colloidal silica system, a composite resin system including colloidal silica nanoparticles, or colloidal silica with a silicon compound; Inorganic systems including alumina or zirconia; And it may include any one selected from the group consisting of organic, inorganic hybrid. Preferably, the binder may be a composite resin binder including silica particles dispersed in a high polar solvent having excellent mixing properties with a flame retardant and an antistatic agent.

The binder may be included in an amount of 1 to 30 parts by weight based on 100 parts by weight of the heat curable composition. More preferably, the binder may be included in an amount of 5 to 30 parts by weight based on 100 parts by weight of the thermosetting composition.

Flame retardant for imparting flame retardancy may include at least one of the group consisting of phosphate ester, melamine, aluminum hydroxide, antimony pentoxide. Phosphoric acid ester-based phosphorus flame retardants may be used for optimal formulation of the thermosetting compositions of the present invention. For example, the flame retardant may be at least one selected from the group consisting of Ammonium Polyphospate, Guanidine Polyphosoate and cyclophospate.

It is preferable to use a liquid flame retardant mainly for the optimum dispersion of the flame retardant, but the solid flame retardant may also be prepared by dispersing the mixture through mixing, ultrasonic dispersion or 3-roll mill using an appropriate dispersant.

The flame retardant may include 1 to 40 parts by weight based on 100 parts by weight of the heat curable composition. More preferably, the flame retardant may be included in an amount of 1 to 30 parts by weight based on 100 parts by weight of the heat curable composition.

Examples of antistatic agents for implementing antistatic properties include conductive polymers such as polyaniline, polypyrrole, and polyethylene dioxy thiophene, inorganic oxides such as ATO, ITO, and ZnO, CNTs, and quaternary ammonium salts such as CNT and graphene. At least one selected from the group consisting of ionic antistatic agents such as cationic / anionic surfactants can be used. In other words, one or two of them can be selected and mixed. Preferably, poly (3,4-ethylenedioxythiophene) -polystyrenesulfonic acid (PEDOT-PSS), which is a polyethylene dioxy thiophene-based conductive polymer, may be used as the antistatic agent. Through this, it is possible to implement the surface resistance of E5 to E9.

The antistatic agent may be included in an amount of 1 to 30 parts by weight based on 100 parts by weight of the heat curable composition. More preferably, the antistatic agent may be included in an amount of 1 to 20 parts by weight based on 100 parts by weight of the thermosetting composition.

Meanwhile, the heat curable composition of the present invention may further include a solvent, a surface conditioner and a silane.

As the solvent, a solvent for improving the mixing and dispersibility of the binder, flame retardant and antistatic agent may be used. For example, the solvent may be a high polar solvent such as distilled water, ethyl alcohol, isopropyl alcohol, methyl alcohol, ethylene glycol, polyethylene glycol, propylene glycol, N-methyl pyrrolidone, and the like. Alternatively, the solvent may be a solvent having a high dielectric constant such as dimethyl sulfoxide or ethylene carbonate, acetone, or methyl ethyl ketone in an ether type polar polar solvent such as ethylene glycol mono ethyl ether, propylene glycol mono ethyl ether, methylene glycol mono ethyl ether, and the like. It may be a solvent included in a small amount within the range of less than. Preferably, 2 to 3 selected from the group consisting of distilled water, ethanol, isopropyl alcohol and ethylene glycol may be selected and mixed.

The solvent may be included 30 to 60 parts by weight based on 100 parts by weight of the heat curable composition.

Surface control agents for lowering the surface tension may be mainly a silicone-based leveling agent. Representative leveling agents are BYK and Dow corning. Leveling agents such as Momentive Inc. are used a lot and in the present invention, BYK-306 from BYK Corp. was used as a surface control agent.

The surface modifier may be included 0.1 to 3.0 parts by weight based on 100 parts by weight of the heat curable composition.

In addition, a small amount of silane may be included to improve adhesion to the substrate and surface hardness. For example, amino silanes such as amino ethoxy propyl silane, amino silane, aminoethylaminopropyl methoxy silane, epoxy silanes such as glycidoxy propyl triethoxy silane, glycidoxy propyl methyldiethoxy silane, phenyltrier Various silanes, such as phenyls, such as a methoxy silane, can be included. Preferably, amino silane or epoxy silane can be used.

The silane may be included in an amount of 1 to 5 parts by weight based on 100 parts by weight of the heat curable composition.

The heat curable antistatic flame retardant coating agent of the present invention is a heat curable binder 5.0 ~ 30.0% by weight, silane 1 ~ 5% by weight silane for improving the surface hardness and adhesion strength antistatic agent PEDOT-PSS (Heraeus) Clevios P) 1 ~ 20% by weight Flame retardant for imparting flame retardancy 1 ~ 30% by weight Mixed solvent capable of mixing the above materials 30 ~ 60% by weight Surface additives for improving surface leveling may contain 0.1 ~ 3% by weight have.

On the other hand, according to the coating method of the present invention, it can be coated on a variety of substrates using the thermosetting composition. For example, the heat curable composition of the present invention may be coated with a curing temperature of 80 ° C. to 250 ° C. and a curing time within 60 minutes. Preferably, the thermosetting composition of the present invention may be coated with a curing temperature of 100 ℃ to 150 ℃ and a curing time of 10 minutes to 30 minutes. Meanwhile, the curing temperature and the curing time may vary depending on the thickness of the coating film and the kind of the substrate.

The coated substrate of the present invention may include a substrate and a coating layer including the heat curable composition on at least one side of the substrate. In this case, the substrate may include any one selected from the group consisting of sheets and films of plastic materials such as PC, PMMA, PVC, PET, PI, and OPP. Preferably, the substrate may be a plastic substrate including any one selected from the group consisting of PC, PET and PI. Or it can be applied to all materials that are not deformed even under curing conditions of 100 ℃ such as antistatic treatment on glass, metal, etc.

The method of coating the thermosetting composition of the present invention is also possible to roll to roll coating, such as flow coating, micro gravure, slot die, Comma coating, spray coating, spin coating is also possible.

Hereinafter, the specific embodiments of the present invention will be described in detail.

However, the following examples are only for illustrating the present invention and the present invention is not limited by the following examples.

Example 1

A composite resin binder (Y company) containing 10 parts by weight of silica particles, 20 parts by weight of distilled water, 10 parts by weight of ethanol, 10 parts by weight of PEDOT-PSS (Heraeus) were placed in a beaker and stirred at 1000 rpm for 20 minutes to prepare a first coating solution. do. In addition, another beaker was added with 30 parts by weight of a cyclophosphate of a phosphate ester, 10 parts by weight of distilled water, amino silane (Dow corning) and 0.5 parts by weight of a surface leveling agent (BYK 306), followed by stirring at 1000 rpm for 20 minutes. 2 prepare a coating solution.

The first coating agent and the second coating agent are mixed at a weight ratio of 1: 1 to prepare a flame retardant antistatic coating agent by stirring at 1000 rpm for about 10 minutes.

Since most of the raw materials are present in a stable state in a high polar aqueous solvent, it is possible to manufacture an environmentally friendly coating without adding a volatile organic compound.

In addition, the reason for the manufacture of a two-part coating agent is to increase the pot life of the coating liquid.

Example 2

A composite resin binder (Y company) containing 10 parts by weight of silica particles, 25 parts by weight of distilled water, 5 parts by weight of ethanol, 10 parts by weight of PEDOT-PSS (Heraeus) were placed in a beaker and stirred at 1000 rpm for 20 minutes to prepare a first coating solution. do. In addition, another beaker was injected with 30 parts by weight of phosphoric acid ester-based flame retardant (Ammonium Polyphospate), 10 parts by weight of distilled water, epoxy silane (Dow corning) and 0.5 parts by weight of surface leveling agent (BYK 306), followed by stirring at 1000 rpm for 20 minutes to form a second coating solution. To prepare.

The coating agent is mixed in a weight ratio of 1: 1 as in Example 1 to prepare a coating agent.

Example 3

Composite resin binder (Y company) containing 10 parts by weight of silica particles, 25 parts by weight of distilled water, 5 parts by weight of ethanol, 10 parts by weight of ATO sol (N company) were added to a beaker and stirred at 1000 rpm for 20 minutes to prepare a first coating solution. do. In addition, another beaker was injected with 30 parts by weight of phosphoric acid ester-based flame retardant (Ammonium Polyphospate), 10 parts by weight of distilled water, epoxy silane (Dow corning) and 0.5 parts by weight of surface leveling agent (BYK 306), followed by stirring at 1000 rpm for 20 minutes to form a second coating solution. To prepare.

The coating agent is mixed in a weight ratio of 1: 1 as in Example 1 to prepare a coating agent.

Comparative Example 1

10 parts by weight of water-based polyurethane resin (Japan G company), 45 parts by weight of distilled water, 15 parts by weight of ethanol, 0.01 parts by weight of amine to improve the dispersibility of the polyurethane resin, 10 parts by weight of PEDOT-PSS (Heraeus) into a beaker Stir at 1000 rpm for 20 minutes and inject 0.5 parts by weight of 10 parts by weight of epoxy silane (Dow corning) and surface leveling agent (BYK 306) and stir at 1000 rpm for 20 minutes to prepare a coating solution.

Comparative Example 2

10 parts by weight of urethane acrylate oligomer (EB-1290-Cytec), 5 parts by weight of 6 functional monomer DPHA (Miwon), 10 parts by weight in an opaque beaker, 10 parts by weight of EC (Ethyl cellosolve), 20 parts by weight of PM (Propylane glycol mono methyl ether), 30 parts by weight of Iso propyl alcohol (IPA), 1 part by weight of a photocuring initiator (I-184-Miwon) surface additive for surface leveling BYK 306 (BYK) After a small amount of addition, 15 minutes of stirring, 10 parts by weight of PEDOT-PSS (Heraeus) was added and stirred for 20 minutes to prepare a UV-curable coating solution.

In order to evaluate the prepared Examples 1 to 3 and Comparative Examples 1 to 2, physical properties were evaluated as follows.

1) Coating film manufacturing

The coating film was formed by flow coating the PC sheet using the coating agent prepared in Examples and Comparative Examples.

In the case of Examples 1 to 3, since it is a heat curing coating agent, the coating agent was sprayed on the PC Sheet (20 mm) plate from the top and coated to the bottom by a natural dropping method, and then cured at 130 ° C. for 15 minutes in a hot air dryer. In the case of 1, since it is a heat drying coating agent, it was dried in a hot air dryer after flow coating for 3 minutes in the same manner as the above method, and then a dry coating film was formed. After drying for 3 minutes to form a cured coating by UV irradiation (400mj / cm).

2) Coating property evaluation

① Surface resistance evaluation: Surface resistance was measured by using a surface resistance measuring instrument (Monroe Electronics, Monroe-291) at a voltage of 10V according to ASTM D-257.

② Pencil hardness evaluation: Surface hardness was measured by pencil hardness tester in accordance with KSM ISO 15184.

③ Flame retardancy evaluation: Evaluated by UL 94 V method

-UL 94 V-0: Fire the coated specimens with a burner for 10 seconds, then remove the burners and ensure that the specimens ignite, that is, the burning time of the specimens shall not exceed 10 seconds, and that 5 coated specimens are The same test shall be made and the total combustion time shall not exceed 50 seconds (10 seconds per unit). At this time, fire shall not ignite on the cotton which lies about 30cm below due to the fire that melts during combustion. If any one of the five specimens does not meet the requirements, the same test shall be carried out with another five specimens. In this case, the total burning time should be within 51-55 seconds (10.2 seconds to 11 seconds).

-UL 94 V-1: Basically, the test method is the same as V-0, and in the case of V-1, the burning time of the fire on the specimen after removing the burner fire should not exceed 30 seconds. The sum of the combustion times should be within 250 seconds. At this time, the fire shall not be ignited by the falling fire melting on the cotton wool installed under the test piece. In addition, if any of the five specimens does not meet the requirements, the other five specimens shall be subjected to the same test, in which case the total combustion time shall be within 251 to 225 seconds.

-UL 94 V-2: V-2 must be burned within 30 seconds after the burner is removed and the total burn time within 10 seconds must be included within 250 seconds. Unlike V-1, cotton firing may occur due to sparks. And if one of the five specimens does not satisfy one during the flame retardant test, the total burning time of the other five specimens shall be within 251 to 255 seconds.

④ Adhesion evaluation: The adhesion measurement was measured by KSM ISO 2409 using 3M Tape. The adhesion test results were classified as follows.

○: very good

△: partly film removal

×: All parts film removal

Table 1 summarizes the measurement properties of the coating films of Examples 1 to 3 and Comparative Examples 1 and 2.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2       Assessment Methods Surface resistance E6 ~ 7 E6 ~ 7 E6 ~ 7 E7-8 E7-8 ASTM D-257 Flame retardant V-0 V-0 V-0 V-2 V-2 UL 94 V Surface hardness H H H 2B H KSM ISO 15184 Adhesion ○ ○ ○ △ ○ KSM ISO 2409

As shown in Table 1, Examples 1 to 3 realized stable surface resistance of E6-7, exhibited excellent flame retardancy, and surface hardness and adhesion were also better than those of the comparative examples.

Features, structures, effects, and the like described in the above embodiments are included in at least one embodiment of the present invention, and are not necessarily limited to only one embodiment. Furthermore, the features, structures, effects, and the like illustrated in the embodiments may be combined or modified with respect to other embodiments by those skilled in the art to which the embodiments belong. Therefore, it should be interpreted that the contents related to such a combination and modification are included in the scope of the present invention.

In addition, the above description has been made with reference to the embodiments, which are merely examples and are not intended to limit the present invention, and those skilled in the art to which the present invention pertains may be illustrated as above without departing from the essential characteristics of the present embodiments. It will be understood that various modifications and applications are not possible. For example, each component specifically shown in the embodiments may be modified. And differences relating to such modifications and applications will have to be construed as being included in the scope of the invention defined in the appended claims.

Claims (11)

A binder containing an aqueous thermosetting inorganic material;
Flame retardant; And
A thermosetting composition having flame retardant and antistatic properties comprising an antistatic agent.
The method of claim 1,
The thermosetting inorganic material,
A silica compound treated by modifying a modified silicate system, silica acrylic organic-inorganic hybrid system, colloidal silica system, composite resin system including nano silica particles or colloidal silica with a silicone compound;
Inorganic systems including alumina or zirconia; And
A thermosetting composition comprising any one selected from the group consisting of organic and inorganic hybrid systems.
The method of claim 1,
The content of the binder is a thermosetting composition, characterized in that 1 to 30 parts by weight.
The method of claim 1,
The flame retardant is an aqueous phosphorus flame retardant,
Ammonium phospate, Guanidine poluphospate and cyclophospate thermosetting composition comprising at least one selected from the group consisting of.
The method of claim 1,
The phosphorus-based flame retardant is a thermosetting composition comprising 1 to 40 parts by weight.
The method of claim 1,
The antistatic agent is polyaniline, polypyrrole, poly (3,4-ethylenedioxythiophene) -polystyrene sulfonic acid (PEDOT-PSS) conductive polymer type, ATO, ITO, ZnO inorganic oxide type, CNT, graphene CNT type, A thermosetting composition comprising at least one selected from the group consisting of quaternary ammonium salts and ionic antistatic agents of cationic / anionic surfactants.
The method of claim 1,
The antistatic agent is a thermosetting composition comprising 1 to 30 parts by weight.
The method of claim 1,
A heat curable composition further comprising a silane, an aqueous solvent and a surface conditioner.
The method of claim 8,
0.1 to 3 parts by weight of the silane, 30 to 60 parts by weight of the aqueous solvent and 0.1 to 3 parts by weight of the surface modifier, characterized in that the thermosetting composition.
The thermosetting composition according to claim 1,
Coating method characterized by coating at a curing temperature of 80 ℃ to 250 ℃ and a curing time within 60 minutes.
materials; And
At least one side of the substrate comprises a coating layer coated with the thermosetting composition according to claim 1,
The substrate is a coating substrate, characterized in that it comprises any one selected from the group consisting of sheets and films of plastic materials such as PC, PMMA, PVC, PET, PI, OPP.

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