KR102151435B1 - 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 thermosetting composition having flame retardancy and antistatic properties of the present invention includes: a binder including an aqueous thermosetting inorganic material; 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 eco-friendly aqueous coating composition for the purpose of implementing antistatic performance and at the same time flame retardancy by using an aqueous inorganic compound as a binder and using PEDOT-PSS.

In order to achieve surface resistance, generally used antistatic coating compositions disperse a conductive material in a solvent such as water and alcohol, and use a water-dispersible polyurethane or acrylic emulsion as a binder to achieve heat drying. Is manufactured. Or, using an organic solvent, which is a volatile organic compound, diluted with a UV-curable oligomer or monomer, prepared in a UV-curable form, and coated on plastic substrates such as PET, PC, PMMA, and PVC in the range of E6 to E9 to achieve charging performance. Are doing. However, in the case of a heat drying antistatic composition using polyurethane or acrylic emulsion as a binder, the surface condition is fragile enough to be scratched by a fingernail and also has a disadvantage in that the field of use is limited due to poor chemical resistance. In addition, in the case of UV-curable antistatic compositions, most of them are made of resins that are vulnerable to fire, such as acrylic, epoxy, and urethane acrylate, and the vulnerability of the plastic sheet to fire is revealed as a disadvantage. In addition, environmental problems have been raised due to the use of organic solvents, and the selection of a coating agent that satisfies all of the flame retardancy and charging properties, as well as environmental problems, is very narrow.

Accordingly, the present invention develops a new water-based eco-friendly coating agent with flame retardancy added to the existing antistatic coating composition and coats it on films such as PC, PMMA Sheet and PET, OPP, PI, thereby improving vulnerability to fire, which is a disadvantage of plastic, and charging. Its purpose is to develop a coating that satisfies all of the prevention performance and is environmentally safe.

The present invention improves the disadvantages of a heat-drying antistatic coating composition with poor flame retardancy, surface hardness, and chemical resistance, and a UV curable antistatic coating composition using an organic solvent of a volatile organic compound and an organic resin such as a monomer or oligomer vulnerable to heat. To provide an eco-friendly coating composition.

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

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

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 flame retardant, and is 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 contains 1 to 40 parts by weight.

The antistatic agent of the present invention is a conductive polymer system of polyaniline, polypyrrole, poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid (PEDOT-PSS), inorganic oxide of ATO, ITO, ZnO, CNT, graphene. It is characterized in that it comprises at least one selected from the group consisting of ionic antistatic agents such as CNT-based, quaternary ammonium salts, and cationic/anionic surfactants.

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

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

The silane of the present invention is characterized in that 0.1 to 3 parts by weight, 30 to 60 parts by weight of the aqueous solvent, and 0.1 to 3 parts by weight of the surface control agent.

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

The coating substrate of the present invention is a substrate; 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 made of plastic materials such as PC, PMMA, PVC, PET, PI, OPP, etc. It characterized in that it comprises a.

The thermosetting coating composition according to the present invention can be applied to plastic products vulnerable to heat such as sheets such as PC, PMMA, PCTG, or films such as PET, PE, PI, and PP. It can be applied to glass and metal, which are materials that are difficult to attach, so it can be applied to all materials as an antistatic flame retardant coating, and due to its low viscosity, it can be applied to flow coating, roll to roll coating, and spray coating.

1 is a coating substrate coated with a thermosetting composition according to the present invention.

Hereinafter, various embodiments of the present document will be described with reference to the accompanying drawings. The examples and terms used therein are not intended to limit the technology described in this document to a specific embodiment, and should be understood to include various modifications, equivalents, and/or substitutes of the corresponding embodiments.

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

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

The binder may include an aqueous thermally curable inorganic material. For example, the thermally curable inorganic material may include a modified silicate type, a silica acrylic organic/inorganic hybrid type, a colloidal silica type, a composite resin type including nano silica particles, or a silica compound treated by modifying colloidal silica with a silicone compound; Inorganic systems including alumina or zirconia; And it may include any one selected from the group consisting of organic and inorganic hybrid systems. Preferably, the binder may be a composite resin-based binder including silica particles dispersed in a highly polar solvent having excellent miscibility 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 thermosetting composition. More preferably, the binder may be included in 5 to 30 parts by weight based on 100 parts by weight of the thermally curable composition.

The flame retardant for imparting flame retardancy may include at least any one from the group consisting of phosphate ester, melamine, aluminum hydroxide, and antimony pentoxide. Phosphorus-based flame retardants based on phosphoric acid esters may be used for optimal formulation of the thermosetting composition 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.

For optimal dispersion of flame retardants, it is preferable to use liquid flame retardants, but solid flame retardants may be dispersed through mixing, ultrasonic dispersion, or 3-roll mill using an appropriate dispersant to prepare a dispersion.

The flame retardant may be included in 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 1 to 30 parts by weight based on 100 parts by weight of the heat curable composition.

Antistatic agents to implement antistatic are conductive polymers such as polyaniline, polypyrrole, polyethylene dioxythiophene, inorganic oxides such as ATO, ITO, ZnO, CNTs such as CNT, graphene, quaternary ammonium salts , At least one selected from the group consisting of ionic antistatic agents such as cationic/anionic surfactants may be used. In other words, it is possible to mix and use one or two of them. Preferably, poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid (PEDOT-PSS), which is a polyethylene dioxythiophene-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 1 to 30 parts by weight based on 100 parts by weight of the thermosetting composition. More preferably, the antistatic agent may be included in 1 to 20 parts by weight based on 100 parts by weight of the heat curable composition.

On the other hand, the thermosetting composition of the present invention may further include a solvent, a surface modifier, and a silane.

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

The solvent may be included in an amount of 30 to 60 parts by weight based on 100 parts by weight of the thermally curable composition.

As a surface modifier to lower the surface tension, a silicone-based leveling agent may be mainly used. Typical leveling agents are BYK and Dow Corning. Leveling agents such as Momentive are widely used, and BYK-306 of BYK is used as a surface control agent in the present invention.

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

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

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

The thermally curable antistatic flame retardant coating agent of the present invention is an antistatic agent PEDOT-PSS (Heraeus) for realizing charging performance of 5.0 to 30.0% by weight of a thermally curable binder, 1 to 5% by weight of silane for improving surface hardness and adhesion. Clevios P) 1~20% by weight of flame retardant material for imparting flame retardancy 1~30% by weight of mixed solvent that can mix the above materials 30~60% by weight of surface additive 0.1~3% by weight of surface additive to improve surface leveling have.

Meanwhile, according to the coating method of the present invention, it may be coated on various substrates using the thermosetting composition. For example, the thermosetting composition of the present invention may be coated at 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 at a curing temperature of 100° C. to 150° C. and a curing time of 10 minutes to 30 minutes. Meanwhile, the curing temperature and curing time may vary depending on the thickness of the coating film and the type of the substrate.

The coating substrate of the present invention may include a substrate and a coating layer including the thermosetting 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 made 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. Alternatively, it can be applied to all materials that do not deform even under curing conditions of about 100 ℃ such as antistatic treatment on substrates such as glass and metal.

The method of coating the thermosetting composition of the present invention can be roll-to-roll coating such as flow coating, microgravure, slot die, and comma coating, and spray coating and spin coating are also possible.

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

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 containing 10 parts by weight of silica particles (Y company), 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, in another beaker, 30 parts by weight of a phosphoric acid ester-based flame retardant (Cyclophospate), 10 parts by weight of distilled water, and 0.5 parts by weight of amino silane (Dow Corning), and 0.5 parts by weight of a surface leveling agent (BYK 306) were injected, and then stirred 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 and stirred at 1000 rpm for about 10 minutes to prepare a flame-retardant antistatic coating.

Since most of the above raw materials exist in a stable state in a high polarity aqueous solvent, it is possible to manufacture an eco-friendly coating agent in which no volatile organic compounds are added.

In addition, the reason for manufacturing a two-component coating agent is to increase the storage stability (pot life) of the coating solution.

Example 2

Composite resin-based binder containing 10 parts by weight of silica particles (Y company), 25 parts by weight of distilled water, 5 parts by weight of Ethanol, 10 parts by weight of PEDOT-PSS (Heraeus) were put in a beaker and stirred at 1000 rpm for 20 minutes to prepare a first coating solution. do. In addition, 30 parts by weight of phosphoric acid ester-based flame retardant (Ammonium Polyphospate), 10 parts by weight of distilled water, epoxy silane (Dow Corning), 0.5 parts by weight of surface leveling agent (BYK 306) were injected and then stirred at 1000 rpm for 20 minutes to obtain a second coating solution. To manufacture.

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

Example 3

A composite resin binder containing 10 parts by weight of silica particles (Y company), 25 parts by weight of distilled water, 5 parts by weight of Ethanol, and 10 parts by weight of ATO sol (Japan N company) were added to a beaker and stirred at 1000 rpm for 20 minutes to prepare a first coating solution. do. In addition, 30 parts by weight of phosphoric acid ester-based flame retardant (Ammonium Polyphospate), 10 parts by weight of distilled water, epoxy silane (Dow Corning), 0.5 parts by weight of surface leveling agent (BYK 306) were injected and then stirred at 1000 rpm for 20 minutes to obtain a second coating solution. To manufacture.

The coating agent was 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 a water-dispersible polyurethane resin (Japan G), 45 parts by weight of distilled water, 15 parts by weight of Ethanol, 0.01 parts by weight of amine that improves the dispersibility of polyurethane resin, 10 parts by weight of PEDOT-PSS (Heraeus) into a beaker After stirring at 1000 rpm for 20 minutes, 10 parts by weight of epoxy silane (Dow Corning) and 0.5 parts by weight of surface leveling agent (BYK 306) were injected and stirred 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 of weighed 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 IPA (Iso propyl alcohol), 1 part by weight of photocuring initiator to initiate UV curing (I-184-Miwon) Surface additive for surface leveling BYK 306 (BYK) After adding this small amount and stirring for 15 minutes, 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 property evaluation was performed as follows.

1) Manufacture of coating film

A 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 agent, the coating agent was sprayed on a PC sheet (20 mm) plate from the top, coated to the bottom in a natural fall method, and then cured at 130 degrees for 15 minutes in a hot air dryer. In the case of 1, since it is a heat drying coating agent, in the same manner as above, after flow coating, drying for 3 minutes in a hot air dryer was formed, and a dry film was formed.In the case of Comparative Example 2, since it is a UV curable type, as above, the hot air dryer after flow coating After drying for 3 minutes, UV irradiation (400mj/cm) was performed to form a cured coating film.

2) Evaluation of coating properties

① Surface resistance evaluation: A surface resistance tester (Monroe Electronics, Monroe-291) was used to measure the surface resistance according to ASTM D-257 with a voltage of 10V.

②Evaluation of pencil hardness: The pencil hardness was measured in accordance with KSM ISO 15184 using an anaerobic pencil hardness tester.

③ Flame retardancy evaluation: evaluated by UL 94 V method

-UL 94 V-0: After igniting the coated specimen with a burner for 10 seconds, the burner is removed and the time the specimen is on fire, i.e., the time the specimen burns, should not exceed 10 seconds. The same test is carried out, and the total burning time should not exceed 50 seconds (10 seconds per piece). At this time, fire should not be ignited on the cotton wool lying below about 30cm by sparks that melt and fall during combustion. At this time, if any one of the five specimens does not satisfy the requirements, another five specimens should be tested in the same way. In this case, the total combustion time should be within 51 to 55 seconds (10.2 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, and the same test was performed 10 times. The sum of burning times must be within 250 seconds. At this time, fire should not be ignited by sparks that melt and fall on the cotton wool installed under the specimen during combustion. In addition, if one of the five specimens does not meet the requirements, another five specimens should be subjected to the same test, in which case the total burning time should be within 251 to 225 seconds.

-UL 94 V-2: For V-2, after removing the burner fire, the burning time on the specimen must be within 30 seconds, and as in the case of V-1, the total of 10 burning times must enter within 250 seconds. , Unlike V-1, cotton ignition may occur due to fire. And if one is not satisfied during the flame retardant test on 5 pieces/1 set, the total burning time of the other 5 pieces shall be within 251~255 seconds.

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

○: Very good

△: Partially detached

×: All parts defilm

In Table 1 below, the measurement properties of the coating films of Examples 1 to 3 and Comparative Examples 1 to 2 are summarized.

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 Adherence ○ ○ ○ △ ○ KSM ISO 2409

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

Features, structures, effects, and the like described in the above-described 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 each embodiment may be combined or modified for other embodiments by a person having ordinary knowledge in the field to which the embodiments belong. Accordingly, contents related to such combinations and modifications should be interpreted as being included in the scope of the present invention.

In addition, although the embodiments have been described above, these are only examples and do not limit the present invention, and those of ordinary skill in the field to which the present invention pertains are illustrated above within the scope not departing from the essential characteristics of the present embodiment. It will be seen that various modifications and applications that are not available are possible. For example, each component specifically shown in the embodiments can be modified and implemented. And differences related to these modifications and applications should be construed as being included in the scope of the present invention defined in the appended claims.

Claims (11)

A binder containing silica particles,
An aqueous solvent containing distilled water and ethanol, and
A first coating liquid containing an antistatic agent including at least one of poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid (PEDOT-PSS) and ATO; And
An aqueous phosphorus-based flame retardant comprising any one of Cyclophospate and Ammonium phospate,
Distilled water,
A silane comprising any one of an amino silane and an epoxy silane, and
Including; a second coating solution containing a surface control agent,
When Cyclophospate is included as an aqueous phosphorus-based flame retardant in the second coating solution, amino silane is included as a silane,
When Ammonium phospate is included as an aqueous phosphorus-based flame retardant, epoxy silane is included as a silane,
The first coating solution and the second coating solution are mixed in a weight ratio of 1:1, a thermosetting composition having flame retardancy and antistatic properties.
delete The method of claim 1,
The content of the binder is a thermosetting composition, characterized in that 1 to 30 parts by weight.
delete The method of claim 1,
The thermally curable composition, characterized in that the water-based phosphorus-based flame retardant comprises 1 to 40 parts by weight.
delete The method of claim 1,
The thermosetting composition, characterized in that the antistatic agent comprises 1 to 30 parts by weight.
delete delete The thermosetting composition according to any one of claims 1, 3, 5 and 7,
Coating method, characterized in that coating at a curing temperature of 80 ℃ to 250 ℃ and a curing time of 60 minutes.
materials; And
A coating layer coated with the thermosetting composition according to any one of claims 1, 3, 5, and 7 on at least one side of the substrate,
The substrate is a coated substrate comprising any one selected from the group consisting of sheets and films made of plastic materials such as PC, PMMA, PVC, PET, PI, and OPP.

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