KR101685674B1

KR101685674B1 - Flame retardant acrylic composition

Info

Publication number: KR101685674B1
Application number: KR1020150118005A
Authority: KR
Inventors: 최헌식; 김지언
Original assignee: 최헌식; 김지언; 주식회사 이솜엔지니어링
Priority date: 2015-08-21
Filing date: 2015-08-21
Publication date: 2016-12-12

Abstract

The present invention relates to a flame retardant acrylic composition containing a first acrylic compound; and a flame retardant mixture including a first flame retardant containing phosphorus compounds physically dispersed in the first acrylic compound and a second flame retardant containing acrylamide-based compounds chemically bonded to the first acrylic compound. The present invention provides acrylic resin having excellent flame retardance with a UL94 V2 level or higher and thermal resistance of heat deflection temperature of 90 degrees or higher while maintaining transparency using the composition.

Description

[0001] Flame retardant acrylic composition [0002]

The present invention relates to a flame-retardant acrylic composition and a method for producing the same, and more specifically, to an acrylic composition having excellent flame retardancy without deterioration in heat resistance and transparency of an acrylic resin produced using the composition and a method for producing the same.

In the flame retarding method of plastics, the production of heat-resistant plastics by changing the molecular structure, the chemical bonding of flame retardant components (reactive flame retardant) in the plastic structure, the physical addition of flame retardant to plastics (additive type flame retardant) There is a method of improving heat resistance by changing product design.

Flame retardants are generally divided into additive, reactive, and combination flame retardants. Reactive flame retardants continue to have a flame retardant effect without blooming, regardless of external conditions, and are mainly used in thermosetting plastics. On the contrary, additive type flame retardant is mainly used for thermoplastic plastics. In this case, plasticizer plays a plasticizing role when it is compatible with plastic, and serves as a filler. Unlike the reactive flame retardant, the addition type flame retardant may be blooming on the surface of the plastic depending on its structure and external conditions. Combination type flame retardants exhibit flame retarding synergistic effect or inhibitory effect depending on the combination type.

On the other hand, high performance and versatility are demanded for exterior or automobile materials of electric and electronic products in recent years. In particular, there is an increasing demand for flame retardancy that guarantees stability against fire with high texture and scratch resistance. Acrylic resins, particularly polymethyl methacrylate (PMMA) resins, which are capable of exhibiting scratch resistance as a commonly used resin, are excellent in transparency and weatherability, and have excellent mechanical strength, surface gloss, and adhesion. However, it is disadvantageous in that the impact resistance and the flame retardancy are very low.

In order to simultaneously achieve scratch resistance and flame retardancy, a method of adding a flame retardant capable of exhibiting flame retardancy when polymethylmethacrylate (PMMA) resin having excellent scratch resistance and pencil hardness of 3H to 4H has been tried. However, in order to exhibit flame retardancy, a high content of a flame retardant should be added. Therefore, this method suffers from the environmental restriction that the flame retardant monomer can be extracted from the resin to the outside, and the mechanical properties (heat resistance, transparency, etc.) of the resin are lowered.

In addition, for scratch resistance and flame retardancy, acrylic resins, particularly polymethyl methacrylate resins, can be mixed with polycarbonate resins and the like, which are excellent in mechanical strength and flame retardancy. However, when mixed with a polycarbonate resin or the like which is a high refractive index resin, transparency and deterioration of coloring property may be caused due to a difference in refractive index. In addition, in order to have excellent compatibility with a polycarbonate resin, the acrylic resin must have a high refractive index.

When a phosphorus-based flame retardant is used alone for the flame retardation of a plastic resin including an acrylic resin, a large amount of phosphorus-based flame retardant must be used, thereby lowering transparency and heat resistance. When used, they generally exist in one molecule at the same time, or they are injected separately. In the case of a nitrogen-based flame retardant, there is no product having transparency so that transparency, which is one of the advantages of plastic, is deteriorated.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made in an effort to solve the above problems, and an object of the present invention is to provide an acrylic composition capable of imparting excellent heat resistance and flame retardancy while maintaining transparency of an acrylic resin to be produced.

However, the objects of the present invention are not limited to the above-mentioned objects, and other objects not mentioned can be clearly understood by those skilled in the art from the following description.

The present invention relates to a first acrylic compound; A flame retardant mixture comprising a first flame retardant comprising a phosphorus compound and a second flame retardant comprising an acrylamide compound; And a surfactant comprising an Acryl group and a Phosphate group.

The phosphorus compound is a cyclic phosphorus compound and provides a flame retardant acrylic composition having a specific gravity of 1.2 to 1.5 and a viscosity of 50,000 to 500,000 CPS at 25 캜.

The acrylamide-based compound is a compound having a glass transition temperature (Tg) in a polymer that is higher than a glass transition temperature (Tg) when the first acrylic compound is a polymer, and more specifically, And a temperature (Tg) of 80 to 150 ° C.

Also, the first flame retardant may be contained in an amount of 15 to 60 parts by weight based on 100 parts by weight of the first acrylic compound, the second flame retardant may be included in an amount of 1 to 25 parts by weight based on 100 parts by weight of the first acrylic compound, 1 < / RTI > to 100 parts by weight of the acrylic compound.

Also, the surfactant may be at least one selected from the group consisting of (2-methacryloyloxyethyl) phosphate, 2-hydroxyethyl methacrylate phosphate, Bis (2-methacryloxyethyl) phosphate and Monoacryloxyethyl phosphate.

The first acrylic compound may be at least one selected from the group consisting of Methyl Acrylate (MA), Ethyl Acrylate, Propyl Acrylate, Butyl Acrylate, 2-ethylhexyl acrylate, Ethyl methacrylate, methyl methacrylate (MMA), ethyl methacrylate, propyl methacrylate, butyl methacrylate and benzyl methacrylate, Based on the total weight of the flame-retardant acrylic composition.

Also, the flame-retardant acrylic resin composition is cured to prepare a specimen having a thickness of 3 or 10 mm, and a flame retardancy acrylic composition having a flame retardancy of not less than V2 and a heat distortion temperature of not less than 90 ° C as measured according to UL94.

By using the cyclic phosphorus compound, the phosphorus compound having a high boiling point and a high viscosity can produce a high flame retarding effect even when a small amount is used, and there is no fear of migration and no deterioration in heat resistance.

Further, the present invention can prevent deterioration of heat resistance due to the use of a phosphorus compound by using an acrylamide-based compound having a high glass transition temperature (Tg) when it is a polymer.

In addition, the cyclic phosphorus compound having a high specific gravity generally has difficulty in mixing the first acrylic compound with no solvent, and when mixed at a certain ratio or more, there is a tendency of entanglement. In the case of using an acrylic group and a phosphate ) Group can be used to prevent the above-described phenomenon.

According to the composition according to one embodiment of the present invention, it is possible to provide an acrylic resin composition having excellent flame retardancy of UL 94 V2 grade or higher while maintaining transparency and having excellent heat resistance at a heat distortion temperature of 90 캜 or higher.

1 is a view showing a reaction mechanism of an acrylic compound according to an embodiment of the present invention.
2 is a schematic view illustrating a method of manufacturing an acrylic plate using an acrylic composition according to an embodiment of the present invention.

Before describing the present invention in detail, it is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the invention, which is defined solely by the appended claims. shall. All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art unless otherwise stated.

Throughout this specification and claims, the word "comprise", "comprises", "comprising" means including a stated article, step or group of articles, and steps, , Step, or group of objects, or a group of steps.

On the contrary, the various embodiments of the present invention can be combined with any other embodiments as long as there is no clear counterpoint. Any feature that is specifically or advantageously indicated as being advantageous may be combined with any other feature or feature that is indicated as being preferred or advantageous. Hereinafter, embodiments of the present invention and effects thereof will be described with reference to the accompanying drawings.

The flame-retardant acrylic composition according to an embodiment of the present invention includes a first acrylic compound; A flame retardant mixture comprising a first flame retardant comprising a phosphorus compound and a second flame retardant comprising an acrylamide compound; And a surfactant comprising an Acryl group and a Phosphate group.

The present invention uses a first flame retardant containing a phosphorus compound and a second flame retarder containing an acrylamide compound. The phosphorus compound used as the first flame retardant is a cyclic phosphorus compound having a high boiling point and the acrylamide compound used as the second flame retardant has a glass transition temperature (Tg) when the polymer is a polymer of the first acrylic compound By using an acrylamide-based compound having a glass transition temperature (Tg) higher than the glass transition temperature (Tg) of the glass transition temperature (Tg), flame retardancy can be prevented while preventing deterioration in transparency and prevention of deterioration in heat resistance due to use of the phosphorus compound.

The first acrylic compound according to the present invention may be selected from the group consisting of Methyl Acrylate (MA), Ethyl Acrylate, Propyl Acrylate, Butyl Acrylate, 2-ethylhexyl acrylate 2-ethylhexyl acrylate, methyl methacrylate (MMA), ethyl methacrylate, propyl methacrylate, butyl methacrylate and benzyl methacrylate Methacrylate), and the like.

Preferably, methyl methacrylate (MMA) is used, and it is preferable that methyl methacrylate (MA) and ethyl acrylate (EA) are each contained in an amount of 30 wt% or less based on the first acrylic compound.

The phosphorus compound included in the first flame retardant according to an embodiment of the present invention is physically dispersed in the first acrylic compound and the acrylamide compound contained in the second flame retardant is chemically bonded to the first acrylic compound to impart flame retardancy do. There has been a problem that transparency is lowered due to an increase in haze of an acrylic resin due to addition of a phosphorus-based flame retardant only to the conventional flame retardant and the heat distortion temperature is greatly decreased to deteriorate heat resistance. However, according to the present invention, It is possible to prevent deterioration of the heat resistance due to heat.

The phosphorus compound included in the first flame retardant according to an embodiment of the present invention includes at least one selected from the group consisting of trimethyl phosphate (TMP), triethyl phosphate (TEP), resorcinol diphosphate (RDP), and cyclic phosphate .

Preferably, it should preferably contain a cyclic phosphorate compound. Examples of the cyclic phosphorus compound include 9,10-Dihydro-9-Oxa-10-Phosphaphenantrene-10-Oxide (DOPO), Bis [(5-Ethyl-2-methyl-2-oxido-1,3,2-dioxaphosphinan- -yl) methyl] methylphosphonate and (5-Ethyl-2-methyl-2-oxido-1,3,2-dioxaphosphinan-5-yl) methyl methyl methylphosphonate.

Even when the cyclic phosphorus compound is used in combination with at least one of trimethyl phosphate (TMP), triethyl phosphate (TEP) and resorcinol diphosphate (RDP), it is preferable that the cyclic phosphorous compound has a content of not less than 70 wt% And it is possible to satisfy the excellent physical properties of the flame retardant acrylic composition of the present invention in the range of not less than 70% by weight of the cyclic phosphorus compound.

In addition, the phosphorus compound included in the first flame retardant according to an embodiment of the present invention preferably uses a phosphorus compound having a specific gravity of 1.2 to 1.5 and a high boiling point. A high flame-retardant phosphorous compound having a high phosphorus content can be used to achieve a high flame retarding effect even if a small amount is used.

Also, the phosphorus compound contained in the first flame retardant according to an embodiment of the present invention preferably has a viscosity of 50,000 to 500,000 CPS at 25 캜, more preferably 100,000 to 300,000 CP and a high viscosity. When such a high-viscosity phosphorous compound as described above is used as a flame retardant, there is no fear of migration, and the effect of plasticity of the additive type flame retardant is not exerted and heat resistance is not deteriorated.

The first flame retardant is contained in an amount of 15 to 60 parts by weight based on 100 parts by weight of the first acrylic compound. If it is contained in an amount of less than 15 parts by weight, there is a problem that a flame retardant effect is not exhibited. If it exceeds 60 parts by weight, the heat distortion temperature is lowered and the viscosity of the flame retardant mixture is high. Also, there is an effect of having excellent flame retardancy and processability within the above range. Depending on the use of the composition, the thinner the specimen, the larger the amount of the first flame retardant may be added.

The acrylamide-based compound contained in the second flame retardant according to an embodiment of the present invention may be at least one selected from the group consisting of ACMO (acryloyl morpholine), NIPAM (isopropyl acryl amide), HEAA (N- (2-hydroxyethyl) acryl amide), DMAPAA -diethyl acryl amide), N, N-diethyl acryl amide (DMAA) and Derivatives thereof.

Also, the acrylamide-based compound contained in the second flame retardant according to an embodiment of the present invention may have a glass transition temperature (Tg) higher than the glass transition temperature (Tg) when the first acrylic compound is a polymer, Based compound is preferably used. Preferably, the glass transition temperature in the case of a polymer of an acrylamide-based compound is 80 to 150 ° C. If the temperature is lower than 80 ° C, the effect of complementing heat resistance is insignificant. If the temperature is higher than 150 ° C, the raw material is mostly present in a powdery state rather than a liquid phase.

INDUSTRIAL APPLICABILITY The present invention can prevent deterioration of heat resistance due to the use of a phosphorus compound by using an acrylamide-based compound having a high glass transition temperature, which is not conventionally used as a flame retardant. Most of the flame retardant effect is expressed by the phosphorus compound, and the acrylamide compound doubles the effect of the phosphorus compound.

The second flame retardant is contained in an amount of 1 to 25 parts by weight based on 100 parts by weight of the first acrylic compound. When the amount of the flame retardant is less than 1 part by weight, the flame retardancy is deteriorated. When the amount exceeds 25 parts by weight, the total amount of the flame retardant is increased.

Particularly, when a phosphorus compound having a high specific gravity such as a cyclic phosphorus compound which is not conventionally used as a flame retardant of conventional acrylic compounds is used, it is difficult to mix a solventless compound with an acrylic compound, and when mixed at a specific ratio or more, Lt; / RTI >

Accordingly, the acrylic composition according to an embodiment of the present invention introduces a surfactant having both an acrylic group and a phosphate group. As the surfactant, it is preferable to use at least one selected from the group consisting of (2-methacryloyloxyethyl) phosphate, 2-hydroxyethyl methacrylate phosphate, Bis (2-methacryloxyethyl) phosphate and Monoacryloxyethyl phosphate.

The surfactant according to one embodiment of the present invention is contained in an amount of 0.01 to 1.0 part by weight based on 100 parts by weight of the total composition. When the amount of the surfactant is less than 0.01 part by weight, miscibility with the acrylic mixture may deteriorate. When the amount of the surfactant is more than 1.0 part by weight, the surfactant may deteriorate the mixing property. When the amount of the first acrylic compound is more than 1.0 part by weight, the balance between the phosphorus compound and the first acrylic compound is deteriorated due to the excess amount of the surfactant during the progress of the curing.

In general, when a reaction initiator is added to a flame-retardant acrylic composition in a large amount to accelerate the reaction, the reaction should be cured at a low temperature (53 to 55 ° C) because of the reaction heat. In case of 3 mm product curing, It takes 24 hours. Also, a thicker product has a problem that it is difficult to reduce the reaction time due to a large amount of internal heat.

Accordingly, the flame retardant acrylic composition of the present invention further includes a second acrylic compound for controlling the reaction heat, so that the curing reaction time can be reduced without boiling. For example, at least one selected from the group consisting of hexanediol dimethacrylate (HDDMA), polyethylene glycol dimethacrylate (PEGDMA), ethylene glycol dimethacrylate (EGDMA) and diethylene glycol dimethacrylate (DEGDMA) can be used.

The second acrylic compound is contained in the composition and acts as chain transfer or molecular weight control, so that the boiling phenomenon can be controlled by controlling the reaction heat when curing. As shown in FIG. 1, since the first acrylic compound monomer further contains a second acrylic compound, the growth rate is slow, the reaction is terminated after the growth to some extent and the molecular weight is low, but the reaction rate is slow and stable And the adherence due to reaction heat and shrinkage is reduced.

The second acrylic compound according to the present invention is contained in an amount of 0.02 to 5 parts by weight based on 100 parts by weight of the first acrylic compound. If it is contained in an amount of less than 0.02 parts by weight, the reaction heat can not be controlled. If the amount of the component is more than 5 parts by weight, the molecular weight becomes too small, and the physical properties (surface hardness, heat distortion temperature, etc.) decrease.

The flame retardant acrylic composition according to the present invention can be used as a flame retardant acrylic composition in the form of a coating composition containing a nucleating agent, a coupling agent, a filler, a plasticizer, an impact modifier, a lubricant, an antibacterial agent, a releasing agent, a heat stabilizer, an antioxidant, a light stabilizer, a compatibilizer, , A dye, a flame retardant, and a mixture thereof, but is not limited thereto.

The present invention provides a molded article made of a flame retardant acrylic composition having the above composition. The molding method may be applied by extrusion, injection molding or casting, but is not limited thereto. The molded article produced from the flame-retardant acrylic composition having the composition according to the present invention has excellent flame retardancy of UL94 V2 grade or higher while maintaining transparency, as shown in Experimental Examples to be described later, and has excellent heat resistance at a heat distortion temperature of 90 deg. The soundproof panel formed of the acrylic composition according to the present invention has a visible light transmittance (KS L 2514) of 90% or more and a load deformation temperature (KS M ISO 75-2) of 90 ° C or more to be.

The acrylic plate material can be produced using the flame retardant acrylic composition according to the present invention. The flame retardant acrylic composition according to the present invention is particularly suitable for producing an acrylic plate used for soundproof walls. Since the acrylic plate used for the sound barrier is required to have properties such as visible light transmittance (KS L 2514) of 85% or more and load deformation temperature (KSM ISO 75-2) of 85 ° C or more, The flame retardant acrylic composition according to the present invention having excellent flame retardance, transparency and strength can be used.

A casting method may be used to produce an acrylic plate using the flame retardant acrylic composition according to the present invention. Alternatively, an acrylic plate may be continuously manufactured using a steel conveyor belt or a glass mold may be used. A variety of acrylic plates can be manufactured using steel mold.

It is advantageous to produce an acrylic plate by using a steel conveyor belt in order to mass-produce small items according to the use of the acrylic plate to be manufactured and to reduce the manufacturing cost. In order to produce various molded articles, It is preferable to use a mold molding method in which the degree of freedom such as thickness is high and additional sanding operation is not required and loss of raw material cost is small.

Example

&Lt; Preparation of acrylic composition >

Example 1

To 20.83 g of cyclic phosphate, 4.15 g of DMAA and 0.03 g of Acrly Phosphate were mixed and mixed to prepare a flame retardant mixture containing a surfactant.

25 g of the flame retardant mixture containing the above prepared surfactant was mixed and stirred into 100 g of the first acrylic compound in which MMA and PMMA were mixed in an 8: 2 ratio to prepare an acrylic composition.

Example 2

To 15.68 g of cyclic phosphate, 3.13 g of DMAA and 0.01 g of Acrly Phosphate were mixed and mixed to prepare a flame retardant mixture containing surfactant.

18.82 g of the flame retarder mixture prepared above was mixed and stirred with 100 g of the first acrylic compound in which MMA and PMMA were mixed in an amount of 8: 2 to prepare an acrylic composition.

Example 3

To 16.63 g of cyclic phosphate, 8.25 g of DMAA and 0.13 g of Acrly Phosphate were mixed and mixed to prepare a surfactant-containing flame retardant mixture.

25 g of the flame retarder mixture prepared above was mixed and stirred with 100 g of the first acrylic compound in which MMA and PMMA were mixed at a ratio of 8: 2 to prepare an acrylic composition.

Example 4

To the 55.53 g of cyclic phosphate, 11.07 g of DMAA and 0.07 g of Acrly Phosphate were mixed and mixed to prepare a surfactant-containing flame retardant mixture.

66.67 g of the flame retardant mixture prepared above was mixed and stirred with 100 g of the first acrylic compound in which MMA and PMMA were mixed in an amount of 8: 2 to prepare an acrylic composition.

Example 5

To 44.77 g of cyclic phosphate, 8.92 g of DMAA and 0.15 g of Acrly Phosphate were mixed and mixed to prepare a flame retardant mixture containing a surfactant.

53.84 g of the flame retardant mixture prepared above was mixed and stirred with 100 g of the first acrylic compound in which MMA and PMMA were mixed at a ratio of 8: 2, to prepare an acrylic composition.

Example 6

To 44.33 g of cyclic phosphate, 22.17 g of DMAA and 0.17 g of Acrly Phosphate were mixed and mixed to prepare a flame retardant mixture containing a surfactant.

66.67 g of the flame retardant mixture prepared above was mixed and stirred with 100 g of the first acrylic compound in which MMA and PMMA were mixed in an amount of 8: 2, to prepare an acrylic composition.

Example 7

To 28.37 g of cyclic phosphate, 15.10 g of TMP, 12.61 g of DMAA and 0.42 g of Acrly Phosphate were mixed and mixed to prepare a flame retardant mixture containing surfactant.

56.50 g of the flame retarder mixture prepared above was mixed and stirred with 100 g of the first acrylic compound in which MMA and PMMA were mixed at a ratio of 8: 2 to prepare an acrylic composition.

Example 8

25 g of the prepared flame retardant mixture and 0.1 g of HDDMA were mixed and stirred into 100 g of the first acrylic compound in which MMA and PMMA were mixed at a ratio of 8: 2 to prepare an acrylic composition.

Example 9

53.84 g of the flame retardant mixture prepared above and 0.1 g of HDDMA were mixed and stirred into 100 g of the first acrylic compound in which MMA and PMMA were mixed at a ratio of 8: 2, to prepare an acrylic composition.

Example 10

25 g of the prepared flame retardant mixture and 0.1 g of EGDMA were mixed and stirred into 100 g of the first acrylic compound in which MMA and PMMA were mixed at a ratio of 8: 2 to prepare an acrylic composition.

Comparative Example 1

MMA and PMMA were mixed at 8: 2 and stirred to prepare an acrylic composition.

Comparative Example 2

25 g of DMAA was mixed and stirred with 100 g of the first acrylic compound in which MMA and PMMA were mixed in an 8: 2 ratio to prepare an acrylic composition.

Comparative Example 3

5.50g of cyclic phosphate, 5.50g of DMAA and 0.11g of Acrly Phosphate were mixed and mixed to prepare a flame retardant mixture containing surfactant.

11.11 g of the flame retarder mixture prepared above was mixed with 100 g of the first acrylic compound in which MMA and PMMA were mixed in an amount of 8: 2, followed by stirring. Then, 0.05 g of initiator was added and cured to prepare an acrylic cured product.

Comparative Example 4

28.47 g of DMAA and 0.14 g of Acrly Phosphate were mixed with 14.24 g of cyclic phosphate and mixed to prepare a flame retardant mixture containing a surfactant.

42.86 g of the flame retardant mixture prepared above was mixed and stirred with 100 g of the first acrylic compound in which MMA and PMMA were mixed in an amount of 8: 2, thereby preparing an acrylic composition.

Comparative Example 5

To 6.84 g of cyclic phosphate, 34.18 g of DMAA and 2.74 g of Acrly Phosphate were mixed and mixed to prepare a flame retardant mixture containing a surfactant.

43.75 g of the flame retardant mixture prepared above was mixed and stirred with 100 g of the first acrylic compound in which MMA and PMMA were mixed at a ratio of 8: 2 to prepare an acrylic composition.

Comparative Example 6

25 g of triphenyl phosphate was mixed with 100 g of the first acrylic compound in which MMA and PMMA were mixed in an amount of 8: 2, followed by stirring to prepare an acrylic composition.

Comparative Example 7

Mixture of 23.87g of triphenyl phosphate and 0.13g of Ethanol Amine was mixed to prepare a flame retardant mixture containing surfactant.

24 g of the flame retardant mixture prepared above was mixed and stirred with 80 g of the first acrylic compound in which MMA and PMMA were mixed in an amount of 8: 2 to prepare an acrylic composition.

The first acrylic compound First flame retardant Second flame retardant Surfactants The second acrylic compound ingredient weight
(g) ingredient weight
(g) ingredient weight
(g) ingredient weight
(g) ingredient weight
(g) Example 1 MMA 100 C.P. 20.83 DMAA 4.15 A.P. 0.03 - - Example 2 MMA 100 C.P. 15.68 DMAA 3.13 A.P. 0.01 - - Example 3 MMA 100 C.P. 16.63 DMAA 8.25 A.P. 0.13 - - Example 4 MMA 100 C.P. 55.53 DMAA 11.07 A.P. 0.07 - - Example 5 MMA 100 C.P. 44.77 DMAA 8.92 A.P. 0.15 - - Example 6 MMA 100 C.P. 44.33 DMAA 22.17 A.P. 0.17 - - Example 7 MMA 100 C.P. + TMP 28.37 + 15.10 DMAA 12.61 A.P. 0.42 - - Example 8 MMA 100 C.P. 16.63 DMAA 8.25 A.P. 0.13 HDDMA 0.1 Example 9 MMA 100 C.P. 44.77 DMAA 8.92 A.P. 0.15 HDDMA 0.5 Implementation 10 MMA 100 C.P. 16.63 DMAA 8.25 A.P. 0.13 EGDMA 0.3 Comparative Example 1 MMA 100 - - - - - - - - Comparative Example 2 MMA 100 - - DMAA 25.00 - - - - Comparative Example 3 MMA 100 C.P. 5.50 DMAA 5.50 A.P. 0.11 - - Comparative Example 4 MMA 100 C.P. 14.24 DMAA 28.47 A.P. 0.14 - - Comparative Example 5 MMA 100 C.P. 6.84 DMAA 34.18 A.P. 2.74 - - Comparative Example 6 MMA 100 T.P. 25.00 - - - - - - Comparative Example 7 MMA 100 T.P. 23.87 - - E.A. 0.13 - -

C.P. : Cyclic Phosphate

T.P: Triphenyl Phosphate

A.P. : Acrly Phosphate

E.A. : Ethanol Amine

<Production of Acrylic Sheet>

0.05 g of Azobisisobutyronitrile (AIBN) was added to the acrylic composition prepared according to Examples and Comparative Examples, and an acrylic plate was manufactured using a steel conveyor belt. Fig. 2 is a schematic view of the manufacturing method.

Experimental Example

(1) Measurement of flammability

The flame resistance of the specimens having a thickness of 3 or 10 mm was measured by a vertical test method of UL (Underwriter's Laboratory) 94. Table 2 shows the measurement results.

(2) Measurement of transmittance

The optical spectrum was measured at a width of 1 nm in the range of 250 to 2500 nm using a UV-Vis-NIR spectrometer (Shimadzu, Solidspec-3700) for a sample having a thickness of 3 or 10 mm and the resultant value was measured according to KS L 2514 , The visible light transmittance was calculated, and the results are shown in Table 2.

(3) Heat resistance measurement (heat distortion temperature Tg)

For a specimen of thickness 3 or 10 mm, when a load of 0.254 mm is deformed by two loads based on a high load (1.8 MP) and a low load (0.45 MP) using a load deflection temperature measuring device (QC-654) The heat resistance was measured by the temperature (heat distortion temperature) (ASTM D648). Table 2 shows the measurement results.

(4) Strength measurement

The pencil hardness of the 3 or 10 mm thick specimen was measured by the evaluation method specified in JIS K5401. The higher the H value, the stronger the scratch performance.

(5) Flow Mark

The presence or absence of the flow mark was visually observed with respect to the thickness of 3 or 10 mm. If the composition is not properly mixed after the curing reaction of the resin composition proceeds, or when the mixed ballast is broken, a flow mark is generated. Therefore, it can be evaluated that the compatibility is improved without the flow mark.

(6) Reaction heat control experiment

For the 3 or 10 mm thick specimens, the minimum curing time that did not cause the boiling phenomenon was measured to confirm the reaction heat control when curing.

thickness
(mm) Flame retardancy Transmittance
(%) Tg (占 폚) Pencil hardness Flow mark Curing time (Hr) Example 1 10 V0 93 100 3H none 24 Example 2 10 V2 93 103 3H none 24 Example 3 10 V2 93 105 3H none 24 Example 4 3 V0 90 90 2H none 12 Example 5 3 V2 90 95 2H none 12 Example 6 3 V2 90 95 2H none 12 Example 7 3 V1 92 95 3H none 6 Example 8 10 V0 93 103 3H none 12 Example 9 3 V0 90 95 2H none 6 Example 10 10 V0 93 103 3H has exist 12 Comparative Example 1 3, 10 Fail 93 105 3H none 12, 24 Comparative Example 2 10 Fail 93 110 3H none 24 Comparative Example 3 10 Fail 93 105 3H none 24 Comparative Example 4 3 Fail 93 110 2H none 12 Comparative Example 5 10 V0 93 105 3H has exist 24 Comparative Example 6 3 HB 90 90 1H to 2H none 12 Comparative Example 7 10 HB 85 90 1H has exist 24

As shown in Table 2, the acrylic resin according to the embodiment of the present invention is provided with flame retardancy, has an excellent flame retardancy of UL94 V2 or more, has translucency equal to that of conventional acrylic resin, and has a heat distortion temperature of 90 ° C or more It is found that a flame-retardant acrylic resin having excellent heat resistance is provided. The scratch resistance exhibited by the pencil hardness is also excellent, and the flow mark is not exhibited.

The features, structures, effects, and the like illustrated in the above-described embodiments can be combined and modified in other embodiments by those skilled in the art to which the embodiments belong. Therefore, it should be understood that the present invention is not limited to these combinations and modifications.

Claims

A first acrylic compound;
A flame retardant mixture comprising a first flame retardant comprising a phosphorus compound and a second flame retardant comprising an acrylamide based compound; And
A surfactant comprising an Acryl group and a Phosphate group,
Wherein the first flame retardant is contained in an amount of 15 to 60 parts by weight, the second flame retardant is contained in an amount of 1 to 25 parts by weight, and the surfactant is contained in an amount of 0.01 to 1.0 part by weight based on 100 parts by weight of the first acrylic compound.

The method according to claim 1,
Wherein the phosphorus compound is a cyclic phosphorus compound.

3. The method of claim 2,
Wherein the phosphorus compound has a specific gravity of 1.2 to 1.5.

The method of claim 3,
Wherein the phosphorus compound has a viscosity of 50,000 to 500,000 CPS at 25 占 폚.

The method according to claim 1,
Wherein the acrylamide-based compound is a compound having a glass transition temperature (Tg) when the polymer is higher than a glass transition temperature (Tg) when the first acrylic compound is a polymer.

6. The method of claim 5,
Wherein the glass transition temperature (Tg) when the acrylamide-based compound is a polymer is 80 to 150 占 폚.

delete

The method according to claim 1,
Wherein the surfactant is at least one selected from the group consisting of (2-methacryloyloxyethyl) phosphate, 2-hydroxyethyl methacrylate phosphate, Bis (2-methacryloxyethyl) phosphate and Monoacryloxyethyl phosphate.

10. The method of claim 9,
The first acrylic compound may be selected from the group consisting of Methyl Acrylate (MA), Ethyl Acrylate, Propyl Acrylate, Butyl Acrylate, 2-Ethylhexyl Acrylate, Acrylate, methyl methacrylate (MMA), ethyl methacrylate, propyl methacrylate, butyl methacrylate, and benzyl methacrylate. Wherein the flame retardant acrylic composition is at least one selected from the group consisting of the flame retardant acrylic composition.

The method according to claim 1,
Wherein the flame-retardant acrylic composition further comprises a second acrylic compound,
Wherein the second acrylic compound comprises at least one selected from the group consisting of hexanediol dimethacrylate (HDDMA), polyethylene glycol dimethacrylate (PEGDMA), ethylene glycol dimethacrylate (EGDMA), and diethylene glycol dimethacrylate (DEGDMA).

12. The method of claim 11,
And the second acrylic compound is contained in an amount of 0.02 to 5 parts by weight based on 100 parts by weight of the first acrylic compound.

The method according to claim 1,
Wherein the flame retardant acrylic composition is cured to produce a specimen having a thickness of 3 or 10 mm and a flame retardancy measured according to UL94 is not less than V2.

The method according to claim 1,
The flame retardant acrylic composition according to claim 1, wherein the flame retardant acrylic resin composition has a heat distortion temperature of 90 ° C or higher.