KR20200124874A - Flame resistant resin composition and fabrication method of thereof - Google Patents

Abstract

A flame retardant resin composition according to the present invention comprises: a silane mixture; an ABS mixture comprising acrylonitrile, butadiene rubber and styrene; an inorganic flame retardant; and a nitrogen-based flame retardant, wherein the silane mixture includes methacryloxypropyltrimethoxysilane and boric acid. The flame retardant resin composition exhibits an excellent flame retardant effect without using a halogen-based flame retardant.

Description

Flame resistant resin composition and fabrication method of thereof

The present invention relates to a flame-retardant resin composition, characterized in that a silane mixture containing boric acid and methacryloxypropyltrimethoxysilane is added to impart flame retardancy to an ABS resin.

Acrylonitrile-butadiene-styrene copolymer resin, commonly referred to as ABS resin, is a resin manufactured by copolymerization of acrylonitrile, butadiene and styrene groups as the name suggests. It has excellent mechanical strength and excellent aesthetics, so it is not only for everyday life products but also for buildings. It is also used for interior and exterior materials.

However, ABS resin has extremely low resistance to combustion, is easily ignited by an external fire, and acts as an energy source during ignition, making it difficult to extinguish and spread fire. For this reason, a number of studies have been conducted to impart flame retardancy to ABS resins.

Typically, a flame retardant is added to impart flame retardancy to a resin composition such as an ABS resin, and conventionally, a number of halogen flame retardants including a halogen compound such as chlorine or bromine have been used. The halogen-based flame retardant has an advantage of excellent flame retardant properties, but there is a problem of releasing toxic gases such as dioxins during combustion, and thus regulations are being strengthened.

In addition, conventional materials added to impart flame retardancy to ABS resins include antimony trioxide or antimony pentoxide, but when such antimony oxide is added to the ABS resin, there is a problem that the mechanical properties of the ABS resin are deteriorated.

As a result, it is urgent to develop a flame retardant that has excellent flame retardancy and does not cause a decrease in mechanical strength when applied to an ABS resin while avoiding the emission of toxic gases by not using a halogen-based flame retardant.

Korean Patent Application Publication No. 10-2003-0046054

It is an object of the present invention to provide a flame-retardant resin composition that exhibits excellent flame-retardant effect without using a halogen-based flame retardant.

Another object of the present invention is to provide a flame retardant resin composition having excellent physical properties such as tensile strength and flexural strength.

Flame-retardant resin composition according to the present invention is a silane mixture; ABS mixture comprising acrylonitrile, butadiene rubber and styrene; Inorganic flame retardants; And a nitrogen-based flame retardant, and the silane mixture includes methacryloxypropyltrimethoxysilane and boric acid.

In the flame-retardant resin composition according to an embodiment of the present invention, the silane mixture may include at least one dialkoxysilane compound selected from dimethoxydiphenylsilane and dimethoxydimethylsilane.

In the flame-retardant resin composition according to an embodiment of the present invention, the silane mixture may further include at least one trimethoxysilane compound selected from methyltrimethoxysilane and phenyltrimethoxysilane.

In the flame retardant resin composition according to an embodiment of the present invention, the inorganic flame retardant may be at least one selected from alumina hydrate and magnesium hydroxide.

In the flame-retardant resin composition according to an embodiment of the present invention, the nitrogen-based flame retardant may be one or two or more selected from melamine cyanurate, triazine, isocyanurate, urea and guanidine.

In the flame-retardant resin composition according to an embodiment of the present invention, the flame-retardant resin composition contains 70 to 120 parts by weight of a silane mixture, 20 to 40 parts by weight of an inorganic flame retardant, and 5 to 20 parts by weight of a nitrogen-based flame retardant based on 100 parts by weight of the ABS mixture. I can.

In the flame-retardant resin composition according to an embodiment of the present invention, the silane mixture may include 5 to 20 parts by weight of boric acid based on 100 parts by weight of methacryloxypropyltrimethoxysilane.

In the flame-retardant resin composition according to an embodiment of the present invention, the weight ratio of the dialkoxysilane compound to the trimethoxysilane compound may be 1:0.1 to 0.35.

The present invention also provides a method for preparing a flame-retardant resin composition, and the method for preparing a flame-retardant resin composition according to the present invention comprises a mixture of methacryloxypropyltrimethoxysilane, boric acid, dialkoxysilane compound, trimethoxysilane compound and a solvent. After preparing a first step of forming a silane network; A second step of preparing a silane mixture by removing a solvent from the mixed solution in which the silane network is formed; And the silane mixture; ABS mixture comprising acrylonitrile, butadiene rubber and styrene; And a third step of mixing an inorganic flame retardant, a nitrogen flame retardant, and an initiator.

The flame-retardant resin composition according to the present invention exhibits excellent flame-retardant effect without using a halogen-based flame retardant by adding a silane mixture containing methacryloxypropyltrimethoxysilane and boric acid when manufacturing an ABS resin, and tensile strength and flexural strength It has the advantage of excellent physical properties such as.

Advantages and features of the embodiments of the present invention, and a method of achieving them will become apparent with reference to the embodiments described later in detail together with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in a variety of different forms, and only these embodiments make the disclosure of the present invention complete, and are common knowledge in the technical field to which the present invention pertains. It is provided to completely inform the scope of the invention to those who have, and the invention is only defined by the scope of the claims. The same reference numerals refer to the same components throughout the specification.

In describing the embodiments of the present invention, if it is determined that a detailed description of a known function or configuration may unnecessarily obscure the subject matter of the present invention, a detailed description thereof will be omitted. In addition, terms to be described later are terms defined in consideration of functions in an embodiment of the present invention and may vary according to the intention or custom of users or operators. Therefore, the definition should be made based on the contents throughout this specification.

Flame-retardant resin composition according to the present invention is a silane mixture; ABS mixture comprising acrylonitrile, butadiene rubber and styrene; Inorganic flame retardants; And a nitrogen-based flame retardant, wherein the silane mixture comprises methacryloxypropyltrimethoxysilane and boric acid.

The applicant of the present invention conducted a study to prevent degradation of the physical properties of the manufactured resin while imparting flame retardancy to the ABS resin, and as a result of the study, a silane network was formed by mixing methacryloxypropyltrimethoxysilane and boric acid. It is formed, and by adding an additional silane mixture in which boron atoms are mixed together between networks, there is an advantage that high flame retardancy can be exhibited without deteriorating physical properties.

In the flame-retardant resin composition according to an embodiment of the present invention, the silane mixture may further include a dialkoxy silane compound and a trimethoxysilane compound. Since the silane mixture further includes a dialkoxy silane and a trimethoxysilane compound, it is possible to form a silane network by promoting the formation of the silane network and minimizing residual silane compounds.

Specifically, in the flame-retardant resin composition according to an embodiment of the present invention, the dialkoxysilane compound may be at least one selected from dimethoxydiphenylsilane and dimethoxydimethylsilane, and the trimethoxysilane The compound may be at least one selected from methyltrimethoxysilane and phenyltrimethoxysilane. When the flame-retardant resin composition according to an embodiment of the present invention contains the above-described dialkoxysilane compound and trimethoxysilane compound, the accessibility to silicon atoms is controlled in the process of forming a silane network, and thus silicon at an excessively high speed. There is an advantage in that a silane network can be efficiently formed while preventing a problem in which boron atoms are not uniformly distributed due to the formation of a network.

That is, if the size of the alkyl group included in the dialkoxysilane compound and the trimethoxysilane compound is too small, there is a problem in that the reaction proceeds rapidly due to too fast access to the silicon atom when the silane network is formed. If the size of the alkyl group contained in the oxysilane compound is too large, the reaction rate may be too slow, and from the viewpoint of preventing such a problem, the dialkoxysilane compound is dimethoxydiphenylsilane and dimethoxydimethyl It may be one or more selected from silane (Dimethoxydimethylsilane), and the trimethoxysilane compound may be one or more selected from methyltrimethoxysilane and phenyltrimethoxysilane.

Preferably, the weight ratio of the dialkoxysilane compound: the trimethoxysilane compound may be 1:0.1 to 0.35, specifically 1:0.12 to 0.3, and if the silane mixture does not cause a decrease in physical properties of the ABS resin in this range, However, it has the advantage of securing flame retardancy of V-1 or higher, preferably V-0 grade.

Specifically, the silane mixture satisfies the weight ratio of the above-described dialkoxysilane compound and trimethoxy silane compound, and 200 to 350 parts by weight of dialkoxysilane compound, 30 to 80 parts by weight based on 100 parts by weight of methacryloxypropyltrimethoxysilane. It may contain a trimethoxysilane compound, 5 to 20 parts by weight of boric acid. With the formation of sufficient crosslinking in this range, there is an advantage of being able to form a sufficient bond with the ABS resin later by the acrylic group contained in methacryloxypropyltrimethoxysilane.

At this time, when boric acid is added in a small amount than the above range, it is difficult to achieve the effect of the addition of boric acid.Moreover, considering that boric acid acts as an acid that acts as a catalyst when forming a silane network, when a small amount of boric acid is added, the formation of a silane network is difficult. There is a problem that can be hindered. In addition, when boric acid is added in a larger amount than the above-described range, there is a problem in that too many boron atoms are distributed in the silane network, resulting in deterioration of physical properties.

Specifically, the silane mixture in the flame-retardant resin composition according to an embodiment of the present invention comprises the above-described methacryloxypropyltrimethoxysilane, boric acid, dialkoxysilane compound, and trimethoxy silane compound, and a mixture of water and isopropyl alcohol. After mixing as a solvent and performing a reaction to form a silane network, the solvent may be removed through solvent extraction. By passing through this process, it is possible to prevent the problem that water and alcohol affect the reactivity of the initiator when forming the ABS resin later.

In this case, the solvent may be a mixture of water and an alcohol having 1 to 4 carbon atoms. At this time, water reacts with the alkoxy group of the silane compound to affect the formation of a silane network, and alcohol may serve as a solvent. In this case, the added water may be 80 to 130 parts by weight based on 100 parts by weight of methacryloxypropyltrimethoxysilane, and the alcohol having 1 to 4 carbon atoms may be included in 300 to 550 parts by weight, but the present invention is not limited thereto. .

The flame-retardant resin composition according to an embodiment of the present invention includes an ABS (acrylonitrile-butadiene-styrene) mixture including acrylonitrile, butadiene rubber, and styrene. At this time, the contents of acrylonitrile, butadiene rubber, and styrene contained in the ABS mixture may vary depending on the use of the ABS resin to be prepared, required physical properties, etc., and the present invention is not limited thereto. As a specific and non-limiting example, the weight ratio of acrylonitrile: butadiene rubber: styrene contained in the ABS mixture may be mixed in a weight ratio of 1:1.5 to 4:3 to 7, but the present invention is not limited thereto. .

In addition, the flame-retardant resin composition according to an embodiment of the present invention may include an initiator. In this case, the initiator may be used without limitation if it is an initiator used to initiate polymerization of the ABS resin. As a specific and non-limiting example, the initiator may be one or more selected from benzoyl peroxide (BPO) or 2,2'-azo-bis-isobutyrylnitrile (AIBN), but the present invention is not limited thereto. Further, from the viewpoint of a manufacturing method, it is obvious that when the ABS resin is polymerized, a reaction environment can be set according to the use temperature of each initiator, and the present invention is not limited thereto.

Furthermore, the flame-retardant resin composition according to the present invention may additionally include a non-halogen-based flame retardant such as an inorganic flame retardant and a nitrogen-based flame retardant, and flame retardancy may be further improved by such an additional flame retardant. Preferably, the inorganic flame retardant may be one or two or more selected from alumina hydrate and magnesium hydroxide, and the nitrogen-based flame retardant may be one or two or more selected from melamine cyanurate, triazine, isocyanurate, urea and guanidine. I can. When the above-described inorganic flame retardant and nitrogen-based flame retardant are used together with the above-described silane mixture, the silane mixture and dispersion are easily dispersed when mixing the flame-retardant resin composition, so that a uniform resin composition can be prepared. It has the advantage of showing excellent flame retardancy effect.

At this time, the flame-retardant resin composition may include 70 to 120 parts by weight of a silane mixture, 20 to 40 parts by weight of an inorganic flame retardant, and 5 to 20 parts by weight of a nitrogen-based flame retardant relative to 100 parts by weight of the ABS mixture, and within this range, the physical properties of the ABS resin It has the advantage of preventing deterioration and promoting excellent flame retardancy.

The present invention also provides a method for producing a flame retardant resin composition. The flame-retardant resin composition manufacturing method according to the present invention comprises a first step of forming a silane network after preparing a mixture by mixing methacryloxypropyltrimethoxysilane, boric acid, dialkoxysilane compound, trimethoxysilane compound, and a solvent; A second step of preparing a silane mixture by removing a solvent from the mixed solution in which the silane network is formed; And the silane mixture; ABS mixture comprising acrylonitrile, butadiene rubber and styrene; And a third step of mixing an inorganic flame retardant, a nitrogen flame retardant, and an initiator.

More specifically, the third step is 3-1 step of first mixing the ABS mixture and the initiator to initiate polymerization; 3-2 step of polymerization by adding the silane mixture to the polymerization-initiated ABS mixture; And 3-3 step of adding an inorganic flame retardant and a nitrogen flame retardant after the polymerization step. That is, in the method for preparing a flame-retardant resin composition according to an embodiment of the present invention, first, polymerization of the ABS resin is initiated, polymerization of the ABS resin is performed above the intraday level, and then a silane mixture is added to perform polymerization of the acrylic group and the ABS resin in the silane mixture. It can be done additionally. By adding the silane mixture after polymerization is started in this way, it is possible to prepare a flame-retardant resin composition in which the silane mixture is uniformly distributed while preventing a chemical reaction of the initiator by water and alcohol, which may be partially included in the silane mixture.

In this case, step 3-1 may be performed under conditions for initiating a polymerization reaction by an initiator, and it is obvious that specific conditions may vary depending on the type of initiator included. However, in step 3-1, in order to prevent a problem in which the polymerization is rapidly initiated and the reaction is completed before the silane mixture is added, the reaction may be performed at a temperature lower than the initiation temperature of a commonly used initiator. For example, when the initiator is BPO, polymerization can be performed at a temperature of 50 to 75°C in step 3-1, and by performing polymerization under such conditions, the silane mixture and crosslinking are sufficiently performed so that separation, etc., does not occur. There is an advantage that it is possible to manufacture ABS resin.

In this case, the solvent may be a mixture of water and an alcohol having 1 to 4 carbon atoms, and by simultaneously using water and alcohol as a solvent, formation of a silane network may be promoted and uniform dispersion may be achieved. Furthermore, the method for preparing a flame-retardant resin composition according to the present invention prevents the initiator from being deformed due to a reaction between the initiator and water or alcohol, which are inevitably introduced during the production of the ABS resin after the formation of a silane network and then undergo a solvent extraction step. I can.

The detailed materials and contents of the silane mixture, ABS mixture, inorganic flame retardant, and nitrogen-based flame retardant used in the method for preparing the flame retardant resin composition described above are the same as those of the flame retardant resin composition described above, and detailed information will be omitted to avoid redundant description.

Hereinafter, the present invention will be described in detail by examples and comparative examples. The following examples are only intended to aid understanding of the present invention, and the scope of the present invention is not limited by the following examples.

[Production Example 1]

Preparation of silane mixture

Dimethoxydiphenylsilane 35g, dimethoxydimethylsilane 35g, methyltrimethoxysilane 5g, phenyltrimethoxysilane 5g, methacryloxypropyltrimethoxysilane 25g, boric acid 2.5g, distilled water 25g and 100 g of isopropyl alcohol was put into a mixing vessel, stirred at 60° C. for 5 hours, and then distilled water and isopropyl alcohol solvent were removed to prepare a silane mixture having a silane network.

2. Manufacturing of ABS resin

After dissolving 20 g of acrylonitrile, 18 g of butadiene, and 62 g of styrene in 50 g of ethylbenzene, a polymerization solution was prepared by adding 0.01 g of benzoyl peroxide (BPO) as an initiator, and the polymerization solution was heated to a temperature of 60°C. Then, the polymerization was carried out in one step, and 100 g of the silane mixture prepared in the step of preparing the silane mixture described above was added in portions by 10 g per minute while stirring while maintaining at 60°C. After the addition of the silane mixture was completed, 20 g of Mg(OH) ₂ , 10 g of alumina trihydrate, and 10 g of guanidine were added, followed by additional polymerization by heating to 70°C and terminating the reaction. .

[Production Example 2]

It was prepared in the same manner as in Preparation Example 1, but in the preparation step of the silane mixture, 30 g of dimethoxydiphenylsilane and dimethoxydimethylsilane were each added to prepare an ABS resin composition.

[Production Example 3]

It was prepared in the same manner as in Preparation Example 1, but 0.5 g of boric acid was added in the preparation step of the silane mixture to prepare an ABS resin composition.

[Production Example 4]

It was prepared in the same manner as in Preparation Example 1, but an ABS resin composition was prepared by adding 10 g of boric acid.

[Production Example 5]

It was prepared in the same manner as in Preparation Example 1, but by adding 1 g of methyltrimethoxysilane and phenyltrimethoxysilane, respectively, to prepare an ABS resin composition.

[Production Example 6]

It was prepared in the same manner as in Preparation Example 1, but 15 g of methyltrimethoxysilane and phenyltrimethoxysilane were each added to prepare an ABS resin composition.

[Production Example 7]

It was prepared in the same manner as in Preparation Example 1, but 50 g of a silane mixture was mixed in the manufacturing step of the ABS resin to prepare an ABS resin composition.

[Production Example 8]

It was prepared in the same manner as in Preparation Example 1, but 150 g of a silane mixture was mixed in the manufacturing step of the ABS resin to prepare an ABS resin composition.

[Comparative Production Example 1]

It was prepared in the same manner as in Preparation Example 1, but the ABS resin composition was prepared without adding a silane mixture in the manufacturing step of the ABS resin.

[Comparative Production Example 2]

It was prepared in the same manner as in Preparation Example 1, but in the step of preparing the silane mixture, 3 g of 0.01 N hydrochloric acid was added without adding boric acid to prepare an ABS resin composition.

[Comparative Production Example 3]

It was prepared in the same manner as in Preparation Example 1, but without adding Mg(OH) ₂ , alumina trihydrate, and guanidine, and instead of adding 40 g of antimony trioxide having an average particle diameter of 0.4 μm to prepare an ABS resin composition.

[Comparative Production Example 4]

It was prepared in the same manner as in Preparation Example 1, but the ABS resin composition was prepared without adding methacryloxypropyltrimethoxysilane in the preparation step of the silane mixture.

As a result of the preparation, it was found that the silane mixture and the ABS resin did not form a single phase and were separated, and accordingly, it was confirmed that it was impossible to perform additional experiments. This is considered to be a phenomenon that occurs because crosslinking does not occur between the silane mixture and the ABS resin.

Confirmation of flame retardancy of ABS resin composition

According to the UL-94 flame retardancy determination test method, it was determined by testing for 1/16 inch thickness, and the results are shown in Table 1.

Measurement of impact strength of ABS resin composition

The ABS resin compositions prepared in Preparation Examples and Comparative Examples were measured for impact strength against ⅛ inch thickness by ASTM D256 test method, and are shown in Table 1.

Confirmation of fall impact of ABS resin composition

It was evaluated under the conditions of a load of 18 kg and a height of 85 cm by ASTM D648 test method, and the results are shown in Table 1.

Flame retardancy Impact strength
(Kg·cm/cm) Fall impact
(J) Manufacturing Example 1 V-0 24 37 Manufacturing Example 2 V-0 24 38 Manufacturing Example 3 V-0 19 35 Manufacturing Example 4 V-1 17 34 Manufacturing Example 5 V-0 18.5 34 Manufacturing Example 6 V-0 16 35 Manufacturing Example 7 V-0 21 33 Manufacturing Example 8 V-0 20 31 Comparative Preparation Example 1 V-1 13 30 Comparative Preparation Example 2 V-1 14.5 28 Comparative Preparation Example 3 V-2 15 29

Referring to Table 1, it can be seen that the ABS resin composition according to the preparation example of the present invention exhibits high flame retardancy. Furthermore, it can be seen that the impact strength and falling impact of the ABS resin corresponding to Preparation Example 1 are significantly higher compared to the case where the content of boric acid is relatively large or small, or the content of the trimethoxy silane compound is large or small. It is judged to be the effect that the silane network is well formed in the range of the content including 1.

On the other hand, in the case of Comparative Example 1 without the addition of the silane mixture, Comparative Example 2 without the addition of boric acid or Comparative Example 3 in which antimony trioxide was added instead of the inorganic flame retardant and nitrogen-based flame retardant had lower impact strength than the Preparation Example of the present invention. can confirm.

Claims (9)

Silane mixture; ABS mixture comprising acrylonitrile, butadiene rubber and styrene; Inorganic flame retardants; And a nitrogen-based flame retardant,
The silane mixture is a flame retardant resin composition comprising methacryloxypropyltrimethoxysilane and boric acid. The method of claim 1,
The silane mixture is a flame-retardant resin composition comprising at least one dialkoxysilane compound selected from dimethoxydiphenylsilane and dimethoxydimethylsilane. The method of claim 2,
The silane mixture further comprises one or more trimethoxysilane compounds selected from methyltrimethoxysilane and phenyltrimethoxysilane. The method of claim 1,
The inorganic flame retardant is at least one flame retardant resin composition selected from alumina hydrate and magnesium hydroxide. The method of claim 1,
The nitrogen-based flame retardant is one or two or more selected from melamine cyanurate, triazine, isocyanurate, urea and guanidine. The method of claim 1,
The flame-retardant resin composition comprises 70 to 120 parts by weight of a silane mixture, 20 to 40 parts by weight of an inorganic flame retardant, and 5 to 20 parts by weight of a nitrogen-based flame retardant based on 100 parts by weight of the ABS mixture. The method of claim 1,
The silane mixture is a flame-retardant resin composition comprising 5 to 20 parts by weight of boric acid based on 100 parts by weight of methacryloxypropyltrimethoxysilane. The method of claim 3,
The weight ratio of the dialkoxysilane compound: the trimethoxysilane compound is 1:0.1 to 0.35 flame retardant resin composition. A first step of forming a silane network after preparing a mixed solution by mixing methacryloxypropyltrimethoxysilane, boric acid, dialkoxysilane compound, trimethoxysilane compound, and a solvent; A second step of preparing a silane mixture by removing a solvent from the mixed solution in which the silane network is formed; And the silane mixture; ABS mixture comprising acrylonitrile, butadiene rubber and styrene; Flame-retardant resin composition manufacturing method comprising a third step of mixing an inorganic flame retardant, a nitrogen-based flame retardant and an initiator.