KR102257396B1 - Silicone type flame retardant supplement - Google Patents

Abstract

The present invention relates to a silicone-based flame retardant agent which is manufactured by reacting 25 to 35 parts by weight of silica; 40 to 60 parts by weight of polyphenylene ether; 40 to 50 parts by weight of silicone polymer; 1 to 10 parts by weight of 3-glycidoxypropyltrimethoxysilane; 1 to 10 parts by weight of methyltetrahydrophthalic anhydride; 1 to 10 parts by weight of 4,4'-bis(alpha, alpha-dimethylbenzyl)diphenylamine; 1 to 10 parts by weight of pentaerythritol tetrastearate; 5 to 15 parts by weight of N,N'-(1,3-phenylene)dimaleimide; and 1 to 2 parts by weight of 1,3-bis(tert-butylperoxyisopropyl)benzene. According to the present invention, the silicone-based flame-retardant auxiliary agent is be added to a resin having insulating properties to increase flame retardancy and low dielectric constant properties and increase dispersibility and processability while having flame retardant and low dielectric constant properties.

Description

Silicon type flame retardant supplement

The present invention relates to a silicone-based flame retardant aid, and more specifically, 25 to 35 parts by weight of silica, 40 to 60 parts by weight of polyphenylene ether, 40 to 50 parts by weight of silicone polymer, 3-glycidoxypropyltrimethoxysilane 1 To 10 parts by weight, 1 to 10 parts by weight of methyltetrahydrophthalic anhydride, 1 to 10 parts by weight of 4,4'-bis(alpha, alpha-dimethylbenzyl)diphenylamine, 1 to 10 parts by weight of pentaerythritol tetrastearate, Prepared by reacting 5 to 15 parts by weight of N,N'-(1,3-phenylene)dimaleimide and 1 to 2 parts by weight of 1,3-bis(tert-butylperoxyisopropyl)benzene, It is added to a resin to improve flame retardancy and low dielectric constant characteristics, and has flame retardancy and low dielectric constant characteristics, while improving dispersibility and improves the processability of a silicone-based flame retardant aid.

Wires and cables are coated with an insulating resin composition, and a representative example of the insulating resin composition may be a polyvinyl chloride resin composition, but the polyvinyl chloride resin composition has a problem of generating harmful gases in case of fire, In recent years, in order to improve the mechanical properties and thermal stability of a non-polar polyolefin resin, a base resin formed by mixing a polar polyolefin resin with a flame retardant, a flame retardant auxiliary as described in the following patent documents, etc. are mixed to form a polyolefin resin having insulation and flame retardancy. Compositions are widely used as coatings for wires and cables.

<Patent Literature>

Registered Patent No. 10-0717820 (registered on May 07, 2007) "Flame-retardant auxiliary providing improved surface quality and anti-corrosion properties"

However, in recent years, due to the development of information and communication, a large amount of information must be processed at high speed, so the resin composition covering cables, etc., must have not only insulation and flame retardancy, but also a low dielectric constant, and the polyolefin resin composition uses a polar polyolefin resin. , There is a problem that the electrical characteristics (dielectric loss characteristics) are deteriorated. It may be considered to add an additive to the polyolefin resin composition so that the polyolefin resin composition has a low dielectric constant, but there is a problem in that processability is poor when an additive is added to the polyolefin resin composition, and the additive is processed through coating, etc. In this case, it is possible to improve processability and dispersibility, but there is a problem in that economic efficiency is inferior due to several additional processes.

The present invention was devised to solve the above problems,

An object of the present invention is to provide a silicone-based flame retardant aid that is added to a resin having insulating properties to improve flame retardancy and low dielectric constant characteristics.

In addition, an object of the present invention is to provide a silicone-based flame retardant aid capable of improving dispersibility and improving processability while having flame retardancy and low dielectric constant characteristics.

The present invention is implemented by an embodiment having the following configuration in order to achieve the above object.

According to an embodiment of the present invention, the silicone-based flame retardant aid according to the present invention is silica, polyphenylene ether, silicone polymer, 3-glycidoxypropyltrimethoxysilane, methyltetrahydrophthalic anhydride, 4,4'-bis (Alpha, alpha-dimethylbenzyl) diphenylamine, pentaerythritol tetrastearate, N,N'-(1,3-phenylene)dimaleimide and 1,3-bis(tert-butylperoxyisopropyl)benzene It is characterized in that it is prepared by reacting.

According to another embodiment of the present invention, the silicone-based flame retardant aid according to the present invention is silica 25 to 35 parts by weight, polyphenylene ether 40 to 60 parts by weight, silicone polymer 40 to 50 parts by weight, 3-glycidoxypropyl trime. 1 to 10 parts by weight of oxysilane, 1 to 10 parts by weight of methyltetrahydrophthalic anhydride, 1 to 10 parts by weight of 4,4'-bis(alpha, alpha-dimethylbenzyl)diphenylamine, 1 to 10 parts by weight of pentaerythritol tetrastearate It is prepared by reacting 5 to 15 parts by weight of N,N'-(1,3-phenylene)dimaleimide and 1 to 2 parts by weight of 1,3-bis(tert-butylperoxyisopropyl)benzene by weight. It is characterized.

According to another embodiment of the present invention, the flame retardant resin composition according to the present invention comprises 100 parts by weight of a base resin, 20 to 50 parts by weight of a flame retardant, 5 to 15 parts by weight of a flame retardant aid, and 3,3-thiodipropio It contains 0.1 to 2 parts by weight of nate, 0.1 to 2 parts by weight of hydroxyphenylbenzotriazole, and 1 to 3 parts by weight of a crosslinking agent, and the flame retardant auxiliary is characterized in that the flame retardant auxiliary of claim 2 is used.

The present invention can obtain the following effects by the above embodiment.

The present invention has an effect of improving flame retardancy and low dielectric constant properties by being added to an insulating resin.

In addition, the present invention has an effect of improving dispersibility and improving processability while having flame retardancy and low dielectric constant characteristics.

Hereinafter, the silicone-based flame retardant aid according to the present invention will be described in detail. Unless otherwise defined, all terms in this specification are the same as the general meaning of the terms understood by those of ordinary skill in the art to which the present invention belongs. According to the definitions used in the specification. In addition, detailed descriptions of known functions and configurations that may unnecessarily obscure the subject matter of the present invention will be omitted. Throughout the specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless specifically stated to the contrary.

The silicone-based flame retardant aid according to an embodiment of the present invention is a material that is added to the resin together with a flame retardant to improve the flame retardancy of the resin, and is 25 to 35 parts by weight of silica, 40 to 60 parts by weight of polyphenylene ether, and 40 to 50 of the silicone polymer. 1 to 10 parts by weight of 3-glycidoxypropyltrimethoxysilane, 1 to 10 parts by weight of methyltetrahydrophthalic anhydride, 1 to 10 of 4,4'-bis(alpha, alpha-dimethylbenzyl)diphenylamine Parts by weight, 1 to 10 parts by weight of pentaerythritol tetrastearate, 5 to 15 parts by weight of N,N'-(1,3-phenylene)dimaleimide, and 1,3-bis(tert-butylperoxyisopropyl) It is characterized in that it is prepared by reacting 1 to 2 parts by weight of benzene. The flame retardant aid has a particle shape, has a certain size, but preferably has an average particle size of 0.001 to 1 mm, and was completed to overcome the disadvantages of the flame retardant aid made of silica and silicone polymer and provide additional functions.

The silica (Silica) is a composition used to improve the flame retardancy of the resin, is used in the range of 25 to 35 parts by weight, and is preferably used in the range of 27 to 33 parts by weight. The silica is a known silica-based compound used in a flame retardant aid, and when agglomerated, it has a disadvantage of deteriorating flame retardancy and processability of the resin, and thus the silica is coated to prevent agglomeration and improve the processability of the resin. The silica not only improves flame retardancy, but also has low-dielectric properties, thereby improving the low-dielectric properties of the resin.

The polyphenylene ether (Polyphenylene Ether) is a composition used to improve the low dielectric constant characteristics of the resin, is used in the range of 40 to 60 parts by weight, and is preferably used in the range of 45 to 55 parts by weight. The polyphenylene ether has insulating properties and electrical properties with low dielectric loss, as well as self-extinguishing properties, thereby improving flame retardancy. As the polyphenylene ether, a modified PPE resin (eg, Noryl IC780, etc.) in which a small amount of polystyrene is blended may be used.

The silicone polymer is a composition used to improve the flame retardancy of the resin, and is used in the range of 40 to 50 parts by weight, and is preferably used in the range of 43 to 48 parts by weight. The silicone polymer is a silica-based known compound used for flame retardant aids, and when agglomerated, it has a disadvantage of deteriorating flame retardancy and processability of the resin, and thus the silicone polymer is coated to prevent agglomeration and improve the processability of the resin. As the silicone polymer, various conventional materials may be used, for example, polydimethyl siloxane (PDMS) may be used, and more preferably, an oily PDMS particle may be emulsified in water (Latex). The silicone polymer not only improves flame retardancy, but also improves the processability of the resin due to its small surface tension.

The 3-Glycidoxypropyltrimethoxysilane is a composition used to increase the bonding strength of the composition constituting the flame retardant aid, and is used in the range of 1 to 10 parts by weight, and preferably 2 to 4 parts by weight. It is used in the sub-range.

The methyltetrahydrophthalic anhydride is a composition used to increase miscibility with the resin, and is used in the range of 1 to 10 parts by weight, and is preferably used in the range of 3 to 5 parts by weight.

The 4,4'-bis (alpha, alpha-dimethylbenzyl) diphenylamine (4,4'-bis (α, α-dimethybenzyl) diphenylamine) changes color by heat, changes in mechanical and electrical properties, unnecessary surface reactions It is used in the range of 1 to 10 parts by weight, and is preferably used in the range of 3 to 5 parts by weight.

The pentaerythritol tetrastearate is a composition used to improve processability by improving the flow of the resin during processing of the resin, and is used in the range of 1 to 10 parts by weight, and preferably in the range of 3 to 7 parts by weight. Is used.

The N,N'-(1,3-phenylene)dimaleimide (N,N'-(1,3-phenylene)dimaleimide) is a composition used for crosslinking polyphenylene ether, and 5 to 15 weights It is used in the range of parts and is preferably used in the range of 7 to 13 parts by weight.

The 1,3-bis (tert-butylperoxyisopropyl) benzene (1,3-bis ( tert- butylperoxyisopropyl) benzene) is a constitution that promotes crosslinking, and is preferably used in the range of 1 to 3 parts by weight.

Flame-retardant resin composition according to another embodiment of the present invention is 100 parts by weight of a base resin comprising a non-polar polyolefin resin and a polar polyolefin resin, 20 to 50 parts by weight of a flame retardant, 5 to 15 parts by weight of a flame retardant aid, and 3,3- 0.1 to 2 parts by weight of thiodipropionate, 0.1 to 2 parts by weight of hydroxyphenylbenzotriazole, and 1 to 3 parts by weight of a crosslinking agent.

The base resin is a raw material for coating materials such as electric wires and cables, and includes 65 parts by weight of a non-polar polyolefin resin and 35 parts by weight of a polar polyolefin resin, and the non-polar polyolefin resin is preferably a low-density polyethylene, and the polar polyolefin resin is ethylene ethyl. It is preferred that an acrylate is used.

The flame retardant is added to the base resin to impart flame retardancy. It is preferable to use 20 to 50 parts by weight based on 100 parts by weight of the base resin, and a known conventional flame retardant may be used.

The flame retardant aid is added to the base resin together with the flame retardant to improve flame retardancy. It is preferable to use 5 to 15 parts by weight based on 100 parts by weight of the base resin, and the flame retardant aid described above is used.

The distearyl 3,3-thiodipropionate (Distearyl 3,3-thiodipropionate) is added to the base resin to impart an antioxidant function, and 0.1 to 2 parts by weight is used based on 100 parts by weight of the base resin. It is desirable.

The hydroxyphenylbenzotriazole is added to the base resin to improve stability against ultraviolet rays, and 0.1 to 2 parts by weight is preferably used based on 100 parts by weight of the base resin.

The crosslinking agent is a configuration used to increase physical properties and heat resistance for insulating purposes by crosslinking. It is preferable to use 1 to 3 parts by weight based on 100 parts by weight of the base resin, and a known conventional crosslinking agent (e.g., Dicumyl Peroxide Etc.) can be used.

Hereinafter, the present invention will be described in more detail through examples. However, these are only for describing the present invention in more detail, and the scope of the present invention is not limited thereto.

<Example 1> Preparation of flame retardant auxiliary

1. Flame retardant aid 1

(1) A first solution was prepared by dissolving 50 parts by weight of polyphenylene ether (Noryl IC780) in an organic solvent (acetone).

(2) A second solution was prepared by dispersing 30 parts by weight of silica powder in an organic solvent.

(3) Mixing the first solution and the second solution, PDMS latex (including 45 parts by weight of PDMS), 3 parts by weight of 3-glycidoxypropyltrimethoxysilane, 4 parts by weight of methyltetrahydrophthalic anhydride, 4,4 '-Bis(alpha,alpha-dimethylbenzyl)diphenylamine 4 parts by weight, pentaerythritol tetrastearate 5 parts by weight, N,N'-(1,3-phenylene)dimaleimide (N,N'-( 1,3-phenylene)dimaleimide) 10 parts by weight and 2 parts by weight of 1,3-bis(tert-butylperoxyisopropyl)benzene were further mixed to prepare a reaction solution.

(4) Put the reaction solution into a tank where water was added to dissolve the organic solvent (acetone) in water to separate the organic solvent, obtain agglomerates, dry in a fluidized bed dryer until the moisture content is less than 1%, and pulverize. Thus, a particulate flame retardant aid 1 was obtained.

2. Flame retardant aid 2

Except for using a styrene acrylonitrile copolymer in place of polyphenylene ether, the other conditions were the same as in Example 1 1 to prepare a flame retardant aid 2.

3. Flame retardant aid 3

Flame retardant aid 3 was prepared in the same manner as in Example 1 except that silica was not used and PDMS latex (including 75 parts by weight of PDMS) was used.

4. Flame retardant aid 4

Flame retardant aid 4 was prepared in the same manner as in Example 1 except that PDMS latex was not used and 75 parts by weight of silica were used.

5. Flame retardant aid 5

Except that 3-glycidoxypropyltrimethoxysilane was not used, the other conditions were the same as in Example 1 1 to prepare a flame retardant auxiliary 5.

6. Flame retardant aid 6

Except that methyl tetrahydrophthalic anhydride was not used, other conditions were the same as in Example 1 to prepare a flame retardant aid 6.

<Example 2> Flame retardancy evaluation

1. Flame retardant evaluation samples 1 to 6 having a thickness of 1/16 inch were prepared by mixing 100 parts by weight of a base resin, 40 parts by weight of a flame retardant, 10 parts by weight of a flame retardant auxiliary, and 2 parts by weight of a crosslinking agent. As a base resin, low density polyethylene and ethylene ethyl acrylate were mixed in a weight ratio of 65:35, aluminum hydroxide surface-treated with silane was used as a flame retardant, dicumyl peroxide was used as a crosslinking agent, and flame retardant evaluation sample 1 To 6 used flame retardant aids 1 to 6, respectively.

2. Flame retardancy evaluation For samples 1 to 6, the appropriate ratio, cotton burning, combustion rate and flame retardancy were evaluated according to UL94, and the results are shown in Table 1.

3. Looking at Table 1, it can be seen that when only silica is used without silicone polymer, flame retardancy is poor, and when miscibility with resin is poor, combustion rate is decreased.

Flame retardant evaluation sample Proper ratio Cotton burning Burn rate (sec) Flame retardancy One 0/10 0/10 5 V0 2 0/10 0/10 6 V0 3 0/10 0/10 4 V0 4 0/10 0/10 10 V0 5 0/10 0/10 6 V0 6 0/10 0/10 8 V0

<Example 3> Evaluation of dispersion degree and processability

1. Using 95 parts by weight of LDPE and 5 parts by weight of a flame retardant auxiliary, master batch samples 1 to 6 were prepared. For the master batch samples 1 to 6, flame retardant aids 1 to 6 were used, respectively.

2. Dispersion evaluation

(1) For the master batch samples 1 to 6, the dispersion form and the dispersed particle size were checked by SEM, and the dispersibility was evaluated and shown in Table 2. The dispersibility was evaluated by checking the SEM image, and the dispersibility was poor when there were approximately 20% or more of particles of 100 μm or more due to agglomeration of particles.

(2) Looking at Table 2, it can be seen that the dispersibility is inferior when a silicone polymer is not used and only silica is used, or a methyl tetrahydrophthalic anhydride, which improves miscibility with a resin, is not used.

Master batch sample One 2 3 4 5 6 Dispersibility good good good Bad good Bad

3. Processability evaluation

(1) The master batch samples 1 and 3 to 6 were tested by extruding the ^{specimen at a constant shear rate (~400s -1} ) using a Thermofisher's rheodrove7 single screw (die diameter is 1.5mm, L=20d). . As a test evaluation item, the pressure is measured after 90 minutes from the start of extrusion (measured using a pressure gauge of an extruder), and the melt crack removal time (melting crack phenomenon can be visually detected in the state of the strand discharged at the beginning of extrusion. This phenomenon is removed), and the results are shown in Table 3. In addition, by checking the time at which the extruded plastic accumulates at the die exit surface, the order in which the build-up occurs first for the master batches 1 and 3 to 6 was confirmed.

(2) Looking at Table 3, it can be seen that the internal pressure reduction and melting crack removal time of the master batch sample 4 are the lowest, and when 3-glycidoxypropyltrimethoxysilane or methyltetrahydrophthalic anhydride is not used It can be seen that the reduction and melting crack removal time are relatively inferior. In addition, if the order of build-up occurs first for master batch 1 and 4 to 6, the build-up appears in the order of master batch 4, master batch 6, master batch 5, master batch 1, and master batch 3, reducing internal pressure and It can be seen that the result is similar to the evaluation result for the melt crack removal time.

Master batch sample start(bar) 90 minutes (bar) Melt crack removal time (minutes) One 293 240 18 3 293 235 16 4 293 263 53 5 293 246 31 6 293 250 36

<Example 4> Permittivity evaluation

1. After mixing 100 parts by weight of the base resin, 10 parts by weight of the flame retardant and 2 parts by weight of the crosslinking agent, prepare samples 1 to 4 for dielectric constant evaluation in the form of a film, and 8 GHz for the dielectric constant evaluation samples 1 to 4 using a dielectric analyzer. The dielectric constant was measured at. As the base resin, low density polyethylene and ethylene ethyl acrylate were mixed in a weight ratio of 65:35, dicumyl peroxide was used as a crosslinking agent, and flame retardant aids 1 to 4 were used for dielectric constant evaluation samples 1 to 4, respectively.

2. Looking at the dielectric constant measurement results of the dielectric constant evaluation samples 1 to 4, it was confirmed that the dielectric constant evaluation sample 1 has a lower dielectric constant than that of the dielectric constant evaluation sample 2, and that the dielectric constant evaluation sample 2 has a lower dielectric constant than the dielectric constant evaluation samples 3 and 4. . Through this, it can be seen that it is possible to have a low dielectric constant when polyphenylene ether and/or an appropriate amount of silica is used in the flame retardant aid.

In the above, the applicant has described the preferred embodiments of the present invention, but such embodiments are only one embodiment that implements the technical idea of the present invention, and any change or modification of the present invention as long as the technical idea of the present invention is implemented. It should be construed as falling within the scope.

Claims (3)

Silica 25 to 35 parts by weight, polyphenylene ether 40 to 60 parts by weight, silicone polymer 40 to 50 parts by weight, 3-glycidoxypropyltrimethoxysilane 1 to 10 parts by weight, methyltetrahydrophthalic anhydride 1 to 10 parts Parts, 1 to 10 parts by weight of 4,4'-bis(alpha, alpha-dimethylbenzyl)diphenylamine, 1 to 10 parts by weight of pentaerythritol tetrastearate, N,N'-(1,3-phenylene)di 5 to 15 parts by weight of a silicone-based flame retardant aid prepared by reacting 5 to 15 parts by weight of maleimide and 1 to 2 parts by weight of 1,3-bis(tert-butylperoxyisopropyl)benzene, 100 parts by weight of the base resin, 20 to the flame retardant A flame-retardant resin composition comprising 50 parts by weight, 0.1 to 2 parts by weight of distearyl thi 3,3-thiodipropionate, 0.1 to 2 parts by weight of hydroxyphenylbenzotriazole, and 1 to 3 parts by weight of a crosslinking agent. delete delete