JP5243653B1 - Flame-retardant resin composition and molded body using the same - Google Patents

Abstract

To provide a flame retardant resin composition capable of achieving both excellent mechanical properties and excellent flame retardancy, and a molded body using the same.
SOLUTION: A polyolefin resin, a flame retardant containing a phosphate compound, and a fluorine-based drip inhibitor, wherein the flame retardant is blended at a ratio of 95 to 130 parts by mass with respect to 100 parts by mass of the polyolefin resin, A flame retardant resin composition in which a fluorine-based anti-drip agent is blended at a ratio of 0.2 parts by mass or more with respect to 100 parts by mass of a polyolefin resin.
[Selection figure] None

Description

  The present invention relates to a flame retardant resin composition and a molded body using the same.

  In recent years, in office automation equipment such as televisions, personal computers, and printers, building materials, automobile interior materials, electronic parts, and the like, the demand for flame retardance has become stricter from the viewpoint of fire prevention. Therefore, materials having high flame retardancy are used for these.

  As such a highly flame retardant material, a flame retardant synthetic resin composition in which a phosphate compound and an anti-drip agent are blended with a synthetic resin has been proposed (see Patent Document 1 below). Patent Document 1 discloses that 5 to 70 parts by mass of a phosphate compound and 0.05 to 5 parts by mass of an anti-drip agent are blended with respect to 100 parts by mass of a synthetic resin.

JP 2003-26935 A

  By the way, the flame retardant resin composition is required to satisfy both excellent mechanical properties and excellent flame retardancy.

  However, the flame retardant synthetic resin composition described in Patent Document 1 still has room for improvement in terms of flame retardancy.

  The present invention has been made in view of the above circumstances, and provides a flame retardant resin composition capable of achieving both excellent mechanical properties and excellent flame retardancy, and a molded body using the same. The purpose is to do.

  In order to solve the above-mentioned problems, the present inventor conducted research on a resin composition containing a polyolefin resin, a flame retardant containing a phosphate compound, and a fluorine-based anti-drip agent. Here, since the resin composition described in Patent Document 1 still has room for improvement in terms of flame retardancy, it was considered to increase the blending amount of the flame retardant with respect to the polyolefin resin. However, the flame retardancy could still not be improved by adding a slightly larger amount of the phosphate compound than 70 parts by mass with respect to 100 parts by mass of the synthetic resin. However, the present inventor can solve the above problems with a flame retardant resin composition in which the blending amount of the phosphate compound with respect to 100 parts by mass of the synthetic resin is a specific range in a range larger than 70 parts by mass. As a result, the present invention has been completed.

That is, the present invention includes a polyolefin resin, a flame retardant containing a phosphate compound, and a fluorine-based drip inhibitor, and the flame retardant is in a ratio of 95 to 130 parts by mass with respect to 100 parts by mass of the polyolefin resin. And the fluorine-based anti-drip agent is blended in a proportion of 0.2 parts by mass or more with respect to 100 parts by mass of the polyolefin resin, the polyolefin resin contains a polypropylene resin, and the crystallinity of the polyolefin resin is 20 Ru 50% der a flame retardant resin composition.

  According to the flame-retardant resin composition of the present invention, it is possible to achieve both excellent mechanical properties and excellent flame retardancy.

  When the polyolefin resin contains a polypropylene resin, if the crystallinity of the polyolefin resin is within the above range, the mechanical properties of the flame retardant resin composition are superior to those when the crystallinity is outside the above range. Characteristics are obtained. Specifically, when the crystallinity of the polyolefin resin is within the above range, superior tensile strength can be obtained as compared with the case where the crystallinity is less than the lower limit of the above range. Further, when the crystallinity of the polyolefin resin is within the above range, more excellent tensile elongation can be obtained as compared with the case where the crystallinity exceeds the upper limit of the above range. The inventor presumes the reason why such an effect is obtained as follows. That is, first, the crystallinity of the polyolefin resin being 20 to 50% as described above means that the polyolefin resin has a crystal part and an amorphous part. And since a flame retardant tends to exist in the vicinity of an amorphous part, when the degree of crystallinity is 50% or less, the ratio of an amorphous part becomes large and a flame retardant becomes difficult to float in polyolefin resin. Therefore, it is considered that the flame retardant resin composition is less likely to break during tension, and the tensile elongation is increased. On the other hand, when the degree of crystallinity is 20% or more, there are relatively many crystal parts that determine the strength during the tensile test, and as a result, the tensile strength is considered to increase.

The present invention also includes a polyolefin resin, a flame retardant containing a phosphate compound, and a fluorine-based drip inhibitor, and the flame retardant is in a ratio of 95 to 130 parts by mass with respect to 100 parts by mass of the polyolefin resin. And the fluorine anti-drip agent is blended in a proportion of 0.2 parts by mass or more with respect to 100 parts by mass of the polyolefin resin , the polyolefin resin contains a polyethylene resin, and the crystallinity of the polyolefin resin is 25. ~ 45% .

  When the polyolefin resin contains a polyethylene resin, if the crystallinity of the polyolefin resin is within the above range, the mechanical properties of the flame retardant resin composition are superior to those of the case where the crystallinity is outside the above range. Characteristics are obtained. Specifically, when the crystallinity of the polyolefin resin is within the above range, superior tensile strength can be obtained as compared with the case where the crystallinity is less than the lower limit of the above range. Further, when the crystallinity of the polyolefin resin is within the above range, more excellent tensile elongation can be obtained as compared with the case where the crystallinity exceeds the upper limit of the above range. In addition, this inventor estimates that the reason such an effect is acquired is the same as the case where polyolefin resin contains a polypropylene resin.

（上記一般式（１）中、ｍは１〜１００の整数を表す。） In the flame retardant resin composition, the phosphate compound reacts phosphoric acid represented by the following general formula (1) with an amine compound having at least one amino group in the molecule. It is preferable to contain the salt obtained by this.

(In the general formula (1), m represents an integer of 1 to 100.)

  In this case, more excellent mechanical properties and flame retardancy can be obtained.

  In the flame retardant resin composition, the amine compound is preferably composed of a mixture of a diamine containing a piperazine ring and an amine compound containing a triazine ring.

  In this case, compared with the case where an amine compound is comprised with mixtures other than the said mixture, the flame retardance of a flame-retardant resin composition improves.

  In the flame retardant resin composition, it is preferable that the flame retardant further contains pentaerythritol.

  In this case, compared with the case where a flame retardant does not contain a pentaerythritol, the flame retardance of a flame retardant resin composition improves more.

  Moreover, this invention is a molded object containing the flame-retardant resin composition mentioned above.

In the present invention, “crystallinity” means the following formula:
Xc = Hm / H _m0
(In the above formula, Xc represents the degree of crystallization, Hm represents the heat of fusion, and H _m0 represents the heat of crystallization of 100%.)
Is defined by Here, Hm is a melting heat peak observed when the above-described polyolefin resin is once melted with DSC (DSC320 manufactured by SII), cooled at 10 ° C./min, and then heated at 10 ° C./min. The heat of fusion of As H _m0 , a value of 209 J / g is used when the polyolefin resin contains a polypropylene resin as a main component, and a value of 277 J / g is used when the polyolefin resin contains a polyethylene resin as a main component. Here, the “main component” refers to a component contained in the polyolefin resin at a ratio of 50% by mass or more.

  ADVANTAGE OF THE INVENTION According to this invention, the flame retardant resin composition which can make the outstanding mechanical characteristic and the outstanding flame retardance compatible, and a molded object using the same are provided.

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

  The flame retardant resin composition of the present invention contains a polyolefin resin, a flame retardant containing a phosphate compound, and a fluorine-based drip inhibitor. And a flame retardant is mix | blended in the ratio of 95-130 mass parts with respect to 100 mass parts of polyolefin resin, and a fluorine-type anti-drip agent is 0.2 mass of fluoro-drip inhibitors with respect to 100 mass parts of polyolefin resins. It is blended at a ratio of at least parts.

  According to this flame retardant resin composition, it is possible to achieve both excellent mechanical properties and excellent flame retardancy.

  Hereinafter, each of the above-described polyolefin resin, flame retardant, and fluorine-based drip inhibitor will be described in detail.

(Polyolefin resin)
The polyolefin resin is not particularly limited. Examples of the polyolefin resin include polyethylene, polypropylene, polybutene, ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), and ethylene-propylene copolymer. Examples include coalescence. These can be used alone or in combination of two or more.

  When the polyolefin resin contains a polypropylene resin, the crystallinity of the polyolefin resin is preferably 20 to 50%.

  When the polyolefin resin contains a polypropylene resin, if the crystallinity of the polyolefin resin is within the above range, the mechanical properties of the flame retardant resin composition are superior to those when the crystallinity is outside the above range. Characteristics are obtained. Specifically, when the crystallinity of the polyolefin resin is within the above range, superior tensile strength can be obtained as compared with the case where the crystallinity is less than the lower limit of the above range. Further, when the crystallinity of the polyolefin resin is within the above range, more excellent tensile elongation can be obtained as compared with the case where the crystallinity exceeds the upper limit of the above range.

  The degree of crystallinity of the polyolefin resin including the polypropylene resin is more preferably 25 to 45%.

  In addition to the polypropylene resin, the polyolefin resin may include a resin having a crystallinity lower than that of the polypropylene resin. In this case, the tensile elongation of the flame retardant resin composition is further improved as compared with the case where the polyolefin resin is composed only of the polypropylene resin. Examples of the resin having a crystallinity lower than that of the polypropylene resin include a modified polypropylene resin.

  When the polyolefin resin contains a polyethylene resin, the crystallinity of the polyolefin resin is preferably 25 to 45%.

  When the crystallinity of the polyolefin resin is within the above range, more excellent mechanical properties can be obtained in the flame retardant resin composition than when the crystallinity is outside the above range. Specifically, when the crystallinity of the polyolefin resin is within the above range, superior tensile strength can be obtained as compared with the case where the crystallinity is less than the lower limit of the above range. Further, when the crystallinity of the polyolefin resin is within the above range, more excellent tensile elongation can be obtained as compared with the case where the crystallinity exceeds the upper limit of the above range.

  The crystallinity of the polyolefin resin including the polyethylene resin is more preferably 30 to 45%.

  The polyolefin resin may include a resin having a crystallinity lower than that of the polyethylene resin, in addition to the polyethylene resin. In this case, the tensile elongation of the flame retardant resin composition is further improved as compared with the case where the polyolefin resin is composed only of the polyethylene resin. Examples of the resin having a crystallinity lower than that of the polyethylene resin include EVA.

(Flame retardants)
A flame retardant should just contain a phosphate compound. Therefore, a flame retardant may be comprised only with a phosphate compound, and may be comprised with the mixture of a phosphate compound and flame retardants other than a phosphate compound.

Here, the phosphate compound is preferably a salt obtained by reacting phosphoric acid represented by the following general formula (1) with an amine compound having at least one amino group in the molecule.

  In the general formula (1), m represents an integer of 1 to 100. It is particularly preferable that m is 1 or 2. In this case, compared with the case where m is 3 or more, the flame retardance of a flame retardant resin composition improves more.

  Examples of the amine compound include an aliphatic diamine, an amine compound containing a piperazine ring, and an amine compound containing a triazine ring. As the aliphatic diamine, those having 1 to 15 carbon atoms are preferably used. Examples of such aliphatic diamines include N, N, N ′, N′-tetramethyldiaminomethane, ethylenedidiamine, N, N′-dimethylethylenediamine, N, N′-diethylethylenediamine, and N, N-dimethyl. Ethylenediamine, N, N-diethylethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-diethylethylenediamine, 1,2-propanediamine, 1,3-propanediamine, Examples include tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane and 1,10-diaminodecane. These can be used alone or in combination of two or more.

  Examples of the amine compound containing a piperazine ring include piperazine, trans-2,5-dimethylpiperazine, 1,4-bis (2-aminoethyl) piperazine, and 1,4-bis (3-aminopropyl) piperazine. These can be used alone or in combination of two or more.

  Examples of amine compounds containing a triazine ring include melamine, acetoguanamine, benzoguanamine, acrylic guanamine, 2,4-diamino-6-nonyl-1,3,5-triazine, 2,4-diamino-6-hydroxy-1, 3,5-triazine, 2-amino-4,6-dihydroxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6 -Ethoxy-1,3,5-triazine, 2,4-diamino-6-propoxy-1,3,5-triazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2, Examples include 4-diamino-6-mercapto-1,3,5-triazine and 2-amino-4,6-dimercapto-1,3,5-triazine. These can be used alone or in combination of two or more.

  The amine compound is preferably composed of a mixture of an amine compound containing a piperazine ring and an amine compound containing a triazine ring. In this case, compared with the case where an amine compound is comprised with mixtures other than the said mixture, the flame retardance of a flame-retardant resin composition improves more. Here, the content of the amine compound including the piperazine ring in the mixture is preferably 55 to 20% by mass. In this case, compared with the case where the content rate of the amine compound containing the piperazine ring in the mixture is out of the above range, the flame retardancy of the flame retardant resin composition is further improved.

  Examples of flame retardants other than phosphate compounds include pentaerythritol. In this case, the flame retardancy of the flame retardant resin composition is further improved.

  When the flame retardant contains a phosphate compound and a flame retardant other than the phosphate compound, the content of the phosphate compound in the flame retardant is preferably 60 to 95% by mass. In this case, the flame retardancy of the flame retardant resin composition is further improved as compared with the case where the content of the phosphate compound in the flame retardant is out of the above range. The content of the phosphate compound in the flame retardant is more preferably 75 to 90% by mass.

  A flame retardant is mix | blended in the ratio of 95-130 mass parts with respect to 100 mass parts of polyolefin resin. The flame retardance of a flame retardant resin composition falls that the compounding quantity of the flame retardant with respect to 100 mass parts of polyolefin resins is less than 95 mass parts. On the other hand, when the blending amount of the flame retardant with respect to 100 parts by mass of the polyolefin resin exceeds 130 parts by mass, the mechanical properties of the flame retardant resin composition are deteriorated.

  When the polyolefin resin contains a polypropylene resin as a main component, the blending amount of the flame retardant with respect to 100 parts by mass of the polyolefin resin is preferably 95 to 120 parts by mass, and more preferably 95 to 115 parts by mass. Moreover, when polyolefin resin contains a polyethylene resin as a main component, Preferably it is 100-130 mass parts, More preferably, it is 110-115 mass parts.

(Fluorine anti-drip agent)
The fluorine anti-drip agent only needs to contain fluorine and be able to prevent dripping during combustion. Examples of such fluorine anti-drip agents include polytetrafluoroethylene, Examples thereof include fluorine resins such as polyvinylidene fluoride and polyhexafluoropropylene.

  A fluorine-type anti-drip agent is mix | blended in the ratio of 0.2 mass part or more with respect to 100 mass parts of polyolefin resin. When the blending amount of the fluorine-based anti-drip agent with respect to 100 parts by mass of the polyolefin resin is less than 0.2 parts by mass, the anti-drip effect is reduced and the flame retardancy of the flame-retardant resin composition is reduced.

  The blending amount of the fluorine-based anti-drip agent with respect to 100 parts by mass of the polyolefin resin is preferably 0.3 parts by mass or more. In this case, compared with the case where the compounding quantity of a fluorine-type drip inhibitor is less than 0.3 mass part, the flame retardance of a flame-retardant resin composition improves more. However, the blending amount of the fluorine-based anti-drip agent with respect to 100 parts by mass of the polyolefin resin is preferably less than 1.0 part by mass. In this case, the tensile elongation of the flame retardant resin composition is further improved as compared with the case where the blending amount of the fluorine-based anti-drip agent is 1.0 part by mass or more.

  The fluorine-based anti-drip agent may be blended as a fluorine-based anti-drip agent-containing mixed powder composed of a mixture with a fluorine-free organic polymer not containing fluorine. In this case, the mixed powder containing a fluorine-based anti-drip agent is easy to handle and has excellent dispersibility. The mixed powder containing the fluorine-based anti-drip agent is not particularly limited, but the mixed powder containing the fluorine-based anti-drip agent includes a polytetrafluoroethylene-containing mixed material composed of polytetrafluoroethylene particles and an organic polymer. Powder or the like is preferably used. Examples of the organic polymer include an organic polymer containing 10% by mass or more of an aromatic vinyl monomer, an organic polymer containing 10% by mass or more of an acrylate ester monomer, or cyanide. Examples thereof include an organic polymer containing 10% by mass or more of a vinyl monomer. You may use these individually or in combination of 2 or more types. The content of polytetrafluoroethylene in the polytetrafluoroethylene-containing mixed powder is preferably 0.1 to 90% by mass.

  The flame retardant resin composition may further contain an antioxidant, an ultraviolet degradation inhibitor, a processing aid, a color pigment, a lubricant, and a filler as necessary.

  The flame retardant resin composition can be obtained by kneading a polyolefin resin, a flame retardant, a fluorine-based drip inhibitor and the like. The kneading can be performed with a kneading machine such as a Banbury mixer, a tumbler, a pressure kneader, a kneading extruder, a twin screw extruder, a mixing roll, and the like.

  Moreover, this invention is a molded object containing the flame-retardant resin composition mentioned above. Since this molded body contains a flame retardant resin composition that can achieve both excellent mechanical properties and excellent flame retardancy, various properties that require both excellent mechanical properties and excellent flame retardancy are required. It is applicable to the use of. Examples of such applications include a television back panel, a capacitor case, an insulating film inside a keyboard, a panel inside a heater, a flame retardant sheet for a building, and an automobile dashboard. In addition, a molded object may further contain glass fiber etc. depending on a use.

  The molded body can be obtained by molding the flame retardant resin composition using, for example, an extrusion molding method or an injection molding method.

  Hereinafter, the content of the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples.

(Examples 1 to 13, Reference Example 1 and Comparative Examples 1 to 3)
(A) Polyolefin resin, (B) Flame retardant and (C) Fluorine-based anti-drip agent are blended in the blending amounts shown in Table 1 or Table 2, and kneaded at 160 ° C. for 15 minutes with a Banbury mixer. A resin composition was obtained. In Tables 1 and 2, the unit of the blending amount of each blending component is part by mass.

Specific examples of the (A) polyolefin resin, (B) flame retardant, and (C) fluorine drip inhibitor were as follows.
(A) Polyolefin resin (A1) Homopolypropylene resin Product name: E-111G, Prime Polymer Co., Ltd. (A2) Modified polypropylene resin Product name: Tafmer PN2060, Mitsui Chemicals, Inc. (A3) Polyethylene product name: Excellen GMH CB5001, Sumitomo Chemical Co., Ltd. (A4) ethylene-vinyl acetate copolymer (EVA)
Product name: EVAFLEX EVA460R, manufactured by Mitsui DuPont Chemical Co., Ltd. (B) Flame retardant (B1) Flame retardant composed of piperazine pyrophosphate and melamine pyrophosphate Product name: FP2200, ADEKA (B2) Piperazine pyrophosphate only Product name: MELAPUR200 / 70, made by DSM (B3) Flame retardant made of piperazine pyrophosphate and pentaerythritol Product name: Nonnene R117-3, Maruhishi Oil Chemical Co., Ltd. (C) Fluorine series Anti-drip agent (C1) Polytetrafluoroethylene-containing mixed powder comprising polytetrafluoroethylene particles and an organic polymer (polytetrafluoroethylene content 20% by mass)
Product name: A3000, Mitsubishi Rayon (C2) PTFE
Product name: Polyflon FA500A, manufactured by Daikin

  Next, this flame retardant resin composition was kneaded at 160 ° C. for 15 minutes by a Banbury mixer. Thereafter, the flame retardant resin composition was put into a single screw extruder (L / D = 20, screw shape: full flight screw, manufactured by Mars Seiki Co., Ltd.), and a sheet having a thickness of 0.3 mm was formed from the extruder. Extruded.

The sheets of Examples 1 to 13, Reference Example 1 and Comparative Examples 1 to 3 obtained as described above were evaluated for flame retardancy and mechanical properties as follows.

<Flame retardance>
UL94 test was done about the sheet | seat of Examples 1-13 , Reference Example 1, and Comparative Examples 1-3. The results are shown in Tables 1 and 2. In addition, about the sheet | seat whose flame retardance is V-0, it was set as the pass, and it was set as rejection about the sheet | seat whose flame retardance is V-1 or V-2.
60 seconds or less: Pass over 60 seconds: Fail

<Mechanical properties>
Mechanical properties were indexed by tensile strength and tensile elongation. The tensile strength and tensile elongation were measured by tensile tests based on JIS C3005 for the sheets of Examples 1 to 13, Reference Example 1 and Comparative Examples 1 to 3. The results are shown in Tables 1 and 2. In Tables 1 and 2, the unit of tensile strength is MPa. The pass / fail criteria for mechanical properties were as follows. In the tensile test, the tensile speed was 200 mm / min, and the distance between the marked lines was 20 mm.

From the results shown in Table 1 and Table 2, the sheets of Examples 1 to 13 and Reference Example 1 reached the acceptance criteria for flame retardancy and mechanical properties. In contrast, the sheets of Comparative Examples 1 to 3 did not reach the acceptance criteria for any one of flame retardancy and mechanical properties.

  From the above, according to the flame-retardant resin composition of the present invention, it was confirmed that both excellent mechanical properties and excellent flame retardancy can be achieved.

Claims (6)

A polyolefin resin;
A flame retardant containing a phosphate compound;
A fluorine-based anti-drip agent,
The flame retardant is blended at a ratio of 95 to 130 parts by mass with respect to 100 parts by mass of the polyolefin resin.
The fluorine-based anti-drip agent is blended at a ratio of 0.2 parts by mass or more with respect to 100 parts by mass of the polyolefin resin ,
The polyolefin resin includes a polypropylene resin;
Crystallinity of 20-50% der Ru flame retardant resin composition of the polyolefin resin. A polyolefin resin;
A flame retardant containing a phosphate compound;
A fluorine-based anti-drip agent,
The flame retardant is blended at a ratio of 95 to 130 parts by mass with respect to 100 parts by mass of the polyolefin resin.
The fluorine-based anti-drip agent is blended at a ratio of 0.2 parts by mass or more with respect to 100 parts by mass of the polyolefin resin,
The polyolefin resin includes a polyethylene resin;
A flame retardant resin composition , wherein the polyolefin resin has a crystallinity of 25 to 45%. Wherein the phosphate compound comprises a phosphoric acid represented by the following general formula (1), a salt obtained by reacting an amine compound having at least one amino group in the molecule, according to claim 1 or 2 the flame retardant resin composition according to.

(In the general formula (1), m represents an integer of 1 to 100.) The flame retardant resin composition according to claim 3 , wherein the amine compound is composed of a mixture of an amine compound containing a piperazine ring and an amine compound containing a triazine ring. The flame retardant resin composition according to any one of claims 1 to 4 , wherein the flame retardant further comprises pentaerythritol. The molded object containing the flame-retardant resin composition as described in any one of Claims 1-5 .