JPWO2018163341A1 - Elastomer flame retardant and thermoplastic resin composition containing the flame retardant - Google Patents

Abstract

It is an elastomer flame retardant which has flame retardancy and is capable of further improving the degree of impact, and the elastomer flame retardant is represented by the following formula A-1 or formula A-2, A flame retardant composition in which at least one of the compounds 1 and A-2 (compound (A)) and a phosphate ester flame retardant (compound (B)) are melt mixed, and the flame retardant composition Is a molded article cut from a pellet or sheet containing at least the core layer (C) and the surface layer (D), and the core layer (C) is a weight ratio (A) of the compound (A) to the compound (B) ) / (B) is 15/75 to 40/60, and the skin layer (D) is a thermoplastic resin or a weight ratio (A) / (B) of compound (A) to compound (B) of 95 / 5 to 50/50, wherein the molded body is mixed with a thermoplastic resin.

Description

  The present invention relates to an elastomeric flame retardant capable of simultaneously solving impact modification and flame retardancy of a thermoplastic resin, and a thermoplastic resin composition containing the flame retardant.

The prior art system is to improve the impact strength. In many cases, development of materials and products has been made to ensure the flame retardancy of the composition by improving impact strength by blending elastomers and blending flame retardants.
However, many of the elastomers are styrene-butadiene-styrene copolymers and their hydrogenated products, ethylene-α-olefin elastomer acid anhydride modified, olefin-based terpolymer elastomer acid anhydride modified, and ethylene-α-olefin copolymer epoxy Group-introduced modified products, core-shell elastomers, etc., and their impact strength is improved by incorporation into a thermoplastic resin.

However, the molecular structure has a low oxygen index. Therefore, although it is necessary to increase the amount of the flame retardant to secure the flame retardancy of the whole composition, the elastomer composition is limited to the compounding amount of the elastomer because the effect of the flame retardancy improvement is extremely small. There is. Furthermore, many of phosphorus-based flame retardants are known to significantly reduce the thermal deformation of the thermoplastic resin, and it is difficult to break the three-way trade-off between the thermal deformation temperature, the impact strength, and the flame retardancy. there were.
Furthermore, in CFRP impregnated with a thermosetting resin, attempts have been made to disperse and improve the elastomer and super engineering plastic in an epoxy resin, for example, in order to prevent cracks and adjust the damping rate due to cooling and heating cycles. However, it can not be solved for parts that require flame retardancy, and it is a phenolic resin CFRP.

The prior art relating to elastomeric flame retardants and the prior art relating to layering of thermoplastic resins are as follows. In addition, in patent document 1, this inventor discovered the material, in order to ensure a flame retardance.
There is no relevant literature or patent literature on elastomeric flame retardants. Although a technology for applying a flame retardant to an elastomer compounded composite resin is widely applied, there is no prior art in which the elastomer itself acts as a flame retardant.
For two-layer extrusion, there are known techniques such as core-sheath fibers and two-layer pipe extrusion. These applications include the production of two-layer pellets, which specify the material as a differentiation from the known art and are filed for a die structure.

  The following documents are available for two-layer pellet production. Two-layered olefin resin pellet and method for producing the same (patent document 2), multilayer pellet combining an EVOH specific material and a resin molded product (patent document 3), resin pellet (patent document 4), die apparatus and the same Method for producing multilayer extrusion molded article (patent document 5), extrusion apparatus for multilayer extrusion molded article and method for producing multilayer extrusion molded article using the same (patent document 6), two-layer olefin for insect control resin composition There are a system resin pellet (patent literature 7), a multilayer pellet and its manufacturing method (patent literature 8), a manufacturing method and an apparatus of a multilayer pellet (patent literature 9), etc. In Patent Document 9, a core material and a sheath material are supplied to a die apparatus in which a plurality of extrusion molding parts are arranged along the circumference, and from the respective extrusion molding parts, the sheath material is concentrically arranged around the core material. It is coated and multi-layered strand.

Patent No. 5913756 JP, 2015-105369, A JP, 2009-242591, A (patent 5373306) JP 2008-255277 A Unexamined-Japanese-Patent No. 2006-272629 (patent 4642520) Unexamined-Japanese-Patent No. 2006-272628 (patent 4571531) JP 2005-139329 A (Patent No. 4649104) Japanese Patent Laid-Open No. 2003-048991 JP, 2001-198918, A (patent 4542252)

  The present invention provides an elastomeric flame retardant having flame retardancy and capable of further improving the degree of impact, and a thermoplastic resin composition containing the flame retardant.

  The molten mixture of the compound (A) of the present invention and the compound (B) has an elastomeric property when the compound (A) / compound (B) ratio is rich in the compound (B). For example, the proportion of the compound (B) in the compound (A) and the compound (B) is 60 to 80%, and even at 40%, the impact improving effect is confirmed in the glass fiber composite material system as a result of its elastomericity It is done. On the other hand, when the elastomeric property is higher than 60%, the melt-kneaded melt strand is highly adhesive to the strand cooled by the water bath. For this reason, it was necessary to mix | blend calcium carbonate, aerosil, calcium carbonate etc. to the pellet surface, or to mix | blend anti-blocking agents, such as a silicone, in a cooling water tank. For silicone residue, there is a defect in the flame retardant imparting material to the electronic parts, and a large amount of aerosil mixing limits the working environment, and the mixing of calcium carbonate and talc inorganic fillers is also separated by vibration during transfer As a matter of concern, it was required to be non-tacky so as to withstand use in a wide range of temperature environments, leading to the present invention.

It is industrially practiced to coat the skin layer with a non-adhesive material and a low water absorption material for the purpose of protecting a tacky material and a hygroscopic material. There are also practical examples of pelletization.
The principle principle of whether or not the tacky elastomer flame retardant of the present invention can be made non-tacky and can be made flame-retardant can be confirmed by model experiments using existing technologies that can be put to practical use.

In the skin layer, a melt-kneaded product of a non-adhesive composition of compound (A) / compound (B), in the core layer a kneaded product of compound (B) component at a high concentration ratio, skin layer / core layer / skin layer and 3 Stack. As a result, it was confirmed that there is no tackiness and handling is easy, and that impact strength and flame retardancy are imparted.
This indicates that, in practical use, two kneaders are used, and the strand obtained by extruding the molten resin from both kneaders from the multilayer die is improved in the adhesiveness after the cooling cut. The multilayer die may be double cylindrical or sheet shaped. In the case of a sheet, melt-cut sealing facilitates compounding to the next resin. Multi-layer sheet forming and multi-layer film forming devices operate in their respective industries and are large in terms of creating new businesses for the respective industries. In addition, as a matter of course, by forming a thermoplastic resin excellent in mechanical and heat resistance in the surface layer in-line multi-layered without melt-cut sealing, an extruded product excellent in flame resistance and impact strength can be obtained. .

  The final composition (B) concentration is determined by the layer composition ratio and the component concentration of each compound (B) for the layer configuration and layer ratio in the multilayer. If the material of the skin layer is well dispersed in the thermoplastic resin to be finally blended, the skin layer can be applied as a thermoplastic resin alone.

The elastomer flame retardant according to one embodiment of the present invention is
A flame retardant composition in which at least one of compounds of formula A-1 and formula A-2 (compound (A)) and a phosphate ester flame retardant (compound (B)) are melt mixed, The flame retardant composition is a molded body cut from a pellet or sheet containing at least a core layer (C) and a surface layer (D), and the core layer (C) is a compound (A) and the compound (B) The weight ratio (A) / (B) is 15/75 to 40/60, and the skin layer (D) is a thermoplastic resin, or a weight ratio of the compound (A) to the compound (B) (A) / (B) is 95 / 5-50 / 50, and the said molded object is mixed with the thermoplastic resin.

  In the elastomeric flame retardant, the weight ratio (C) / (D) of the core layer (C) to the skin layer (D) may be 90/10 to 50/50.

  In the elastomer flame retardant, the thermoplastic resin of the skin layer (D) is polycarbonate, polybutylene terephthalate, polyethylene terephthalate, polylactic acid, polyethylene naphthalate, polyarylate, styrene resin, polyphenylene ether, polyolefin, polyamide resin It may be a thermoplastic epoxy resin, and a polymer alloy containing at least one selected from these.

  The thermoplastic resin composition according to an embodiment of the present invention may contain the above-mentioned elastomer flame retardant.

  INDUSTRIAL APPLICABILITY The present invention can provide an elastomeric flame retardant having flame retardancy and capable of further improving the degree of impact, and a thermoplastic resin composition containing the flame retardant.

The schematic diagram which shows the molded object which comprises the elastomer flame retardant which concerns on one Embodiment of this invention. The schematic diagram which shows the other molded object which comprises the elastomer flame retardant which concerns on one Embodiment of this invention. Schematic which shows the formation process of the molded object which comprises the elastomer flame retardant which concerns on one Embodiment of this invention. The figure which shows the detail of the experimental apparatus based on the Example of this invention. The figure which shows the content of the material used for the experiment in the Example and comparative example of this invention.

  Hereinafter, although the embodiment of the present invention will be described with examples, the flame retardant of the present invention and the thermoplastic resin composition containing the flame retardant are limited to the following embodiments or examples only. Of course, various modifications can be made without departing from the scope of the present invention.

  FIG. 1 shows a schematic view of a molded body constituting an elastomer flame retardant according to an embodiment of the present invention. FIG. 2 shows a schematic view of another molded body constituting the elastomer flame retardant according to one embodiment of the present invention. FIG. 3: shows the formation process of the molded object which comprises the elastomer flame retardant which concerns on one Embodiment of this invention.

  The flame retardant composition which comprises the elastomer flame retardant of this invention has a compound (C) by which the compound (A) and the compound (B) were melt-mixed. This flame retardant composition is a molded body cut from pellets or sheets containing at least a core layer (C) and a skin layer (D). And this molded object is mixed with a thermoplastic resin, and the elastomer flame retardant of this invention is formed. The details of the compounds (A), (B) and (C) will be described later.

  As shown in FIG. 1, a molded body 10 constituting the elastomer flame retardant of the present invention includes a core layer 11 and a skin layer 12 covering the entire core layer 11. Moreover, as shown to Fig.2 (a), the molded object 10 may contain the core layer 11, the outer skin layer 12, and the intermediate | middle layer 20 provided between the core layer 11 and the outer skin layer 12 . In this case, the intermediate layer 20 may be a multilayer, and may be constituted of, for example, the core layer 21 and the skin layer 22 (see FIG. 2B).

In the above, it is desirable that the core layer (C) 11, 21 contains more compound (B) than compound (A), for example, the weight ratio of compound (A) to compound (B) (A) / It is desirable that (B) be 15/75 to 40/60.
On the other hand, in the epidermal layers (D) 12 and 22, it is desirable that the compound (A) is the same as the compound (B) or more than the compound (B). For example, the compound (A) and the compound (B) The weight ratio of (A) / (B) is preferably 95/5 to 50/50. Alternatively, the skin layers (D) 12 and 22 may be a thermoplastic resin.

  The weight ratio (C) / (D) of the core layers (C) 11, 21 and the skin layers (D) 12, 22 is preferably 90/10 to 50/50. The weight ratio (C) / (D) is more preferably 60/40, 70/30. If the core layer (C) is less than 10% by weight, the cut section from the sheet becomes thin, and the cut pieces become easy to fuse together. On the other hand, when the core layer (C) exceeds 50 weight ratio, the performance as an impact strength improver is lowered.

  Further, as shown in FIG. 2B, when the molded body 10 has the intermediate layer 20, the core layer 11 is the same as the core layer 21, or more preferably, the compound B is higher than the core layer 21. Concentration is preferred. The skin layer 12 is the same as the skin layer 22, or more preferably, a higher concentration of Compound A relative to the skin layer 22 is desirable.

  The flame retardant composition which comprises the elastomer flame retardant of this invention is a molded object cut | judged from a pellet or a sheet, for example. For example, as shown in FIG. 3 (c), the sheet 1 including the core layer 11 and the skin layer 12 shown in FIG. 3 (a) is cut and divided as shown in FIG. 3 (b). A divided body 10 is formed.

  In addition, the thermoplastic resin composition of this invention may be comprised including the elastomer flame retardant of this invention mentioned above.

<Compound (A)>
The compound (A) consists of at least one of Formula A-1 and Formula A-2. That is, the compound (A) is any of a compound consisting of formula A-1, a compound consisting of formula A-2, and a compound containing formula A-1 and formula A-2.

For example, compound (A) is shown as Table 1 below.

<Compound (B)>
The compound (B) is a phosphoric acid ester compound.
The phosphoric acid ester is not particularly limited, but it is preferable to use a monophosphoric acid ester, a condensed phosphoric acid ester or the like.

  The monophosphate ester is not particularly limited, and, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, Tris (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthylphosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate Phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresyl phosphine oxide, diphenyl methanephosphonate, phenylphosphonic acid Examples include diethyl, resorcinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), phosphaphenanthrene, tris (β-chloropropyl) phosphate and the like.

  The condensed phosphoric acid ester is not particularly limited. For example, trialkyl polyphosphate, resorcinol polyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., trade name PX-) 200), hydroquinone poly (2,6-xylyl) phosphate and condensed phosphoric acid esters such as condensates thereof. Resorcinol polyphenyl phosphate (trade name CR-733S), bisphenol A polycresyl phosphate (trade names CR-741, FP-600, FP-700), aromatic condensed phosphate ester (trade name CR747), resorcinol polyphenyl phosphate (Adeka company make, brand name Adekastab PFR) etc. can be mentioned.

<Composition of Compound (C)>
In the case of the compound (B) which is solid at normal temperature, it is obvious that the compound (A) is solid even if it is mixed in any composition. In order to solidify the liquid compound (B), it depends on the composition with the compound (A) and the viscosity of the compound (A). If the compound (B) is less than 5%, it does not depend on molecular weight, and although it solidifies by mixing with many compounds (A), it is a flame retardant that has both advantages in combination with compound (A) It can not be said that it is a combination. On the other hand, even if the composition containing the liquid compound (B) exceeds 80%, it solidifies, but it has surface tackiness under storage at high temperature for a long time and under the environment of the production site, and a plurality of It will be in a cohesive form. At this time, if mechanical shearing is applied, aggregates are often separated, but there is also an increase in the number of working steps, which is not preferable.
The experiment was carefully conducted to determine the range in which the liquid compound (B) could be solidified relative to the compound (A). It is the result of experiment when the phosphorus concentration of the experimental sample is in the range of 3 to 20%, and it is presumed that the probability is established between the samples having the concentration outside the range, but the experimental result has an extremely simple relationship I found that. It has a very strong correlation with the melt viscosity of the compound (A), and high molecular weight = achieving solidification including proportion of compound (A) with melt viscosity to compound (B) up to 30/70% by weight I understand.

Compound (B) composition% ≦ 14.7 ln (η) − 85 (Formula 1)
Here, η is a viscosity (cps) measured with a Brookfield B-type viscometer (270 ° C.) of a mixture consisting of Formula A-1, Formula A-2, or Formula A-1 and A-2. It is.
In general, liquid condensed phosphoric ester can be included up to about 20% by weight in a composition melt-kneaded with solid polycarbonate resin, but it is observed that when it exceeds 20% by weight, it bleeds out on the product surface Be done. From this, it was impossible to even predict that the compound (B) was mixed with the compound (A) to a considerably high concentration and solidified. Thus, solidification of the liquid compound (B) is extremely significant industrially.

<Thermoplastic resin>
The thermoplastic resin to which the present invention is applied is suitable for an engineering resin, and is, for example, the following resin. However, it is not limited to the resin illustrated below.

(A) Polycarbonate-Based Resin For example, polycarbonate-based resins are aromatic polycarbonates, aliphatic polycarbonates, and aromatic-aliphatic polycarbonates. The aromatic polycarbonate is obtained by reacting an aromatic hydroxy compound or this with a small amount of a polyhydroxy compound with phosgene or a diester of carbonic acid, but also includes one in which the aromatic hydroxy compound is converted to plant-derived isosorbide. It is also possible to use polymers or oligomers containing both terminal phenolic OH groups having siloxane structures for branching agent introduction and flame retardant assist, respectively.
(B) Polyester-based resin For example, polyester-based resin includes polyethylene phthalate, polybutylene terephthalate, polylactic acid, polyethylene naphthalate, LCP, terephthalic acid and / or isophthalic acid, ethylene glycol and / or cyclohexane dimethanol (CHDM), And / or 2, 2-4, 4- tetramethyl 1, 3 cyclobutanediol (TMCD) copolymer (e.g., PETG, PCTG, PCTA, TRITAN, etc., sold by Eastman Chemical).
(C) Polyamide-based resin For example, polyamide-based resin includes polyamide 6, polyamide 6-6, copolyamide 6 / 6-6, polyamide 11, polyamide 12, polyamide 4, polyamide 4-6, polyamide 6-10, and It is an amorphous polyamide.
(D) Polyacrylate resin, polyacrylonitrile resin (e) Polystyrene resin For example, polystyrene resin is high impact polystyrene, syndiotactic polystyrene, polyacrylonitrile butadiene copolymer.
(F) Polyphenylene ether-based resin (g) Polyphenylene sulfide-based resin (h) Polyarylate (i) Urethane-based For example, a urethane-based resin is a thermoplastic polyurethane or a thermoplastic polyurethane elastomer.
(J) Polysulfone (k) Polyether ether ketone (l) Thermoplastic epoxy resin

  In addition, as a thermoplastic resin, the single type | system | group which consists of any one of said (a)-(k), the blend of 2 or more components, and the polymer alloy of 2 or more components are applied. Examples of the polymer alloy include polycarbonate / polyacrylonitrile butadiene / styrene copolymer alloy, polycarbonate / polyethylene terephthalate, polycarbonate / polybutylene terephthalate, polyphenylene ether / high impact polystyrene, polyphenylene ether / polyamide, polyphenylene ether / polypropylene and the like.

Although it is difficult to apply the invention to polyolefin resins alone, blending or alloying is often performed to improve the above-mentioned engineering plastics such as chemical resistance, moldability, appearance, impact strength, flexibility and the like. In this case, the present invention can be used as long as the polyolefin does not exceed 50% by weight relative to the engineering plastics.
As such polyolefins, polyethylene, polypropylene, poly (4-methylpentene) -1, ethylene-alpha olefin copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-based ionomer resin, ethylene- There are propylene copolymer elastomer, ethylene-butene copolymer elastomer, ethylene-hexene copolymer elastomer, ethylene-octene copolymer elastomer, ethylene-propylene-ethylidene norbornene copolymer etc. Also applicable are ABA type elastomers.

As the elastomer, ethylene-propylene-butadiene copolymer, ethylene-propylene-isoprene copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-butadiene-styrene block copolymer And coalesced hydrides, styrene-isoprene-styrene block copolymer hydrides.
Examples of core-shell elastomers include methacrylic acid ester-butadiene-styrene core-shell graft copolymer, methacrylic acid ester-acrylonitrile-styrene-based core-shell graft copolymer, and acrylic acid ester-silicon-styrene-based core-shell graft copolymer. Polymer acrylic acid ester-based core / shell graft copolymers and the like can be mentioned.

  However, when using a thermoplastic resin as a skin layer (D), if the ratio of D layer is 20% or less of the whole, an olefin resin can be utilized independently.

In the thermoplastic resin composition of the present invention, various components known in the prior art, for example, inorganic fillers and others, may be added at the time of mixing or kneading of the raw materials or molding, as desired. Organic fillers, plasticizers, heat stabilizers, UV absorbers, antioxidants, light stabilizers, antistatic agents, conductive carbon, lubricants, nucleating agents, foaming agents, crosslinking agents, radical generators, release agents , Surfactants, antibacterial and antifungal agents, dyes, pigments and the like may be blended.
As a flame retardant aid, montmorillonite, layered inorganic compounds such as clay, carbon nanotubes and the like are preferable.

<Production of composition>
In the method of simultaneously obtaining the flame retardant A, the thermoplastic resin, and the flame retardant B as melt-kneading, various kneaders, such as uniaxial and multi-axial kneaders, Banbury mixer, in the production with a common thermoplastic resin composition After melt-kneading the above components with a roll, Brabender plastogram, etc., a method of cooling and solidifying is applied, but it is not limited.
However, it is even more advantageous in continuous kneaders, such as twin screw extruders. In extruders such as twin-screw extruders, various elements such as screws, kneading discs, rotors, lengths and shapes of cylinders, and positions and numbers of raw material supply ports can be freely rearranged. Depending on the grade of the flame retardant A and the type of the flame retardant B (phosphate ester), they can be appropriately recombined and used. For example, using a twin-screw extruder, set the raw material supply ports at two locations: the first upper cylinder (No. 1 supply) and the upper second cylinder (No. 2 supply) between the first cylinder and the die head. No. 1 supply port and No. 2 supply port (upstream portion), and between the No. 2 supply port and die head (downstream portion), a kneading disc is appropriately disposed and brought to a predetermined temperature. (1) A method of supplying the thermoplastic resin and the flame retardant A from the supply port and supplying the compound B (phosphate ester flame retardant) from the No. 2 and No. 3 supply ports can be mentioned. However, when the compound (B) is a liquid flame retardant, a liquid supply device is required.

There are the following two methods for producing the flame retardants of the compound A and the compound B, but there is no particular limitation as long as the device is capable of mixing the compound B above the melting point of the compound A.
For example, generally, it is possible if it is a tank with a heating jacket and a stirrer. Industrially, this can be industrially incorporated into a liquid flame retardant manufacturing process, and a flame retardant composition (compound C) which is solid at room temperature can be easily obtained by taking-out cooling.
It is possible to utilize a kneader by utilizing the fact that the compound A has a high molecular weight, but in this case also a twin-screw kneader extruder is useful. That is, after the compound A is supplied from the No. 1 supply port and melt-plasticized, the liquid compound B is supplied from the No. 2 supply port, the mixture is kneaded, the strand is extruded from the die, water cooled, air cooled and desired with the strand cutter. It is possible to obtain pellets cut to the size of.
When the obtained flame retardant pellet is further mixed with a thermoplastic resin, it is preferable to obtain the composition by the same melt-kneading extruder, but it may be mixed with the raw material directly during molding.

  The method for molding the thermoplastic resin composition of the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, that is, injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum molding, From various molding methods such as plug-assisted pressure forming, film forming, sheet forming, rotational forming, laminate forming, foam forming, etc., it is appropriately selected according to the formulation of the thermoplastic resin composition, the use of the packaging container, etc. be able to.

  In addition, although the elastomer flame retardant of this invention mixes and forms the molded object comprised by a flame retardant composition with a thermoplastic resin, it is not limited to this. For example, instead of the thermoplastic resin, the molded body may be mixed with the thermosetting resin. In this case, the stress at the time of curing can be relaxed, and as a result, the impact strength can be improved.

[Example]
Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these examples.
FIG. 4 shows the experimental apparatus used in the example of the present invention. FIG. 5 shows the contents of the materials used in the experiments regarding the examples and comparative examples of the present invention.

<Example of production of flame retardant alloy and comparative example>
Example 1
The first step is the formation of the skin layer.
First, 80 parts of FRX-Polymer's Nokia-100L from the first feed section of Japan Steel Works Co., Ltd.'s 2-shaft kneader TEX30α and 20 parts of the second feed from the second feed of ADEKA's flame retardant FP600 Be done. Then, screw rotation is set at 230 rpm, cylinder temperature is set to 230 ° C. under the first feed, and 190 ° C. under the second feed, compounded under the setting extrusion conditions of 5 kg / hr., Cooled by a water tank, and cut with a pelletizer Pellets are made.
Next, the pellet is heated and pressed once. This creates a sheet. The heating conditions are a temperature of 210 ° C. and a pressure of 3 MPa. The sheet size is 200 mm in width, 200 mm in length, and 0.25 mm in thickness.

The second step is multilayering of the compound of the core layer and the sheet obtained in the first step.
The compound composition of the core layer changes the ratio of the material system at the time of using the first step, and makes 30 parts of Sofia-100L and 70 parts of FP600, the temperature under the first feed is 220 ° C., the temperature under the second feed The extrusion was performed under the same conditions as others, except that the temperature was 190 ° C. However, the die is loaded with a hanger coat die having a width of 150 mm and a die gap of 2 mm at the tip of the kneader. The film used in the first step is placed on a metal press sheet, and a 2 mm-thick sheet of T-die molten material corresponding to the core layer to be discharged is laminated in accordance with the outflow. Next, the same kind of film is laminated from the top, and the skin layer / core layer / skin layer three-layer sheet is obtained by cooling while being weakly pressed with a pressure of 1 MPa in a cooling press. After cooling, the sheet is cut into about 5 to 7 mm with scissors.
There is no surging in the extrusion of the skin layer and in the extrusion of the core layer, which is a stable compound. The three-layer sheet had no stickiness, and no trouble due to stickiness was observed even when it was cut with scissors.

Dry-blend 16 parts of the cut three-layer pellet and 39 parts of Mitsubishi Engineering Plastics Co., Ltd. sales polycarbonate (Iupilon S2000), carry out glass fiber and compound with TEX30α (condition II) made by Nippon Steel Works, and make the pellet obtain. 45 parts of glass fibers having a cylinder temperature of 260 ° C. are fed from the middle of the kneader cylinder (Nitto Boseki glass fiber (CF 3 PE 937)).
Next, the pellet obtained is subjected to hot pressing with a Toyo Test Instruments Co., Ltd. Mini Test Press-10 to produce a UL evaluation test piece and a Charpy impact test piece. As a result, the UL94 flame retardant V0 V notched Charpy impact strength has a very high physical property of 16 kJ / m ² . It was confirmed that both flame retardancy and impact strength were satisfactory.

Example 2
In the flame retardant formulation in the first step (skin layer) molding of Example-1, 60 parts of Sofia-100L and 40 parts of FP600 are used, and the other experiment is performed in the same manner as in Example-1.
By this, substantially the same good results were obtained.

[Example 3]
In Example 1, A-2 type which is a copolymer of PC with the FRX grade of the second step (core layer), wherein 90 parts of Sofia-100L of the first step (skin layer) and 10 parts of FP600 are used. The experiment was carried out in the same manner as in Example 1 except for changing to Nof-CO 60 of
As a result, it was found that the Charpy impact strength was very high at 18 J / m ^2, and the flame retardancy maintained V0.

Example 4
In Example 1, the flame retardant NOFIO-100L in the molding of the first step (skin layer) is switched to NOF-9000, and the second step is the application of NOF-CO 60 in Example 3 under the other conditions of Example A polycarbonate composition was obtained in the same manner as -1.
Also in this case, the molten composition obtained in the first step solidified easily, could form a film, and was not tacky. Furthermore, by adopting the A-2 type which is a copolymer with PC for the core layer, the elastomer property is higher, and as a result, the impact of the glass fiber reinforced polycarbonate is high, and the flame retardancy can be secured.

Example 5
A film of polycarbonate (Mitsubishi Engineering Plastics sales Iupilon S2000) containing no flame retardant in the surface layer is prepared, and the composition of Example 1 is multilayered in the core layer. However, the ratio of core layers is 0.8.
As a result, there was no tackiness of the multilayered flame retardant, and the impact of the final glass fiber reinforced polycarbonate was high, and the flame retardancy could be secured.

[Example 6]
The material in the first step is an extrusion film made of Mitsubishi Engineering Plastics Co., Ltd. product polybutylene phthalate (nearly PBT) (Novaduran 5010) alone as an extruded film, and the second step in the process is 30 parts of A-2 type Sofia-CO60. And 70 parts of FP600, and the ratio of the skin layer to the core layer is 0.9.
In Example 6, there was no tackiness of this multilayered flame retardant, and there was no problem in compounding with the PBT resin in the next step. In the glass fiber PBT compound, the number of flame retardant parts in three layers was increased to 18 parts. As a result, the impact strength in the PBT system was as high as 12 J / m ² and the flame retardancy was also confirmed as V0. It can be seen that the practical value is high when this example is compared with comparative example-4.

Comparative Example 1
In the first step, a flame retardant NOF-100L used in Example 1 is once formed into a pellet by a twin-screw kneader as in the example. Thereafter, a composition consisting of 16 parts of this sample, 37 parts of polycarbonate resin and 45 parts of glass fiber was compounded by a twin-screw kneader, and the quality after producing test pieces similar to the example was evaluated. The notched Charpy impact strength was 5.5 J / m ² , and the flame resistance was dripped and at the V2 level. This comparative example also reproduces that the flame retardancy is improved by forming the flame retardant alloy of the compound (B) component even in Japanese Patent No. 5913756. Here, v-notched impact strength is listed as a comparison target.

Comparative Example 2
In the first step, 30 parts of Sofia-100L and 70 parts of FP600 are melt-kneaded and extruded. However, it was confirmed that the melt strand had high viscosity, and pelletization after water cooling had a problem in production stability such that the work was stopped, such as being caught in a pelletizer. However, it was found that the strand itself is flexible as an elastomer, and that the strand of the single Sofia of Comparative Example 1 is characterized by being brittle. However, it did not reach v-notched Charpy impact and flame resistance evaluation

Comparative Example 3
In a twin-screw kneader, 16 parts of the flame retardant composition of only the skin layer not containing the core layer in Example 2 and 39 parts of polycarbonate resin and 45 parts of glass fibers are compounded in Example-2.
As for the flame retardancy, the reproducibility of Patent No. 5913756 is obtained at V0, and the Charpy impact strength is a relatively high value of 8.8 J / m ² , but the impact value of Example 2 is far It turned out to be high.

Comparative Example 4
The PBT 5010 used in Example 6 is compounded by blending 18 wt% of a phosphorus-based flame retardant FP600 and 45 wt% of glass fibers. At the stage of passing the extruded strand through the water bath, it was found that the flame retardant FP600 was floating on the surface of the water bath, and the obtained pellet was slightly sticky. The v-notched Charpy impact strength of this composition was 8 J / m ² . In the flame retardancy evaluation, there was a drip and it was V2.

Comparative Example 5
In Example 1, the core layer ratio is 0.95. In this case, it was found that the tackiness was strong at the time of sheet cutting and it was unsuitable for compounding with a thermoplastic resin.

Comparative Example 6
In Example 1, the core layer ratio is 0.25. In this case, there was no problem in the compound with the thermoplastic resin at the time of sheet cutting, but it was found that the impact strength is lower than that of Example 1.
Although this level is also highly rated as compared with the conventional flame retardant system, in the present invention, it was determined that the claimed core layer ratio is suitable.

<Effect>
As typical flame retardants, halogen-based flame retardants, red phosphorus, phosphine-based flame retardants, condensed phosphoric acid esters, and intumescent flame retardants are exemplified.
However, when these flame retardants are blended into a thermoplastic resin to impart flame retardancy, mechanical properties and thermal properties are reduced.
Therefore, the elastomer is compounded to recover the impact strength. However, except for fluorine-based and silicone-based elastomers, general-purpose elastomers rather reduce the flame retardant effect. In addition, silicone-based and fluorine-based elastomers sometimes have poor compatibility with resins, and the impact strength does not improve so much.
In order to solve such contradiction, a compound which is an elastomer and is also a flame retardant and which is also compatible with the thermoplastic resin is desired. However, there is no prior art document or patent for such technology.
Therefore, the inventors of the present invention have been described in Patent Document 1 in which a composition having a specific dispersion form obtained by melt-kneading compound (A) and compound (B) under specific conditions is compound (A) and compound (B) respectively. It has been found that the flame retardancy is superior to the case where the thermoplastic resin is blended alone.

  In the composition of the compound (A) and the compound (B) according to the present invention, it was found that the composition has an elastomeric property in a specific range by increasing the concentration of the compound (B). However, in this composition range, the strand after melt-kneading is sticky. Therefore, the present invention uses a non-adhesive (A) / (B) composition or a thermoplastic resin as a skin layer, and a (A) / (B) composition with particularly high elastomeric property as a core layer, and a thermoplastic resin It was found that both the impact strength and the flame retardance are satisfied by blending in

As described above, with regard to imparting flame retardancy to products that protect the safety and security of our lives from fire, on the other hand, there are demands for thin-walled, lightweight products due to environmental problems and various high strength and high heat resistant materials from high functional requirements. It is difficult to match this flame retardancy with such a demand, and there is a trade-off relationship with conventional flame retardants. Although the present invention can not be satisfied with a single flame retardant, it has been proved that the combination of the advantages and disadvantages and the opposite flame retardant gives a novel idea and solid quality to be said to be "flame retardant alloy".
On the other hand, manufacturing bases for such materials are globalizing, and plants that are compounded with resin and flame retardant are also shifting along with local production at final customers. Under such conditions, it is not possible to expect the same level as the conventional viscous liquid flame retardant handling process capability. And storage conditions and severe conditions are easily assumed. At this time, the industrial meaning that the viscous liquid flame retardant can be solidified is extremely high.

Furthermore, the greatest feature of the present invention is an elastomeric flame retardant. Conventionally, various elastomers have been used as impact strength. However, as described above, the flame retardancy was not provided in the first place, and it was necessary to additionally add a flame retardant from the outside. In such cases, the flame retardancy is insufficient, and in order to cover it, the product thickness has been increased to cope with it, but the scope of application is limited among the recent light weight and thickness reduction. ing.
In Patent Document 1 of the inventor, it has been clearly shown that excellent flame retardancy is imparted in the formation of a composite with glass fibers and the like. In the past, it was difficult to make the glass fiber composite flame-retardant because glass fibers act as a combustion gas passage during combustion, but the present invention improves the impact strength of the glass fiber composite material system and makes it difficult. The industrial meaning of imparting flammability is very large.
As mentioned above, the elastomer flame retardant of the present invention can act as an impact modifier and a flame retardant.

  The present invention relates to an elastomeric flame retardant capable of simultaneously solving impact modification and flame retardancy of a thermoplastic resin, and a thermoplastic resin composition containing the flame retardant.

The prior art system is to improve the impact strength. In many cases, development of materials and products has been made to ensure the flame retardancy of the composition by improving impact strength by blending elastomers and blending flame retardants.
However, many of the elastomers are styrene-butadiene-styrene copolymers and their hydrogenated products, ethylene-α-olefin elastomer acid anhydride modified, olefin-based terpolymer elastomer acid anhydride modified, and ethylene-α-olefin copolymer epoxy Group-introduced modified products, core-shell elastomers, etc., and their impact strength is improved by incorporation into a thermoplastic resin.

However, the molecular structure has a low oxygen index. Therefore, although it is necessary to increase the amount of the flame retardant to secure the flame retardancy of the whole composition, the elastomer composition is limited to the compounding amount of the elastomer because the effect of the flame retardancy improvement is extremely small. There is. Furthermore, many of phosphorus-based flame retardants are known to significantly reduce the thermal deformation of the thermoplastic resin, and it is difficult to break the three-way trade-off between the thermal deformation temperature, the impact strength, and the flame retardancy. there were.
Furthermore, in CFRP impregnated with a thermosetting resin, attempts have been made to disperse and improve the elastomer and super engineering plastic in an epoxy resin, for example, in order to prevent cracks and adjust the damping rate due to cooling and heating cycles. However, it can not be solved for parts that require flame retardancy, and it is a phenolic resin CFRP.

The prior art relating to elastomeric flame retardants and the prior art relating to layering of thermoplastic resins are as follows. In addition, in patent document 1, this inventor discovered the material, in order to ensure a flame retardance.
There is no relevant literature or patent literature on elastomeric flame retardants. Although a technology for applying a flame retardant to an elastomer compounded composite resin is widely applied, there is no prior art in which the elastomer itself acts as a flame retardant.
For two-layer extrusion, there are known techniques such as core-sheath fibers and two-layer pipe extrusion. These applications include the production of two-layer pellets, which specify the material as a differentiation from the known art and are filed for a die structure.

  The following documents are available for two-layer pellet production. Two-layered olefin resin pellet and method for producing the same (patent document 2), multilayer pellet combining an EVOH specific material and a resin molded product (patent document 3), resin pellet (patent document 4), die apparatus and the same Method for producing multilayer extrusion molded article (patent document 5), extrusion apparatus for multilayer extrusion molded article and method for producing multilayer extrusion molded article using the same (patent document 6), two-layer olefin for insect control resin composition There are a system resin pellet (patent literature 7), a multilayer pellet and its manufacturing method (patent literature 8), a manufacturing method and an apparatus of a multilayer pellet (patent literature 9), etc. In Patent Document 9, a core material and a sheath material are supplied to a die apparatus in which a plurality of extrusion molding parts are arranged along the circumference, and from the respective extrusion molding parts, the sheath material is concentrically arranged around the core material. It is coated and multi-layered strand.

Patent No. 5913756 JP, 2015-105369, A JP, 2009-242591, A (patent 5373306) JP 2008-255277 A Unexamined-Japanese-Patent No. 2006-272629 (patent 4642520) Unexamined-Japanese-Patent No. 2006-272628 (patent 4571531) JP 2005-139329 A (Patent No. 4649104) Japanese Patent Laid-Open No. 2003-048991 JP, 2001-198918, A (patent 4542252)

  The present invention provides an elastomeric flame retardant having flame retardancy and capable of further improving the degree of impact, and a thermoplastic resin composition containing the flame retardant.

  The molten mixture of the compound (A) of the present invention and the compound (B) has an elastomeric property when the compound (A) / compound (B) ratio is rich in the compound (B). For example, the proportion of the compound (B) in the compound (A) and the compound (B) is 60 to 80%, and even at 40%, the impact improving effect is confirmed in the glass fiber composite material system as a result of its elastomericity It is done. On the other hand, when the elastomeric property is higher than 60%, the melt-kneaded melt strand is highly adhesive to the strand cooled by the water bath. For this reason, it was necessary to mix | blend calcium carbonate, aerosil, calcium carbonate etc. to the pellet surface, or to mix | blend anti-blocking agents, such as a silicone, in a cooling water tank. For silicone residue, there is a defect in the flame retardant imparting material to the electronic parts, and a large amount of aerosil mixing limits the working environment, and the mixing of calcium carbonate and talc inorganic fillers is also separated by vibration during transfer As a matter of concern, it was required to be non-tacky so as to withstand use in a wide range of temperature environments, leading to the present invention.

It is industrially practiced to coat the skin layer with a non-adhesive material and a low water absorption material for the purpose of protecting a tacky material and a hygroscopic material. There are also practical examples of pelletization.
The principle principle of whether or not the tacky elastomer flame retardant of the present invention can be made non-tacky and can be made flame-retardant can be confirmed by model experiments using existing technologies that can be put to practical use.

In the skin layer, a melt-kneaded product of a non-adhesive composition of compound (A) / compound (B), in the core layer a kneaded product of compound (B) component at a high concentration ratio, skin layer / core layer / skin layer and 3 Stack. As a result, it was confirmed that there is no tackiness and handling is easy, and that impact strength and flame retardancy are imparted.
This indicates that, in practical use, two kneaders are used, and the strand obtained by extruding the molten resin from both kneaders from the multilayer die is improved in the adhesiveness after the cooling cut. The multilayer die may be double cylindrical or sheet shaped. In the case of a sheet, melt-cut sealing facilitates compounding to the next resin. Multi-layer sheet forming and multi-layer film forming devices operate in their respective industries and are large in terms of creating new businesses for the respective industries. In addition, as a matter of course, by forming a thermoplastic resin excellent in mechanical and heat resistance in the surface layer in-line multi-layered without melt-cut sealing, an extruded product excellent in flame resistance and impact strength can be obtained. .

  The final composition (B) concentration is determined by the layer composition ratio and the component concentration of each compound (B) for the layer configuration and layer ratio in the multilayer. If the material of the skin layer is well dispersed in the thermoplastic resin to be finally blended, the skin layer can be applied as a thermoplastic resin alone.

The elastomer flame retardant according to one embodiment of the present invention is

A flame retardant composition in which at least one of compounds of formula A-1 and formula A-2 (compound (A)) and a phosphate ester flame retardant (compound (B)) are melt mixed, The flame retardant composition is a molded body cut from a pellet or sheet containing at least a core layer (C) and a surface layer (D), and the core layer (C) is a compound (A) and the compound (B) the weight ratio of) (a) / (B) is 25/75 to 40/60, the skin layer (D), the weight ratio of the thermoplastic resin or the compound (a) and said compound (B) (A) / (B) is 95 / 5-50 / 50, and the said molded object is mixed with the thermoplastic resin.

  In the elastomeric flame retardant, the weight ratio (C) / (D) of the core layer (C) to the skin layer (D) may be 90/10 to 50/50.

  In the elastomer flame retardant, the thermoplastic resin of the skin layer (D) is polycarbonate, polybutylene terephthalate, polyethylene terephthalate, polylactic acid, polyethylene naphthalate, polyarylate, styrene resin, polyphenylene ether, polyolefin, polyamide resin It may be a thermoplastic epoxy resin, and a polymer alloy containing at least one selected from these.

  The thermoplastic resin composition according to an embodiment of the present invention may contain the above-mentioned elastomer flame retardant.

  INDUSTRIAL APPLICABILITY The present invention can provide an elastomeric flame retardant having flame retardancy and capable of further improving the degree of impact, and a thermoplastic resin composition containing the flame retardant.

The schematic diagram which shows the molded object which comprises the elastomer flame retardant which concerns on one Embodiment of this invention. The schematic diagram which shows the other molded object which comprises the elastomer flame retardant which concerns on one Embodiment of this invention. Schematic which shows the formation process of the molded object which comprises the elastomer flame retardant which concerns on one Embodiment of this invention.

  Hereinafter, although the embodiment of the present invention will be described with examples, the flame retardant of the present invention and the thermoplastic resin composition containing the flame retardant are limited to the following embodiments or examples only. Of course, various modifications can be made without departing from the scope of the present invention.

  FIG. 1 shows a schematic view of a molded body constituting an elastomer flame retardant according to an embodiment of the present invention. FIG. 2 shows a schematic view of another molded body constituting the elastomer flame retardant according to one embodiment of the present invention. FIG. 3: shows the formation process of the molded object which comprises the elastomer flame retardant which concerns on one Embodiment of this invention.

  The flame retardant composition which comprises the elastomer flame retardant of this invention has a compound (C) by which the compound (A) and the compound (B) were melt-mixed. This flame retardant composition is a molded body cut from pellets or sheets containing at least a core layer (C) and a skin layer (D). And this molded object is mixed with a thermoplastic resin, and the elastomer flame retardant of this invention is formed. The details of the compounds (A), (B) and (C) will be described later.

  As shown in FIG. 1, a molded body 10 constituting the elastomer flame retardant of the present invention includes a core layer 11 and a skin layer 12 covering the entire core layer 11. Moreover, as shown to Fig.2 (a), the molded object 10 may contain the core layer 11, the outer skin layer 12, and the intermediate | middle layer 20 provided between the core layer 11 and the outer skin layer 12 . In this case, the intermediate layer 20 may be a multilayer, and may be constituted of, for example, the core layer 21 and the skin layer 22 (see FIG. 2B).

In the above, it is desirable that the core layer (C) 11, 21 contains more compound (B) than compound (A), for example, the weight ratio of compound (A) to compound (B) (A) / (B) it is desirable that the 25/75 to 40/60.
On the other hand, in the epidermal layers (D) 12 and 22, it is desirable that the compound (A) is the same as the compound (B) or more than the compound (B). For example, the compound (A) and the compound (B) The weight ratio of (A) / (B) is preferably 95/5 to 50/50. Alternatively, the skin layers (D) 12 and 22 may be a thermoplastic resin.

  The weight ratio (C) / (D) of the core layers (C) 11, 21 and the skin layers (D) 12, 22 is preferably 90/10 to 50/50. The weight ratio (C) / (D) is more preferably 60/40, 70/30. If the core layer (C) is less than 10% by weight, the cut section from the sheet becomes thin, and the cut pieces become easy to fuse together. On the other hand, when the core layer (C) exceeds 50 weight ratio, the performance as an impact strength improver is lowered.

  Further, as shown in FIG. 2B, when the molded body 10 has the intermediate layer 20, the core layer 11 is the same as the core layer 21, or more preferably, the compound B is higher than the core layer 21. Concentration is preferred. The skin layer 12 is the same as the skin layer 22, or more preferably, a higher concentration of Compound A relative to the skin layer 22 is desirable.

  The flame retardant composition which comprises the elastomer flame retardant of this invention is a molded object cut | judged from a pellet or a sheet, for example. For example, as shown in FIG. 3 (c), the sheet 1 including the core layer 11 and the skin layer 12 shown in FIG. 3 (a) is cut and divided as shown in FIG. 3 (b). A divided body 10 is formed.

  In addition, the thermoplastic resin composition of this invention may be comprised including the elastomer flame retardant of this invention mentioned above.

<Compound (A)>
The compound (A) consists of at least one of Formula A-1 and Formula A-2. That is, the compound (A) is any of a compound consisting of formula A-1, a compound consisting of formula A-2, and a compound containing formula A-1 and formula A-2.

For example, compound (A) is shown as Table 1 below. FRX OL 1001, FRX OL 3001, FRX OL 5000, FRX 100, FRX CO 35, and FRX CO 60 listed on the left side of Table 1 are products of FRX-Polymer .

<Compound (B)>
The compound (B) is a phosphoric acid ester compound.
The phosphoric acid ester is not particularly limited, but it is preferable to use a monophosphoric acid ester, a condensed phosphoric acid ester or the like.

  The monophosphate ester is not particularly limited, and, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, Tris (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthylphosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate Phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresyl phosphine oxide, diphenyl methanephosphonate, phenylphosphonic acid Examples include diethyl, resorcinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), phosphaphenanthrene, tris (β-chloropropyl) phosphate and the like.

  The condensed phosphoric acid ester is not particularly limited. For example, trialkyl polyphosphate, resorcinol polyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., trade name PX-) 200), hydroquinone poly (2,6-xylyl) phosphate and condensed phosphoric acid esters such as condensates thereof. Resorcinol polyphenyl phosphate (trade name CR-733S), bisphenol A polycresyl phosphate (trade names CR-741, FP-600, FP-700), aromatic condensed phosphate ester (trade name CR747), resorcinol polyphenyl phosphate (Adeka company make, brand name Adekastab PFR) etc. can be mentioned.

<Composition of Compound (C)>
In the case of the compound (B) which is solid at normal temperature, it is obvious that the compound (A) is solid even if it is mixed in any composition. In order to solidify the liquid compound (B), it depends on the composition with the compound (A) and the viscosity of the compound (A). If the compound (B) is less than 5%, it does not depend on molecular weight, and although it solidifies by mixing with many compounds (A), it is a flame retardant that has both advantages in combination with compound (A) It can not be said that it is a combination. On the other hand, even if the composition containing the liquid compound (B) exceeds 80%, it solidifies, but it has surface tackiness under storage at high temperature for a long time and under the environment of the production site, and a plurality of It will be in a cohesive form. At this time, if mechanical shearing is applied, aggregates are often separated, but there is also an increase in the number of working steps, which is not preferable.
The experiment was carefully conducted to determine the range in which the liquid compound (B) could be solidified relative to the compound (A). It is the result of experiment when the phosphorus concentration of the experimental sample is in the range of 3 to 20%, and it is presumed that the probability is established between the samples having the concentration outside the range, but the experimental result has an extremely simple relationship I found that. It has a very strong correlation with the melt viscosity of the compound (A), and high molecular weight = achieving solidification including proportion of compound (A) with melt viscosity to compound (B) up to 30/70% by weight I understand.

Compound (B) composition% ≦ 14.7 ln (η) − 85 (Formula 1)
Here, η is a viscosity (cps) measured with a Brookfield B-type viscometer (270 ° C.) of a mixture consisting of Formula A-1, Formula A-2, or Formula A-1 and A-2. It is.
In general, liquid condensed phosphoric ester can be included up to about 20% by weight in a composition melt-kneaded with solid polycarbonate resin, but it is observed that when it exceeds 20% by weight, it bleeds out on the product surface Be done. From this, it was impossible to even predict that the compound (B) was mixed with the compound (A) to a considerably high concentration and solidified. Thus, solidification of the liquid compound (B) is extremely significant industrially.

<Thermoplastic resin>
The thermoplastic resin to which the present invention is applied is suitable for an engineering resin, and is, for example, the following resin. However, it is not limited to the resin illustrated below.

(A) Polycarbonate-Based Resin For example, polycarbonate-based resins are aromatic polycarbonates, aliphatic polycarbonates, and aromatic-aliphatic polycarbonates. The aromatic polycarbonate is obtained by reacting an aromatic hydroxy compound or this with a small amount of a polyhydroxy compound with phosgene or a diester of carbonic acid, but also includes one in which the aromatic hydroxy compound is converted to plant-derived isosorbide. It is also possible to use polymers or oligomers containing both terminal phenolic OH groups having siloxane structures for branching agent introduction and flame retardant assist, respectively.
(B) Polyester-based resin For example, polyester-based resin includes polyethylene phthalate, polybutylene terephthalate, polylactic acid, polyethylene naphthalate, LCP, terephthalic acid and / or isophthalic acid, ethylene glycol and / or cyclohexane dimethanol (CHDM), And / or 2, 2-4, 4- tetramethyl 1, 3 cyclobutanediol (TMCD) copolymer (e.g., PETG, PCTG, PCTA, TRITAN, etc., sold by Eastman Chemical).
(C) Polyamide-based resin For example, polyamide-based resin includes polyamide 6, polyamide 6-6, copolyamide 6 / 6-6, polyamide 11, polyamide 12, polyamide 4, polyamide 4-6, polyamide 6-10, and It is an amorphous polyamide.
(D) Polyacrylate resin, polyacrylonitrile resin (e) Polystyrene resin For example, polystyrene resin is high impact polystyrene, syndiotactic polystyrene, polyacrylonitrile butadiene copolymer.
(F) Polyphenylene ether-based resin (g) Polyphenylene sulfide-based resin (h) Polyarylate (i) Urethane-based For example, a urethane-based resin is a thermoplastic polyurethane or a thermoplastic polyurethane elastomer.
(J) Polysulfone (k) Polyether ether ketone (l) Thermoplastic epoxy resin

  In addition, as a thermoplastic resin, the single type | system | group which consists of any one of said (a)-(k), the blend of 2 or more components, and the polymer alloy of 2 or more components are applied. Examples of the polymer alloy include polycarbonate / polyacrylonitrile butadiene / styrene copolymer alloy, polycarbonate / polyethylene terephthalate, polycarbonate / polybutylene terephthalate, polyphenylene ether / high impact polystyrene, polyphenylene ether / polyamide, polyphenylene ether / polypropylene and the like.

Although it is difficult to apply the invention to polyolefin resins alone, blending or alloying is often performed to improve the above-mentioned engineering plastics such as chemical resistance, moldability, appearance, impact strength, flexibility and the like. In this case, the present invention can be used as long as the polyolefin does not exceed 50% by weight relative to the engineering plastics.
As such polyolefins, polyethylene, polypropylene, poly (4-methylpentene) -1, ethylene-alpha olefin copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-based ionomer resin, ethylene- There are propylene copolymer elastomer, ethylene-butene copolymer elastomer, ethylene-hexene copolymer elastomer, ethylene-octene copolymer elastomer, ethylene-propylene-ethylidene norbornene copolymer etc. Also applicable are ABA type elastomers.

As the elastomer, ethylene-propylene-butadiene copolymer, ethylene-propylene-isoprene copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-butadiene-styrene block copolymer And coalesced hydrides, styrene-isoprene-styrene block copolymer hydrides.
Examples of core-shell elastomers include methacrylic acid ester-butadiene-styrene core-shell graft copolymer, methacrylic acid ester-acrylonitrile-styrene-based core-shell graft copolymer, and acrylic acid ester-silicon-styrene-based core-shell graft copolymer. Polymer acrylic acid ester-based core / shell graft copolymers and the like can be mentioned.

  However, when using a thermoplastic resin as a skin layer (D), if the ratio of D layer is 20% or less of the whole, an olefin resin can be utilized independently.

In the thermoplastic resin composition of the present invention, various components known in the prior art, for example, inorganic fillers and others, may be added at the time of mixing or kneading of the raw materials or molding, as desired. Organic fillers, plasticizers, heat stabilizers, UV absorbers, antioxidants, light stabilizers, antistatic agents, conductive carbon, lubricants, nucleating agents, foaming agents, crosslinking agents, radical generators, release agents , Surfactants, antibacterial and antifungal agents, dyes, pigments and the like may be blended.
As a flame retardant aid, montmorillonite, layered inorganic compounds such as clay, carbon nanotubes and the like are preferable.

<Production of composition>
In the method of simultaneously obtaining the flame retardant A, the thermoplastic resin, and the flame retardant B as melt-kneading, various kneaders, such as uniaxial and multi-axial kneaders, Banbury mixer, in the production with a common thermoplastic resin composition After melt-kneading the above components with a roll, Brabender plastogram, etc., a method of cooling and solidifying is applied, but it is not limited.
However, it is even more advantageous in continuous kneaders, such as twin screw extruders. In extruders such as twin-screw extruders, various elements such as screws, kneading discs, rotors, lengths and shapes of cylinders, and positions and numbers of raw material supply ports can be freely rearranged. Depending on the grade of the flame retardant A and the type of the flame retardant B (phosphate ester), they can be appropriately recombined and used. For example, using a twin-screw extruder, set the raw material supply ports at two locations: the first upper cylinder (No. 1 supply) and the upper second cylinder (No. 2 supply) between the first cylinder and the die head. No. 1 supply port and No. 2 supply port (upstream portion), and between the No. 2 supply port and die head (downstream portion), a kneading disc is appropriately disposed and brought to a predetermined temperature. (1) A method of supplying the thermoplastic resin and the flame retardant A from the supply port and supplying the compound B (phosphate ester flame retardant) from the No. 2 and No. 3 supply ports can be mentioned. However, when the compound (B) is a liquid flame retardant, a liquid supply device is required.

There are the following two methods for producing the flame retardants of the compound A and the compound B, but there is no particular limitation as long as the device is capable of mixing the compound B above the melting point of the compound A.
For example, generally, it is possible if it is a tank with a heating jacket and a stirrer. Industrially, this can be industrially incorporated into a liquid flame retardant manufacturing process, and a flame retardant composition (compound C) which is solid at room temperature can be easily obtained by taking-out cooling.
It is possible to utilize a kneader by utilizing the fact that the compound A has a high molecular weight, but in this case also a twin-screw kneader extruder is useful. That is, after the compound A is supplied from the No. 1 supply port and melt-plasticized, the liquid compound B is supplied from the No. 2 supply port, the mixture is kneaded, the strand is extruded from the die, water cooled, air cooled and desired with the strand cutter. It is possible to obtain pellets cut to the size of.
When the obtained flame retardant pellet is further mixed with a thermoplastic resin, it is preferable to obtain the composition by the same melt-kneading extruder, but it may be mixed with the raw material directly during molding.

  The method for molding the thermoplastic resin composition of the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, that is, injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum molding, From various molding methods such as plug-assisted pressure forming, film forming, sheet forming, rotational forming, laminate forming, foam forming, etc., it is appropriately selected according to the formulation of the thermoplastic resin composition, the use of the packaging container, etc. be able to.

  In addition, although the elastomer flame retardant of this invention mixes and forms the molded object comprised by a flame retardant composition with a thermoplastic resin, it is not limited to this. For example, instead of the thermoplastic resin, the molded body may be mixed with the thermosetting resin. In this case, the stress at the time of curing can be relaxed, and as a result, the impact strength can be improved.

[Example]
Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these examples. Table 2 below shows the details of the experimental apparatus used in the examples of the present invention, and in the examples of the present invention, a twin-screw kneading extruder, twin-screw kneading, for kneading the flame retardants A and B and the thermoplastic resin. The experiment was carried out using a No. 1 supply port and a No. 2 supply port for the raw material supply port using a machine. The flame retardancy was evaluated in accordance with UL 94, and the impact strength was measured using a Charpy impact apparatus manufactured by Tester Sangyo Co., Ltd.

Table 3 below shows the materials used in the experiments of the examples and comparative examples of the present invention and the experimental results, and the skin layer blending ratio, core layer blending ratio, multilayered flame retardant, resin composition, flame retardancy Experimental data of Charpy impact strength is shown .

Examples according to the present invention and comparative examples will be described below with reference to Tables 3 and 4 .
<Example of production of flame retardant alloy and comparative example>
Example 1
The first step is the formation of the skin layer.
First, 80 parts of FRX-Polymer's Nokia-100L from the first feed section of Japan Steel Works Co., Ltd.'s 2-shaft kneader TEX30α and 20 parts of the second feed from the second feed of ADEKA's flame retardant FP600 Be done. Then, screw rotation is set at 230 rpm, cylinder temperature is set to 230 ° C. under the first feed, and 190 ° C. under the second feed, compounded under the setting extrusion conditions of 5 kg / hr., Cooled by a water tank, and cut with a pelletizer Pellets are made.
Next, the pellet is heated and pressed once. This creates a sheet. The heating conditions are a temperature of 210 ° C. and a pressure of 3 MPa. The sheet size is 200 mm in width, 200 mm in length, and 0.25 mm in thickness.

The second step is multilayering of the compound of the core layer and the sheet obtained in the first step.
The compound composition of the core layer changes the ratio of the material system at the time of using the first step, and makes 30 parts of Sofia-100L and 70 parts of FP600, the temperature under the first feed is 220 ° C., the temperature under the second feed The extrusion was performed under the same conditions as others, except that the temperature was 190 ° C. However, the die is loaded with a hanger coat die having a width of 150 mm and a die gap of 2 mm at the tip of the kneader. The film used in the first step is placed on a metal press sheet, and a 2 mm-thick sheet of T-die molten material corresponding to the core layer to be discharged is laminated in accordance with the outflow. The ratio of the skin layer to the core layer is 0.8 . Next, the same kind of film is laminated from the top, and the skin layer / core layer / skin layer three-layer sheet is obtained by cooling while being weakly pressed with a pressure of 1 MPa in a cooling press. After cooling, the sheet is cut into about 5 to 7 mm with scissors.
There is no surging in the extrusion of the skin layer and in the extrusion of the core layer, which is a stable compound. The three-layer sheet had no stickiness, and no trouble due to stickiness was observed even when it was cut with scissors.

Dry-blend 16 parts of the cut three-layer pellet and 39 parts of Mitsubishi Engineering Plastics Co., Ltd. sales polycarbonate (Iupilon S2000), carry out glass fiber and compound with TEX30α (condition II) made by Nippon Steel Works, and make the pellet obtain. 45 parts of glass fibers having a cylinder temperature of 260 ° C. are fed from the middle of the kneader cylinder (Nitto Boseki glass fiber (CF 3 PE 937)).
Next, the pellet obtained is subjected to hot pressing with a Toyo Test Instruments Co., Ltd. Mini Test Press-10 to produce a UL evaluation test piece and a Charpy impact test piece. As a result, the UL94 flame retardant V0 V notched Charpy impact strength has a very high physical property of 16 kJ / m ² . It was confirmed that both flame retardancy and impact strength were satisfactory.

Example 2
In the flame retardant formulation in the first step (skin layer) molding of Example-1, 60 parts of Sofia-100L and 40 parts of FP600 are used, and the other experiment is performed in the same manner as in Example-1. The ratio of the skin layer to the core layer is 0.8 . By this, substantially the same good results were obtained.

[Example 3]
In Example 1, A-2 type which is a copolymer of PC with the FRX grade of the second step (core layer), wherein 90 parts of Sofia-100L of the first step (skin layer) and 10 parts of FP600 are used. The experiment was carried out in the same manner as in Example 1 except for changing to Nof-CO 60 of The ratio of the skin layer to the core layer is 0.8 .
As a result, it was found that the Charpy impact strength was very high at 18 J / m ^2, and the flame retardancy maintained V0.

Example 4
In Example 1, the flame retardant NOFIO-100L in the molding of the first step (skin layer) is switched to NOF-9000, and the second step is the application of NOF-CO 60 in Example 3 under the other conditions of Example A polycarbonate composition was obtained in the same manner as -1. The ratio of the skin layer to the core layer is 0.8 .
Also in this case, the molten composition obtained in the first step solidified easily, could form a film, and was not tacky. Furthermore, by adopting the A-2 type which is a copolymer with PC for the core layer, the elastomer property is higher, and as a result, the impact of the glass fiber reinforced polycarbonate is high, and the flame retardancy can be secured.

Example 5
A film of polycarbonate (Mitsubishi Engineering Plastics sales Iupilon S2000) containing no flame retardant in the surface layer is prepared, and the composition of Example 1 is multilayered in the core layer. However, the ratio of core layers is 0.8.
As a result, there was no tackiness of the multilayered flame retardant, and the impact of the final glass fiber reinforced polycarbonate was high, and the flame retardancy could be secured.

[Example 6]
The material in the first step is an extrusion film made of Mitsubishi Engineering Plastics Co., Ltd. product polybutylene phthalate (nearly PBT) (Novaduran 5010) alone as an extruded film, and the second step in the process is 30 parts of A-2 type Sofia-CO60. And 70 parts of FP600, and the ratio of the skin layer to the core layer is 0.8 .
In Example 6, there was no tackiness of this multilayered flame retardant, and there was no problem in compounding with the PBT resin in the next step. In the glass fiber PBT compound, the number of flame retardant parts in three layers was increased to 18 parts. As a result, the impact strength in the PBT system was as high as 12 J / m ² and the flame retardancy was also confirmed as V0. It can be seen that the practical value is high when this example is compared with comparative example-4.

Comparative Example 1
In the first step, a flame retardant NOF-100L used in Example 1 is once formed into a pellet by a twin-screw kneader as in the example. Thereafter, a composition consisting of 16 parts of this sample, 37 parts of polycarbonate resin and 45 parts of glass fiber was compounded by a twin-screw kneader, and the quality after producing test pieces similar to the example was evaluated. The notched Charpy impact strength was 5.5 J / m ² , and the flame resistance was dripped and at the V2 level. This comparative example also reproduces that the flame retardancy is improved by forming the flame retardant alloy of the compound (B) component even in Japanese Patent No. 5913756. Here, v-notched impact strength is listed as a comparison target.

Comparative Example 2
In the first step, 30 parts of Sofia-100L and 70 parts of FP600 are melt-kneaded and extruded. However, it was confirmed that the melt strand had high viscosity, and pelletization after water cooling had a problem in production stability such that the work was stopped, such as being caught in a pelletizer. However, it was found that the strand itself is flexible as an elastomer, and that the strand of the single Sofia of Comparative Example 1 is characterized by being brittle. However, it did not reach v-notched Charpy impact and flame resistance evaluation

Comparative Example 3
In a twin-screw kneader, 16 parts of the flame retardant composition of only the skin layer not containing the core layer in Example 2 and 39 parts of polycarbonate resin and 45 parts of glass fibers are compounded in Example-2.
As for the flame retardancy, the reproducibility of Patent No. 5913756 is obtained at V0, and the Charpy impact strength is a relatively high value of 8.8 J / m ² , but the impact value of Example 2 is far It turned out to be high.

Comparative Example 4
The PBT 5010 used in Example 6 is compounded by blending 18 wt% of a phosphorus-based flame retardant FP600 and 45 wt% of glass fibers. At the stage of passing the extruded strand through the water bath, it was found that the flame retardant FP600 was floating on the surface of the water bath, and the obtained pellet was slightly sticky. The v-notched Charpy impact strength of this composition was 8 J / m ² . In the flame retardancy evaluation, there was a drip and it was V2.

Comparative Example 5
In Example 1, the core layer ratio is 0.95. In this case, it was found that the tackiness was strong at the time of sheet cutting and it was unsuitable for compounding with a thermoplastic resin.

Comparative Example 6
In Example 1, the core layer ratio is 0.25. In this case, there was no problem in the compound with the thermoplastic resin at the time of sheet cutting, but it was found that the impact strength is lower than that of Example 1.
Although this level is also highly rated as compared with the conventional flame retardant system, in the present invention, it was determined that the claimed core layer ratio is suitable.

<Effect>
As typical flame retardants, halogen-based flame retardants, red phosphorus, phosphine-based flame retardants, condensed phosphoric acid esters, and intumescent flame retardants are exemplified.
However, when these flame retardants are blended into a thermoplastic resin to impart flame retardancy, mechanical properties and thermal properties are reduced.
Therefore, the elastomer is compounded to recover the impact strength. However, except for fluorine-based and silicone-based elastomers, general-purpose elastomers rather reduce the flame retardant effect. In addition, silicone-based and fluorine-based elastomers sometimes have poor compatibility with resins, and the impact strength does not improve so much.
In order to solve such contradiction, a compound which is an elastomer and is also a flame retardant and which is also compatible with the thermoplastic resin is desired. However, there is no prior art document or patent for such technology.
Therefore, the inventors of the present invention have been described in Patent Document 1 in which a composition having a specific dispersion form obtained by melt-kneading compound (A) and compound (B) under specific conditions is compound (A) and compound (B) respectively. It has been found that the flame retardancy is superior to the case where the thermoplastic resin is blended alone.

  In the composition of the compound (A) and the compound (B) according to the present invention, it was found that the composition has an elastomeric property in a specific range by increasing the concentration of the compound (B). However, in this composition range, the strand after melt-kneading is sticky. Therefore, the present invention uses a non-adhesive (A) / (B) composition or a thermoplastic resin as a skin layer, and a (A) / (B) composition with particularly high elastomeric property as a core layer, and a thermoplastic resin It was found that both the impact strength and the flame retardance are satisfied by blending in

As described above, with regard to imparting flame retardancy to products that protect the safety and security of our lives from fire, on the other hand, there are demands for thin-walled, lightweight products due to environmental problems and various high strength and high heat resistant materials from high functional requirements. It is difficult to match this flame retardancy with such a demand, and there is a trade-off relationship with conventional flame retardants. Although the present invention can not be satisfied with a single flame retardant, it has been proved that the combination of the advantages and disadvantages and the opposite flame retardant gives a novel idea and solid quality to be said to be "flame retardant alloy".
On the other hand, manufacturing bases for such materials are globalizing, and plants that are compounded with resin and flame retardant are also shifting along with local production at final customers. Under such conditions, it is not possible to expect the same level as the conventional viscous liquid flame retardant handling process capability. And storage conditions and severe conditions are easily assumed. At this time, the industrial meaning that the viscous liquid flame retardant can be solidified is extremely high.

Furthermore, the greatest feature of the present invention is an elastomeric flame retardant. Conventionally, various elastomers have been used as impact strength. However, as described above, the flame retardancy was not provided in the first place, and it was necessary to additionally add a flame retardant from the outside. In such cases, the flame retardancy is insufficient, and in order to cover it, the product thickness has been increased to cope with it, but the scope of application is limited among the recent light weight and thickness reduction. ing.
In Patent Document 1 of the inventor, it has been clearly shown that excellent flame retardancy is imparted in the formation of a composite with glass fibers and the like. In the past, it was difficult to make the glass fiber composite flame-retardant because glass fibers act as a combustion gas passage during combustion, but the present invention improves the impact strength of the glass fiber composite material system and makes it difficult. The industrial meaning of imparting flammability is very large.
As mentioned above, the elastomer flame retardant of the present invention can act as an impact modifier and a flame retardant.

Claims (4)

At least one of compounds of formula A-1 and formula A-2 (compound (A)),
It is a flame retardant composition in which a phosphate ester flame retardant (compound (B)) is melt mixed,
The flame retardant composition is a molded body cut from a pellet or sheet containing at least a core layer (C) and a skin layer (D),
The core layer (C) has a weight ratio (A) / (B) of the compound (A) to the compound (B) of 15/75 to 40/60,
The skin layer (D) is a thermoplastic resin, or a weight ratio (A) / (B) of the compound (A) to the compound (B) is 95/5 to 50/50,
An elastomeric flame retardant wherein the molded body is mixed with a thermoplastic resin.   The elastomer flame retardant according to claim 1, wherein a weight ratio (C) / (D) of the core layer (C) to the skin layer (D) is 90/10 to 50/50.   The thermoplastic resin of the skin layer (D) is polycarbonate, polybutylene terephthalate, polyethylene terephthalate, polylactic acid, polyethylene naphthalate, polyarylate, styrene resin, polyphenylene ether, polyolefin, polyamide resin, thermoplastic epoxy resin, The elastomer flame retardant according to claim 1 or 2, which is a polymer alloy containing at least one selected from these. A thermoplastic resin composition comprising the elastomeric flame retardant according to any one of claims 1 to 3.