Thermoplastic resin composition, thermoplastic resin molded article, and method for manufacturing a thermoplastic resin composition

Abstract

To provide a thermoplastic resin composition comprising a cycloolefin-based resin achieving both of flame retardancy and toughness.SOLUTION: There is provided a thermoplastic resin composition comprising a cycloolefin-based resin, a flame retardant and a compatibilizer, wherein after the thermoplastic resin composition is molded to be a strip-like test piece 125 mm long, 13 mm wide and 1.6 mm thick which is subjected to humidity conditioning in a constant-temperature chamber at 23°C and 50% humidity for 48 hours, followed by storing in a constant-temperature chamber at 70°C for 168 hours, a flame retardancy test is carried out according to UL94V and the evaluation is HB or more, and the thermoplastic resin composition is molded to be a strip-like test piece 80 mm long, 10 mm wide and 4 mm thick and a toughness test is carried out at 23°C according to JIS K7110 and the evaluation of the Charpy impact strength is 5 kJ / m2 or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a thermoplastic resin composition, a thermoplastic resin molded article, and a method for producing a thermoplastic resin composition. [Background technology]

[0002] Cyclic olefin resins are amorphous, thermoplastic olefin resins with a cyclic olefin skeleton in their main chain. They possess excellent heat resistance, light weight, dimensional stability, low water absorption, resistance to thermal decomposition, and chemical resistance, and are free from environmentally harmful substances.

[0003] Therefore, cyclic olefin resins are used in a wide range of applications, including optical applications such as optical discs, lenses, and light guide plates, as well as pharmaceutical equipment, high-frequency electronic components, and packaging and containers for pharmaceuticals and food products. For example, Patent Documents 1 and 2 disclose cyclic olefin resins as described above. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2003-080631 [Patent Document 2] Japanese Patent Publication No. 2021-070742 [Overview of the initiative] [Problems that the invention aims to solve]

[0005] As described above, cyclic olefin resins generally have poor flame retardancy. Therefore, adding flame retardants to cyclic olefin resins is considered. However, adding large amounts of flame retardants to cyclic olefin resins can lead to a decrease in toughness as a side effect. If toughening agents are then added to improve the reduced toughness, flame retardancy decreases as a side effect. Thus, it is difficult to achieve both flame retardancy and toughness in cyclic olefin resins.

[0006] The object of the present invention is to provide a thermoplastic resin composition containing a cyclic olefin resin that achieves both flame retardancy and toughness. Another object of the present invention is to provide a thermoplastic resin molded article obtained by molding the thermoplastic resin composition. Yet another object of the present invention is to provide a method for producing the thermoplastic resin composition. [Means for solving the problem]

[0007] This invention relates to the following thermoplastic resin compositions. [1] A cyclic olefin resin, a flame retardant, and a compatibilizer are included, and the material is molded into a strip-shaped test specimen measuring 125 mm in length, 13 mm in width, and 1.6 mm in thickness. This specimen is then conditioned for 48 hours in a constant temperature room at 23°C and 50% humidity, and subsequently stored in a constant temperature room at 70°C for 168 hours. After this, a flame retardancy test is performed in accordance with UL94V, and the evaluation is HB or higher. Furthermore, the material is molded into a strip-shaped test specimen measuring 80 mm in length, 10 mm in width, and 4 mm in thickness, and a toughness test is performed at 23°C in accordance with JIS K7110, with a Charpy impact strength evaluation of 5 kJ / m². 2 The above describes the thermoplastic resin composition. [2] The thermoplastic resin composition according to [1], wherein the cyclic olefin resin, the flame retardant, and the compatibilizer are melt-kneaded together. [3] The thermoplastic resin composition according to [1] or [2], wherein the content of the flame retardant is 35% by weight or less with respect to the total amount of the thermoplastic resin composition. [4] The thermoplastic resin composition according to any one of [1] to [3], wherein the content of the compatibilizer is 25% by weight or less with respect to the total amount of the thermoplastic resin composition. [5] The thermoplastic resin composition according to any one of [1] to [4], wherein the flame retardant is one or more compounds selected from the group consisting of phosphorus compounds, halogen compounds, silicon compounds, and inorganic compounds. [6] The thermoplastic resin composition according to any one of [1] to [5], wherein the compatibilizer is one or more copolymers selected from the group consisting of a copolymer of a monomer having a reactive functional group and another monomer, a copolymer in which a reactive functional group is introduced into a base resin, a graft copolymer in which different types of polymers are chemically bonded in a branched or crosslinked structure in the form of a main chain and a secondary chain, and a block copolymer in which different types of polymers consist of soft blocks and hard blocks. [7] The thermoplastic resin composition according to any one of [1] to [6], wherein the cyclic olefin resin is a copolymer in which at least cycloolefin is used as a monomer and which has arbitrary substituents, the flame retardant is a phosphate ester compound, and the compatibilizer is a copolymer having a reactive functional group.

[0008] This invention relates to the following thermoplastic resin molded articles. [8] A thermoplastic resin molded article obtained by molding any of the thermoplastic resin compositions described in [1] to [7] above.

[0009] This invention relates to a method for producing the following thermoplastic resin compositions. [9] A method for producing a thermoplastic resin composition according to any one of [1] to [7] above, comprising melt-kneading the cyclic olefin resin, the flame retardant, and the compatibilizer. [Effects of the Invention]

[0010] According to the present invention, a thermoplastic resin composition containing a cyclic olefin resin that achieves both flame retardancy and toughness can be provided. Furthermore, according to the present invention, a thermoplastic resin molded article obtained by molding the thermoplastic resin composition can be provided. Furthermore, according to the present invention, a method for producing the thermoplastic resin composition can be provided. [Modes for carrying out the invention]

[0011] A thermoplastic resin composition according to one embodiment of the present invention is characterized by comprising a cyclic olefin resin, a flame retardant, and a compatibilizer.

[0012] When only a cyclic olefin-based resin and a flame retardant are melt-kneaded to obtain a thermoplastic resin composition, it is difficult for the flame retardant to be uniformly dispersed in the cyclic olefin-based resin (hereinafter sometimes abbreviated as resin). The flame retardant that is not dispersed in the resin will bleed out, not only deteriorating the appearance of the molded product, but also reducing the flame retardancy because the required amount of the flame retardant is not contained in the resin. Furthermore, when the flame retardant localizes in the resin and forms aggregates, that part becomes a fracture point and the toughness (impact resistance) decreases.

[0013] In the present embodiment, a thermoplastic resin composition is obtained by melt-kneading a cyclic olefin-based resin and a flame retardant in the presence of a compatibilizer. Thereby, the flame retardant is uniformly dispersed in the resin. The compatibilizer has a structure with high affinity for both the resin and the flame retardant.

[0014] By doing as described above, according to the present embodiment, the bleed-out of the flame retardant is suppressed and the flame retardancy of the thermoplastic resin composition is improved. Also, by melt-kneading in a state where the interaction between the flame retardant and the resin is enhanced, the flame retardant is uniformly dispersed in the resin and the toughness (impact resistance) of the thermoplastic resin composition is improved.

[0015] Specifically, the thermoplastic resin composition according to the present embodiment has an evaluation of HB or higher when a flammability test is conducted in accordance with UL94V described later. It is preferable that the evaluation is V2 or higher, and more preferably V1 or higher.

[0016] Also, the thermoplastic resin composition according to the present embodiment has an evaluation of the Charpy impact strength of 5 kJ / m 2 or more described later. It is preferable that the evaluation is 10 kJ / m 2 or more, and more preferably 15 kJ / m 2 or more.

[0017] Hereinafter, each of the cyclic olefin-based resin, compatibilizer, and flame retardant included in the thermoplastic resin composition according to the present embodiment will be described.

[0018] The cyclic olefin resin is a component that serves as the base of the thermoplastic resin composition according to the embodiment of the present invention.

[0019] In the present embodiment, the cyclic olefin resin is a copolymer using at least cyclic olefin (cycloolefin) as a monomer. Specifically, in the present embodiment, the copolymer is a copolymer of a cyclic olefin and a compound having an α-olefin. Note that this copolymer may have an arbitrary substituent. The arbitrary substituent preferably has an affinity with the compatibilizer. Alternatively, the arbitrary substituent is preferably capable of reacting (bonding) with a reactive functional group, which will be described later, that the compatibilizer may have.

[0020] In the present embodiment, the cyclic olefin is a compound having a ring structure formed of carbon atoms. The number of rings in the cyclic olefin is not particularly limited. Examples of the number of rings in the cyclic olefin include a monocyclic ring, a bicyclic ring, a tricyclic ring, a tetracyclic ring, a pentacyclic ring, and the like.

[0021] The cyclic olefin to be used is not particularly limited and can be appropriately selected according to the purpose.

[0022] Examples of the cyclic olefin include norbornene-based compounds and monocyclic cycloolefins. These may be used alone or in combination of two or more. Note that the norbornene-based compound is a compound containing a norbornene ring.

[0023] The norbornene-based compound to be used is not particularly limited and can be appropriately selected according to the purpose.

[0024] Examples of the norbornene-based compound include bicyclics such as 2-norbornene and norbornadiene, tricyclics such as dicyclopentadiene and dihydrodicyclopentadiene, tetracyclics such as tetracyclododecene, ethylidene tetracyclododecene, and phenyltetracyclododecene, and pentacyclics such as tricyclopentadiene. These may be used alone or in combination of two or more.

[0025] There are no particular restrictions on the α-olefin-containing compound used, and it can be appropriately selected depending on the purpose.

[0026] Examples of compounds containing α-olefins include alkylenes, ethylenes, propylenes, and butylenes. These may be used individually or in combination of two or more.

[0027] The following commercially available products are examples of cyclic olefin resins. Note that recycled materials may also be used instead of commercially available products. Polyplastics Co., Ltd. TOPAS 8007S-04 Mitsui Chemicals, Inc. APEL APL6509T Zeon Corporation ZEONOR1060R JSR Corporation ARTON D4000

[0028] From the viewpoint of achieving both flame retardancy and toughness, the content of cyclic olefin resin is preferably 45% by weight or more, more preferably 55% by weight or more, more preferably 65% ​​by weight or more, and even more preferably 75% by weight or more, relative to the total amount of the thermoplastic resin composition. The upper limit of the content of cyclic olefin resin may be, for example, 90% by weight or less, or 85% by weight or less, relative to the total amount of the thermoplastic resin composition.

[0029] Compatibilizers can enhance the dispersibility and interaction between cyclic olefin resins and flame retardants. Compatibilizers include both reactive and non-reactive types.

[0030] In this embodiment, the reactive compatibilizer has reactive functional groups and can react with the functional groups of the cyclic olefin resin and the flame retardant, thereby enhancing the interaction between them. In this embodiment, the non-reactive compatibilizer has a portion that readily interacts with the cyclic olefin resin and a portion that readily interacts with the flame retardant, thereby enhancing the interaction between them.

[0031] Reactive compatibilizers can be obtained by either 1) copolymerizing a monomer having a reactive functional group with another monomer (a monomer without a reactive functional group), or 2) introducing a reactive functional group into a base resin that does not have a reactive functional group.

[0032] Monomers with reactive functional groups are typically glycidyl (meth)acrylates with epoxy groups, while other monomers include unsaturated hydrocarbons such as ethylene and (meth)acrylic acid esters.

[0033] To introduce reactive functional groups into a base resin, a modifying agent can be graft polymerized onto the base resin. Preferred base resins to which reactive functional groups can be introduced include polyethylene resins, ester resins, (meth)acrylic resins, polypropylene resins, styrene resins, and rubber polymers, due to the ease of introducing reactive functional groups.

[0034] Here, a rubbery polymer is generally a polymer that contains polymers with a glass transition temperature lower than room temperature, and in which some of the molecules are constrained by covalent bonds, ionic bonds, van der Waals forces, entanglement, etc.

[0035] Examples of rubbery polymers include polybutadiene, polyisoprene, random and block copolymers of styrene-butadiene, hydrogenated block copolymers, diene rubbers such as acrylonitrile-butadiene copolymer and butadiene-isoprene copolymer, random and block copolymers of ethylene-propylene, random and block copolymers of ethylene-butene, copolymers of ethylene and α-olefin, ethylene-unsaturated carboxylic acid copolymers such as ethylene-acrylic acid and ethylene-methacrylic acid, ethylene-unsaturated carboxylic acid ester copolymers such as ethylene-acrylic acid ester and ethylene-methacrylic acid ester, and metals in which part of the unsaturated carboxylic acid is present. These include salts such as ethylene-acrylic acid-metal acrylic acid copolymers, ethylene-methacrylic acid-metal methacrylic acid copolymers, acrylic ester-butadiene copolymers, acrylic elastic polymers such as butyl acrylate-butadiene copolymers, ethylene-vinyl acetate copolymers, ethylene-vinyl fatty acid copolymers, ethylene-propylene unconjugated diene terpolymers such as ethylene-propylene-ethylidene norbornene copolymers, and ethylene-propylene-hexadiene copolymers, butylene-isoprene copolymers, chlorinated polyethylene, polyamide elastomers, and polyester elastomers.

[0036] This reactive functional group is not particularly limited as long as it can react with functional groups present in the cyclic olefin resin or flame retardant. Specifically, the reactive functional group can react with the ester group of the cyclic olefin resin or flame retardant, or with the carboxylic acid group produced by its hydrolysis. The reaction with the reactive functional group reinforces the interface between the cyclic olefin resin and the flame retardant.

[0037] Preferred examples of reactive functional groups include at least one selected from amino groups, carboxyl groups, carboxyl metal salts, hydroxyl groups, acid anhydride groups, epoxy groups, isocyanate groups, mercapto groups, oxazoline groups, sulfonic acid groups, and the like. Among these, epoxy groups, acid anhydride groups, and oxazoline groups are more preferred because they are highly reactive and cause fewer side reactions such as decomposition and crosslinking.

[0038] There are no particular restrictions on the number of reactive functional groups per molecular chain, but it is usually preferable to have 1 to 10, and preferably 1 to 5 to minimize side reactions such as crosslinking. It is also acceptable to include molecules that do not have any reactive functional groups, but the smaller the proportion of such molecules, the better.

[0039] The method for graft polymerization of the base resin with a modifier is not particularly limited, but the modifier can be polymerized in the presence of the base resin by methods such as emulsion polymerization, suspension polymerization, bulk polymerization, and solution polymerization. Specifically, the following commercially available products are suitable as reactive compatibilizers.

[0040] NOF Corporation ModiPer A4100 Asahi Kasei Corporation ToughTec M1913 Sumitomo Chemical Co., Ltd. Bond First BF-2C

[0041] Non-reactive compatibilizers are either 1) graft copolymers in which different types of polymers are chemically bonded in a branched or cross-linked structure as a main chain and a secondary chain, or 2) block copolymers in which different types of polymers consist of soft blocks and hard blocks. Examples of different types of polymers include polyolefin resins, ester resins, (meth)acrylic resins, and styrene resins. Specifically, the following commercially available products are examples of non-reactive compatibilizers.

[0042] Asahi Kasei Corporation ToughTec H1062 JSR Corporation DYNARON 9901P NOF Corporation ModiPer A1100

[0043] There are no particular restrictions on the compatibilizer used, and it can be appropriately selected according to the purpose. One of the above compatibilizers may be used alone, or two or more may be used in combination.

[0044] Compatibilizers help to disperse flame retardants in thermoplastic resin compositions, thereby improving flame retardancy and toughness. However, if too much compatibilizer is used, the compatibilizer itself may be flammable, reducing the flame retardancy.

[0045] From the viewpoint of achieving both flame retardancy and toughness, the content of such compatibilizers is preferably 35% by weight or less, more preferably 30% by weight or less, more preferably 25% by weight or less, more preferably 20% by weight or less, and more preferably 15% by weight or less, relative to the total amount of the thermoplastic resin composition. The lower limit of the compatibilizer content may be, for example, 0.1% by weight or more, 1% by weight or more, 5% by weight or more, or 8% by weight or more, relative to the total amount of the thermoplastic resin composition.

[0046] The flame retardant makes a thermoplastic resin composition containing a cyclic olefin resin and a compatibilizer flame-retardant.

[0047] The flame retardant may be an organic flame retardant or an inorganic flame retardant (inorganic compound).

[0048] Examples of organic flame retardants include phosphorus compounds, halogen compounds, bromo compounds, and silicon compounds. Examples of inorganic flame retardants include antimony compounds and metal hydroxides. Note that phosphorus compounds also include red phosphorus and phosphazenes containing nitrogen atoms.

[0049] Phosphorus compounds are typically phosphate ester compounds, and examples of phosphate ester compounds include phosphite esters, phosphate esters, and phosphonic acid esters.

[0050] Specific examples of phosphite esters include triphenyl phosphite, tris(nonylphenyl) phosphite, tris(2,4-di-t-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, and bis(2,4-di-t-butylphenyl) pentaerythritol diphosphite.

[0051] Specific examples of phosphate esters include triphenyl phosphate, tris(nonylphenyl) phosphate, tris(2,4-di-t-butylphenyl) phosphate, distearyl pentaerythritol diphosphate, bis(2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphate, bis(2,4-di-t-butylphenyl) pentaerythritol diphosphate, tributyl phosphate, bisphenol A bis-diphenyl phosphate, and aromatic condensed phosphate esters.

[0052] Specific examples of phosphonic acid esters include dimethyl benzenephosphonate and benzenephosphonic acid esters.

[0053] Examples of bromo compounds include polybromodiphenyl ethers, tetrabromobisphenol-A, brominated epoxy oligomers, and brominated polycarbonate oligomers.

[0054] Specifically, the following commercially available products are examples of flame retardants. Daihachi Chemical Industry Co., Ltd. PX-200 ADEKA Corporation ADEKA Stub FP-2100JC Suzuyu Chemical Co., Ltd. Firecut FCP-680 Osaka Gas Chemical Co., Ltd. OGSOL SI-30-10

[0055] There are no particular restrictions on the flame retardants used, and they can be appropriately selected according to the purpose. One flame retardant may be used alone from the above-mentioned flame retardants, or two or more may be used in combination.

[0056] Flame retardants are useful for making thermoplastic resin compositions flame-retardant. However, too much flame retardant can reduce toughness.

[0057] From the viewpoint of achieving both flame retardancy and toughness, the content of such flame retardants is preferably 50% by weight or less, more preferably 45% by weight or less, more preferably 35% by weight or less, more preferably 30% by weight or less, more preferably 25% by weight or less, and more preferably 15% by weight or less, relative to the total amount of the thermoplastic resin composition. The lower limit of the flame retardant content may be, for example, 1% by weight or more, 5% by weight or more, 8% by weight or more, or 10% by weight or more, relative to the total amount of the thermoplastic resin composition.

[0058] The thermoplastic resin composition according to the embodiment of the present invention may contain any additives as long as they do not impair the objective of the present invention. For example, the performance as a molding resin can be improved by adding polyolefins such as vinyl chloride, polyethylene, and polypropylene, polyamides such as nylon 6 and nylon 66, and various elastomers to the thermoplastic resin composition. Other examples of optional additives include antioxidants (hindered phenols, sulfur-containing organic compounds, phosphorus-containing organic compounds, etc.), heat stabilizers (phenols, acrylates, etc.), ultraviolet absorbers (benzotriazoles, benzophenones, salicylates, etc.), light stabilizers (organicickels, hindered amines, etc.), lubricants (metal salts of higher fatty acids, higher fatty acid amides, etc.), plasticizers (phthalates, phosphates, etc.), pigments (carbon black, titanium dioxide), and dyes.

[0059] Further examples of optional additives include fillers such as metal fibers, aramid fibers, asbestos, potassium titanate whiskers, wollastonite, glass flakes, glass beads, talc, mica, clay, calcium carbonate, barium sulfate, titanium dioxide, and aluminum oxide. The type of these fibrous fillers is not particularly limited as long as they are commonly used to reinforce resins, and can be selected from, for example, long-fiber or short-fiber chopped strands or milled fibers.

[0060] [Uses of thermoplastic resin compositions] (Thermoplastic resin molded product) A thermoplastic resin molded article can be produced using the thermoplastic resin composition of the present invention. This molded article provides a structure that possesses both flame retardancy and good toughness. When manufacturing the molded article, the thermoplastic resin composition can be melted and molded in various molding machines. The molding method can be appropriately selected depending on the form and application of the molded article, and examples include injection molding, extrusion molding, compression molding, injection compression molding, blow molding, calendering, and inflation molding. Furthermore, sheet-like or film-like molded articles obtained by extrusion molding and calendering can be subjected to secondary molding such as vacuum forming or pressure forming.

[0061] The scope of application of molded articles formed from thermoplastic resin compositions according to embodiments of the present invention is not particularly limited, and examples include use in electrical and electronic components, electrical components, exterior parts, and interior parts in fields such as home appliances and automobiles, as well as in various packaging materials, household goods, office supplies, piping, and agricultural materials.

[0062] (electronic equipment) The present invention provides electronic equipment characterized by using the above-mentioned molded articles as components. While not particularly limited, examples of electronic equipment include computers, scanners, copiers, printers, facsimile machines, and OA equipment such as MFPs (MultiFunction Peripherals) that combine these functions. Furthermore, molded articles formed from the thermoplastic resin composition of the present invention are preferably used as exterior or interior components of electronic equipment. [Examples]

[0063] The present invention will be described in detail below using examples, but the present invention is not limited to the following examples.

[0064] [Example 1] Using a KTX-30 twin-screw kneader (manufactured by Kobe Steel, Ltd.), the thermoplastic resin composition of Example 1 was obtained by melt-kneading 70% by weight of TOPAS 8007S-04 (manufactured by Polyplastics Co., Ltd.) as a cyclic olefin resin, 10% by weight of Modiper A4100 (manufactured by NOF Corporation) as a compatibilizer, and 20% by weight of PX-200 (manufactured by Daihachi Chemical Industry Co., Ltd.) as a flame retardant at a cylinder temperature of 260°C and a screw rotation speed of 200 rpm.

[0065] TOPAS 8007S-04 is a cyclic olefin resin using a nobornene-based compound as a monomer. Modiper A4100 is a reactive compatibilizer. PX-200 is a phosphate ester-based flame retardant.

[0066] [Example 2] The thermoplastic resin composition of Example 2 was obtained in the same manner as in Example 1, except that ToughTec H1062 was used as the compatibilizer. ToughTec H1062 is a non-reactive compatibilizer.

[0067] [Example 3] The thermoplastic resin composition of Example 3 was obtained in the same manner as in Example 1, except that FP-2100JC was used as the flame retardant. FP-2100JC is an intomessent flame retardant.

[0068] [Example 4] A thermoplastic resin composition for Example 4 was obtained in the same manner as in Example 1, except that 80% by weight of TOPAS 8007S-04 was used as the cyclic olefin resin, 10% by weight of Modiper A4100 was used as the compatibilizer, and 10% by weight of FCP-680 was used as the flame retardant. FCP-680 is a bromo compound.

[0069] [Example 5] A thermoplastic resin composition of Example 5 was obtained in the same manner as in Example 1, except that SI-30-10 was used as the flame retardant. SI-30-10 is a silicon-based compound.

[0070] [Example 6] The thermoplastic resin composition of Example 6 was obtained in the same manner as in Example 1, except that 60% by weight of TOPAS 8007S-04 was used as the cyclic olefin resin, 10% by weight of Modiper A4100 was used as the compatibilizer, and 30% by weight of aluminum hydroxide was used as the flame retardant.

[0071] [Example 7] The thermoplastic resin composition of Example 7 was obtained in the same manner as in Example 1, except that TOPAS 8007S-04 was used as the cyclic olefin resin at 50% by weight, Modiper A4100 was used as the compatibilizer at 10% by weight, and PX-200 was used as the flame retardant at 40% by weight.

[0072] [Example 8] The thermoplastic resin composition of Example 8 was obtained in the same manner as in Example 1, except that 50% by weight of TOPAS 8007S-04 was used as the cyclic olefin resin, 30% by weight of Modiper A4100 was used as the compatibilizer, and 20% by weight of PX-200 was used as the flame retardant.

[0073] [Example 9] The thermoplastic resin composition of Example 9 was obtained in the same manner as in Example 1, except that ARTOND4000 was used in an amount of 70% by weight as the cyclic olefin resin.

[0074] [Comparative Example 1] Comparative Example 1 was obtained in the same manner as in Example 1, except that 70% by weight of TOPAS8007S-04 was used as the cyclic olefin resin and 30% by weight of PX-200 was used as the flame retardant, and no compatibilizer was used.

[0075] [Comparative Example 2] A thermoplastic resin composition for Comparative Example 2 was obtained in the same manner as in Example 1, except that 80% by weight of TOPAS8007S-04 was used as the cyclic olefin resin, 20% by weight of Modiper A4100 was used as the compatibilizer, and no flame retardant was used.

[0076] [evaluation] The flame retardancy and toughness tests for Examples 1 to 9 and Comparative Examples 1 and 2 obtained as described above were carried out as follows.

[0077] (1) Flame retardancy test After drying the resin composition at 80°C for 4 hours, it was molded into strip-shaped test pieces measuring 125 mm in length, 13 mm in width, and 1.6 mm in thickness, and a flame retardancy test was performed.

[0078] The flame retardancy test was conducted by conditioned the above test specimens in a constant temperature room at 23°C and 50% humidity for 48 hours, then storing them in a constant temperature room at 70°C for 168 hours, and finally performing the test in accordance with the well-known UL94 (UL94V) test (flammability test for plastic materials for equipment components) as defined by Underwriters Laboratories (UL) in the United States. As is well known, UL94V is graded into HB, V2, V1, V0, 5VB, and 5VA, with flame retardancy increasing in this order (HB being the least flame retardant and 5VA being the most flame retardant).

[0079] The test specimens for each example and comparative example were evaluated, and the evaluation results were classified as follows. ◎: 5VA, 5VB, V0 ○: V1 and V2 △:HB ×: notV (non-standard / has practical problems)

[0080] (2) Toughness test (Charpy impact test) After drying the resin composition at 80°C for 4 hours, it was molded into strip-shaped test pieces with a length of 80 mm, a width of 10 mm, and a thickness of 4 mm, and a Charpy impact test was conducted at 23°C in accordance with "JIS K7110" and evaluated according to the following evaluation criteria.

[0081] ◎: 20 kJ / m 2 and above ○: 10 kJ / m 2 10 kJ / m or more and less than 20 kJ / m 2 less than △: 5 kJ / m 2 10 kJ / m or more and less than (no practical problem) 2 ×: 5 kJ / m 2 less than (practical problem)

[0082] The composition of each of the above resin compositions and the evaluation results are shown in Table 1 below.

[0083]

Table 1

[0084]

[0085] <00003)39>When comparing Examples 1 to 9 with Comparative Example 1, Examples 1 to 9 contain a compatibilizer, while Comparative Example 1 does not contain a compatibilizer. In such Examples 1 to 9 and Comparative Example 1, Examples 1 to 9 containing a compatibilizer had good toughness with the measurement result of the Charpy impact test being 5 kJ / m 2 or more, while Comparative Example 1 was 4 kJ / m 2 and had poor toughness. This is considered to be because without a compatibilizer, the flame retardant does not disperse in the thermoplastic resin composition, and the undispersed flame retardant becomes the fracture point.

[0085]

[0086] Example 1 contained a reactive compatibilizer (Modiper A4100), while Example 2 contained a non-reactive compatibilizer (ToughTec H1062). Comparing Example 1 and Example 2, Example 1 showed better flame retardancy and toughness.

[0087] Example 1 contains a phosphate ester-based flame retardant (PX-200), while Example 3 contains an intramescent-based flame retardant (FP-2100JC). Comparing Example 1 and Example 3, Example 1 showed higher flame retardancy and toughness.

[0088] Example 1 contained 20% by weight of a phosphate ester-based flame retardant (PX-200), while Example 4 contained 10% by weight of a bromo-based flame retardant (FCP-680). Comparing Example 1 and Example 4, Example 4 showed higher toughness.

[0089] Example 1 contains a phosphate ester-based flame retardant (PX-200), while Example 5 contains a silica compound-based flame retardant (SI-30-10). Comparing Example 1 and Example 5, Example 1 showed higher flame retardancy and toughness.

[0090] Example 1 contains 70% by weight of cyclic olefin resin and 20% by weight of a flame retardant (Modiper A4100), while Example 6 contains 60% by weight of olefin resin and 30% by weight of a flame retardant (aluminum hydroxide). Comparing Example 1 and Example 6, Example 1 had higher toughness. This indicates that toughness decreases when the proportion of flame retardant is too high.

[0091] Example 1 contains 70% by weight of cyclic olefin resin and 20% by weight of flame retardant (Modiper A4100), while Example 7 contains 50% by weight of olefin resin and 40% by weight of flame retardant (aluminum hydroxide). Comparing Example 1 and Example 7, Example 1 had higher toughness. This indicates that toughness decreases when the proportion of flame retardant is too high.

[0092] Example 1 contains 70% by weight of cyclic olefin resin and 10% by weight of compatibilizer, while Example 8 contains 50% by weight of cyclic rheofin resin and 30% by weight of compatibilizer. Comparing Example 1 and Example 8, Example 1 showed higher flame retardancy and toughness. This indicates that too much compatibilizer reduces flame retardancy and toughness.

[0093] Example 1 uses nobornene as the monomer and contains a cyclic olefin resin (TOPAS8007S-04) having a monocyclic structure, whereas Example 9 uses a compound having a tetracyclododecene structure as the monomer and contains a cyclic olefin resin (ARTOND4000) having a tricyclodecane structure (polycyclic structure). Comparing Example 1 and Example 9, Example 1 showed higher toughness. From this, it is thought that in cyclic olefin resins, a smaller number of ring structures derived from the cyclic olefin monomer results in higher toughness (monocyclic is considered better than polycyclic). [Industrial applicability]

[0094] According to the present invention, a thermoplastic resin composition that achieves both flame retardancy and toughness can be obtained. Therefore, the thermoplastic resin composition of the present invention is expected to be used in various molded articles where flame retardancy and toughness are required.

Claims

1. It contains a cyclic olefin resin, a flame retardant, and a compatibilizer. The material was molded into a rectangular test specimen measuring 125 mm in length, 13 mm in width, and 1.6 mm in thickness. It was then conditioned for 48 hours in a constant temperature chamber at 23°C and 50% humidity, and subsequently stored for 168 hours in a constant temperature chamber at 70°C. Afterward, a flame retardancy test was conducted in accordance with UL94V, and the evaluation was HB or higher. A strip-shaped test specimen measuring 80 mm in length, 10 mm in width, and 4 mm in thickness was formed, and a toughness test was conducted at 23°C in accordance with JIS K7110. The Charpy impact strength was evaluated at 5 kJ / m². ２ That's all. The cyclic olefin resin is a copolymer of a cyclic olefin and a compound having an α-olefin, and the content of the cyclic olefin resin is 45% by weight or more and 85% by weight or less. The flame retardant is one or more compounds selected from the group consisting of phosphorus-based compounds, halogen-based compounds, silicon-based compounds, and inorganic compounds, and the content of the flame retardant is 5% by weight or more and 35% by weight or less. The compatibilizer is one or more copolymers selected from the group consisting of copolymers of monomers having reactive functional groups and other monomers, copolymers in which reactive functional groups are introduced into a base resin, graft copolymers in which different types of polymers are chemically bonded in a branched or crosslinked structure in the form of a main chain and a secondary chain, and block copolymers in which different types of polymers consist of soft blocks and hard blocks, and the content of the compatibilizer is 5% by weight or more and 25% by weight or less. Thermoplastic resin composition.

2. The thermoplastic resin composition according to claim 1, wherein the cyclic olefin resin, the flame retardant, and the compatibilizer are melt-kneaded together.

3. The thermoplastic resin composition according to claim 1 or 2, wherein the cyclic olefin resin is a copolymer in which at least cycloolefin is used as a monomer and which has arbitrary substituents, the flame retardant is a phosphate ester compound, and the compatibilizer is a copolymer having a reactive functional group.

4. A thermoplastic resin molded article obtained by molding the thermoplastic resin composition according to claim 1 or 2.

5. A method for producing a thermoplastic resin composition according to claim 1, comprising melt-kneading the cyclic olefin resin, the flame retardant, and the compatibilizer.

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