WO2023232655A1

WO2023232655A1 - Flame retardant resin composition and molded article thereof

Info

Publication number: WO2023232655A1
Application number: PCT/EP2023/064145
Authority: WO
Inventors: Kota Fujiwara
Original assignee: Bioenvision Technology As
Priority date: 2022-05-31
Filing date: 2023-05-25
Publication date: 2023-12-07
Also published as: JP2023176385A

Abstract

[Problem] Provided is a flame-retardant resin composition from which a molded article having excellent flame-retardancy is obtained. [Solution] A flame-retardant resin composition includes: (A) an olefin-based resin; (B) a phosphorus-based flame-retardant; and (C) a polyhedral oligomeric silsesquioxane (POSS).

Description

FLAME RETARDANT RESIN COMPOSITION AND MOLDED ARTICLE

THEREOF

FIELD OF THE INVENTION

[0001]

The present disclosure relates to a flame-retardant resin composition from which a molded article having excellent flame retardancy is obtained and a molded article thereof.

BACKGROUND ART

[0002]

Polyhedral oligomeric silsesqui oxane (POSS) are known to be used as a flame retardant.

[0003]

Patent Document 1 discloses an invention relating to a transparent flame retardant material including: a main polymer that is acryl, acrylic glass, poly(methyl methacrylate), acrylic resin, plastic, or a combination thereof; a nanostructured filler which is POSS; and at least one crosslinking agent.

[0004]

Patent Document 2 discloses an invention relating to a polymer obtained by polycondensation of: a) at least one phosphorus-containing monomer selected from adducts of: al) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and/or nuclear-sub stituted DOPO derivatives; and a2) at least one unsaturated di- or polycarboxylic acid or an ester or anhydride thereof; b) at least one secondary diamine; and c) an optional different monomer. Paragraph [0064] discloses that POSS can be contained as a flame retardant.

Citation List

Patent Document

[0005]

Patent Document 1 : JP 2020-514491 T

Patent Document 2: JP 2021-500468 T SUMMARY OF THE INVENTION

Technical Problem

[0006]

An object of the present disclosure is to provide a flame-retardant resin composition from which a molded article having excellent flame retardancy is obtained, and a molded article thereof.

Solution to Problem

[0007]

The present disclosure provides a flame-retardant resin composition containing: (A) an olefin-based resin; (B) a phosphorus-based flame-retardant; and (C) a polyhedral oligomeric silsesquioxane (POSS), and a molded article thereof.

Advantageous Effects of Invention

[0008]

By combining the phosphorus-based flame-retardant as the component (B) with a small amount of the POSS as the component (C), the molded article obtained from the flame-retardant resin composition according to the present disclosure has comparable mechanical properties and thermal properties, but can be greatly enhanced in flame retardancy, as compared with molded articles obtained from compositions containing the same phosphorus-based flame retardant.

By adjusting the substituents on the POSS, the properties of the POSS can be tuned to its application. Tuning the chemical nature of the substituents (such as hydrophobicity, charge, polarity...) allows for better mixability of the different components in the composition. Tuning the melting point of the POSS allows the POSS to be more stable in powder or flakes; and make it easier to handle during compounding and/or dispersion, for example in the process of molding an article. If the melting point of the POSS is too low, i.e. below the working temperature during compounding and/or dispersion, then the POSS will melt and not be homogenously dispersed. This better mixability and stability enhance the flame -retard ant properties of the resin composition, and of the molded article thereof.

Description of Embodiments

[0009]

Flame-retardant resin composition For the olefin-based resin, which is the component (A), a homopolymer of an olefin monomer such as ethylene, propylene, or butylene, or a copolymer with a different monomer copolymerizable with the ethylene monomer can be used.

Among these, a propylene-based resin is preferable. The propylene-based resin may be a homopolymer of propylene, or may be a copolymer of propylene and a different copolymerizable monomer.

Other copolymerizable monomers can include: olefin-based monomers, such as a- C2 to 20 chain olefins exemplified by ethylene, 1 -butene, isobutene, 1 -pentene, and 4-methyl-l -pentene, and cyclic olefins; vinyl ester-based monomers, such as vinyl acetate and vinyl propionate; (meth)acrylic monomers, for example, (meth)acrylic acid, alkyl (meth)acrylate, vinyl cyanide-based monomers such as (meth)acrylonitrile; diene-based monomers such as butadiene; unsaturated polyvalent carboxylic acids or acid anhydrides thereof, such as maleic acid, itaconic acid, citraconic acid or acid anhydrides thereof; and imide-based monomers, for example, mal eimide and N-substituted maleimides exemplified by N-alkyl mal eimides such as N-Cl to 4 alkylmaleimides. These copolymerizable monomers can be used alone, or two or more thereof can be used in combination.

More specifically, the polypropylene-based resin can be: homopolypropylene, which is a homopolymer; or a copolymer, for example, a propylene-a2 to 20 chain olefin copolymer (random copolymer, block copolymer, or the like) having a propylene content of 80 mass% or greater such as a propylene-ethylene copolymer, a propylene-butene-1 copolymer, and a propylene-ethylene-butene-1 copolymer.

Among these polypropylene-based resins, homopolypropylene, polypropylene modified with an unsaturated polycarboxylic acid or an acid anhydride thereof, or a combination thereof is preferable.

[0010]

The component (B) is a phosphorus-based flame retardant.

The phosphorus-based flame retardant as the component (B) may include an organic phosphoric acid compound and an organic phosphate salt compound, and an organic phosphate salt compound is preferable.

In a preferred embodiment, component (B) may include phosphate, phosphonate, phosphinate, phosphine or phosphine oxide.

In a preferred embodiment, component (B) is halogen free.

For the organic phosphate salt compound, for example, those described in JP 2017- 43707A can be used. The organic phosphate salt compound can be: an organic phosphate ester compound such as triphenyl phosphate, tricresyl phosphate, bisphenol-A-bisdiphenyl phosphate, or resorcinol-bisdiphenyl phosphate; a phosphate salt compound such as an ammonium polyphosphate salt, a melamine polyphosphate salt, a piperazine polyphosphate salt, a piperazine orthophosphate salt, a melamine pyrophosphate salt, a piperazine pyrophosphate salt, a melamine polyphosphate salt, a melamine orthophosphate salt, calcium phosphate, or magnesium phosphate; or a mixture thereof.

[ 0011]

In the above exemplification of the phosphate salt compounds, compounds in which melamine or piperazine is replaced with N,N,N',N'-tetramethyldiaminomethane, ethylene diamine, N,N'-dimethylethylenediamine, N,N'-diethylethylenediamine, N,N-dimethylethylenedi amine, N,N-diethylethylenediamine, N,N,N',N'- tetramethylethylenediamine, N,N,N',N'-di ethylethylenediamine, 1,2- propanediamine, 1,3-propanediamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9- diaminononane, 1,10-diaminodecane, trans-2,5-dimethylpiperazine, l,4-bis(2- aminoethyl)piperazine, l,4-bis(3-aminopropyl)piperazine, acetoguanamine, benzoguanamine, acrylguanamine, 2,4-diamino-6-nonyl-l,3,5-triazine, 2,4-diamino- 6-hydroxy- 1,3, 5 -triazine, 2-amino-4,6-dihydroxy-l,3,5-triazine, 2,4-diamino-6- methoxy-l,3,5-triazine, 2, 4-diamino-6-eth oxy- 1,3, 5 -triazine, 2,4-diamino-6- propoxy- 1,3, 5 -triazine, 2,4-diamino-6-isopropoxy-l,3,5-triazine, 2,4-diamino-6- mercapto-l,3,5-triazine, 2-amino-4,6-dimercapto-l,3,5-triazine, ammeline, benzguanamine, acetoguanamine, phthalodiguanamine, melamine cyanurate, melamine pyrophosphate, butylenediguanamine, norbornenediguanamine, methylenediguanamine, ethylenedimelamine, trimethylenedimelamine, tetramethylenedimelamine, hexamethylenedimelamine, 1,3-hexylenedimeramine or the like can be similarly used.

Commercially available products can include ADEKA STAB FP2000,

FP2100, FP2200, and FP2500 (mixtures containing a phosphate salt) from ADEKA

CORPORATION, and ammonium polyphosphate.

[0012]

The POSS, which is the component (C), is described for example in JP 2019- 537506 T, WO2018/016367, JP 2014-196494 A and WO2022189024, and is represented by the following structural formula: [Chem. l]

[0013]

In the formula, R is defined as follows, but is not limited thereto, and includes the same R as in known POSS:

Each R may be the same or different.

R represents an alkyl group, aryl group, or cycloalkyl group, for example, having from 1 to 50 carbon atoms, or from 2 to 30 carbon atoms, or from 4 to 18 carbon atoms, such as a substituted or unsubstituted aliphatic hydrocarbon group or an aromatic hydrocarbon group.

The hydrocarbon group can be cyclic, branched or linear.

The hydrocarbon group may be saturated or may include unsaturation.

The hydrocarbon group can be substituted or un substituted.

When the hydrocarbon group has a substituent, it may have one or more groups selected from the group consisting of halogen, methyl, ethyl, isobutyl, isooctyl, cyclopentyl, cyclohexyl, vinyl, styryl, trimethylsiloxyl, tri chloro silyl ethyl, trichlorosilylpropyl, dichlorosilylethyl, chlorosilylethyl, phenyl, chlorobenzyl, cyanoethyl, cyanopropyl, norbornenyl, fluoro, silanol, dimethylsilane, alkoxy, methacrylate, silane, aniline, amine, phenol, and alcohol as substituents in a part of the cyclic, branched or linear hydrocarbon group. In a certain embodiment, the hydrocarbon group is partially fluorinated or perfluorinated.

Preferred examples of R include aminoalkyl groups, p-aminophenyl groups, and p- nitrophenyl groups. R of the POSS can be functionalized with a polar functional group by a routine method.

In a preferred embodiment, the component (C) is halogen free. [0014]

The POSS as the component (C) preferably has an amino group as a functional group R and an alkyl group. These POSS have shown a particularly advantageous combination of flame-retardant properties as well as better mixability properties towards polyolefins / composite, i.e. they are more homogeneously dispersed in the final composition and article.

The alkyl group is preferably an alkyl group having from 3 to 10 carbon atoms, and more preferably a propyl group or an octyl group.

The component (C) is preferably amino-propyl-POSS, amino-octyl-POSS, amino- phenyl-POSS, or amino-vinyl-POSS.

[0015]

A ratio [(C)/(B)] of the component (B) to the component (C) in the flame retardant resin composition according to an embodiment of the present disclosure is preferably from 0.010 to 0.080, more preferably from 0.015 to 0.075, and even more preferably from 0.020 to 0.070, to enhance flame retardancy.

[0016]

As for the contents of the component (A), the component (B), and the component (C) in the flame retardant resin composition according to an embodiment of the present disclosure, relative to 100 parts by mass of the component (A), the content of the component (B) is preferably from 20 to 60 parts by mass, more preferably from 30 to 55 parts by mass, and even more preferably from 35 to 50 parts by mass, and the content of the component (C) is preferably from 0.05 to 5.0 parts by mass, more preferably from 0.1 to 4.5 parts by mass, and even more preferably from 0.5 to 4.0 parts by mass.

[0017]

The flame-retardant resin composition according to an embodiment of the present disclosure can further contain a component (D), an inorganic filler.

For the inorganic filler as the component (D), a type and an amount thereof that are necessary for imparting mechanical properties, thermal properties, and the like according to the application of the molded article obtained from the flame-retardant resin composition.

For the inorganic filler, a fibrous filler or a powdered filler can be used. Examples of the fibrous filler can include glass fibers, carbon fibers, metallic fibers such as stainless fibers, aluminum fibers, and brass fibers, gypsum fibers, ceramic fibers, zirconia fibers, alumina fibers, silica fibers, titanium oxide fibers, silicon carbide fibers, and lock wool.

Examples of the powdered filler can include talc, barium sulfate, and calcium carbonate.

[0018]

The flame-retardant resin composition according to an embodiment of the present disclosure can contain, according to need, a carbonization accelerator, a flameretardant aid, a blowing agent, an antioxidant, a lubricant, and the like as described, for example, in JP 2020-66737 A.

[0019]

The flame-retardant resin composition according to an embodiment of the present disclosure may contain only phosphorus-based flame retardant, which is the component (B), as the flame-retardant, but may also contain a small amount of a different flame-retardant depending on the application.

When a different flame-retardant is contained, a content thereof is preferably set to 10 mass% or less in a total amount of the phosphorus-based flame-retardant as the component (B) and the different flame-retardant.

[0020]

The flame-retardant resin composition according to an embodiment of the present disclosure can further contain a metal oxide to enhance flame retardancy.

Examples of the metal oxide include magnesium oxide, calcium oxide, zinc oxide, manganese oxide, tin oxide, alumina white, iron oxide, copper oxide, alumina trihydrate and magnesium trihydrate.

A content of the metal oxide in the flame-retardant resin composition is preferably from 0.5 to 5 mass%.

[0021]

The flame-retardant resin composition according to an embodiment of the present disclosure can contain, according to need, any other additives including stabilizers [e.g., thermal stabilizers (phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof), antioxidants (such as hindered phenols, hindered amines, and phosphorus-based antioxidants), and UV absorbers (benzophenone-based UV absorbers, benzotriazole-based UV absorbers, and triazine- based UV absorbers)], release agents [e.g., waxes (polyethylene waxes, higher fatty acid esters, and fatty acid amides), and silicone oil], antistatic agents, colorants, and the like.

[0022]

The flame-retardant resin composition according to an embodiment of the present disclosure can be manufactured, for example, by:

(i) a method of premixing respective components in a mixer (a tumbler, a type V blender, a Henschel mixer, a Nauta mixer, a ribbon mixer, a mechanochemical device, an extrusion mixer, or the like), melt-kneading the mixture with a melt kneader (a uniaxial or vent-type twin-screw extruder, or the like), and pelletizing or flaking the melt-kneaded product with a pelletizing means (a pelletizer or the like) or a flaking means;

(ii) a method of preparing a master batch of desired components, mixing the master batch with other components according to need, melt-kneading the mixture with a melt-kneader, and pelletizing the melt-kneaded product; or

(iii) a method of supplying respective components to a melt-kneader, melt-kneading them, and pelletizing the melt-kneaded product.

[0023]

Molded article

The molded article according to an embodiment of the present disclosure is a molded article formed from the flame-retardant resin composition described above and is molded in a shape and a size depending on the application, for example.

As a molding method, a known resin molding method such as an injection molding method, an extrusion molding method, a compression molding method, or a vacuum molding method can be applied.

[0024]

Each aspect disclosed in the present specification can be combined with any other feature disclosed herein.

Note that the configurations, combinations thereof, and the like in each embodiment of the present disclosure are examples, and various configurational additions, omissions, substitutions, and other changes may be made, as appropriate, without departing from the spirit of the disclosure of the present invention. The present disclosure is not limited by the embodiments and is limited only by the claims. Examples

[0025]

Components used

Component (A):

Homopolypropylene: PMB02A available from SunAllomer Ltd.

Acid-modified polypropylene: maleic acid-modified polypropylene, Modic P908 available from Mitsubishi Chemical Corporation

Component(B)

Phosphorus-based flame-retardant: ADEKA STAB FP2100JC available from ADEKA CORPORATION

Component(C)

POSS: Amino-propyl-POSS, SF453 available from Funzionano

Component(D)

Glassfiber: ECS03 T-480 available from Nippon Electric Glass Co., Ltd.

Other

Phenolic antioxidant: Irganox 1010 available from BASF

Phosphorus-based antioxidant agent: Irgafos 168 available from BASF

Calcium stearate: SC- 100 available from SAKAI CHEMICAL INDUSTRY CO., LTD.

[0026]

Examples 1 and 2 and Comparative Example 1

The components (A), (B), and (C) and other components shown in Table 1 were dry-blended.

Then, the mixtures were supplied from the hopper of a twin-screw extruder ("TEX30a" available from the Japan Steel Works, Ltd., at 230°C). Further, the component (D) was supplied from the side feeder. The mixtures were melt-kneaded and shaped to obtain pellets of flame-retardant resin compositions.

The pellets were used and charged into an injection molding machine (FANUC ROBOSHOT a-S150iA available from FANUC Corporation, with the mold at 50°C and the molding temperature at 235°C) to obtain molded articles. The following tests were performed. The results are shown in Tablet .

[0027]

(1) Flame retardancy test Test pieces (resin molded articles) having a thickness of 1.5mm, which were made of the flame-retardant resin compositions of the Examples and the Comparative Examples, were tested in a UL 94 vertical burning test (V test) for bar specimens (125 mm x 13 mm) using a 20 mm flame.

[0028] (2) Tensile strength (MPa)

Measured in accordance with ISO527.

[0029]

(3) Charpy impact strength (kJ/m²)

Notched Charpy impact strength was measured in accordance with ISO 179/leA. [0030]

(4) Load deflection temperature (°C) (1.8MPa)

Load deflection temperature was measured in accordance with ISO75.

[0031]

[Tablel]

In the table, D indicates that dripping occurred during the test, and * indicates that cotton was ignited.

[0032]

As is clear from Tablet, in Examples 1 and 2, it was possible to significantly enhance flame retardancy by blending a very small amount of the component (C) with respect to the component (B), the phosphorus-based flame-retardant.

Industrial Applicability

[0033]

The flame-retardant resin composition of the present disclosure can be utilized for resin components that are required to have flame retardancy, such as housing equipment, electrical and electronic devices, OA equipment, and interior components of automobiles including center console, installation panel, glove box, center cluster, door pocket, kicking plate, battery covers and the like.

Claims

[Claiml]

A flame-retardant resin composition comprising: (A) an olefin-based resin; (B) a phosphorus-based flame retardant; and (C) a polyhedral oligomeric silsesquioxane (POSS).

[Claim2]

The flame-retardant resin composition according to claim 1, wherein [(C)/(B)], a mass ratio of the component (B) to the component (C), is in a range of from 0.010 to 0.080.

[Claim3]

The flame-retardant resin composition according to claim 1 or 2, wherein contents of the component (A), the component (B), and the component (C) are that, relative to 100 parts by mass of the component (A), the content of the component (B) is from 20 to 60 parts by mass and the content of the component (C) is from 0.05 to 5.0 parts by mass.

[Claim4]

The flame-retardant resin composition according to any one of claims 1 to 3, wherein the olefin-based resin as the component (A) comprises a polypropylene.

[Claim5]

The flame-retardant resin composition according to any one of claims 1 to 4, wherein the phosphorus-based flame-retardant as the component (B) is one or more phosphate salts selected from a piperazine orthophosphate salt, a piperazine pyrophosphate salt, a piperazine polyphosphate salt, a melamine orthophosphate salt, a melamine pyrophosphate salt, and a melamine polyphosphate salt.

[Claim6]

The flame-retardant resin composition according to any one of claims 1 to 5, wherein the POSS as the component (C) has an amino group as a functional group and a saturated or unsaturated hydrocarbon group.

[Claim?]

The flame-retardant resin composition according to any one of claims 1 to 6, further comprising (D) an inorganic filler.

[Claim8] A molded article obtained from the flame-retardant resin composition described in any one of claims 1 to 7.