JP3414540B2 - Flame retardant thermoplastic resin composition and molded article thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to flame retardancy, mechanical strength,
The present invention relates to a flame-retardant thermoplastic resin composition having an excellent balance of heat resistance, moldability, appearance of molded products, chemical resistance, dimensional stability and the like, and a molded product thereof. Specifically, it consists of an amorphous thermoplastic resin, a crystalline thermoplastic resin, and a flame retardant, and the amorphous thermoplastic resin forms a matrix (continuous phase) and the crystalline thermoplastic resin forms a matrix. In a flame-retardant thermoplastic resin composition in which a portion and a flame retardant are selectively present in the amorphous thermoplastic resin, a specific amount of fibrous and / or plate-like inorganic filler The present invention relates to a flame-retardant thermoplastic resin composition excellent in flame retardancy, mechanical strength, heat resistance, moldability, chemical resistance, dimensional stability and the like, and a molded product thereof.

[0002]

2. Description of the Related Art A polymer blend composed of a combination of two or more kinds of resins takes advantage of each resin,
It is characterized in that a balanced composition can be obtained by compensating for the disadvantages.In particular, a combination of a crystalline thermoplastic resin and an amorphous thermoplastic resin is highly effective in practical use, and various combinations can be performed. It is being appreciated.

Amorphous thermoplastic resins are generally useful resins having excellent heat resistance and dimensional stability. For example, polyphenylene ether (hereinafter referred to as “PPE”) has excellent heat resistance and impact resistance. However, the moldability is extremely poor, and it has the drawback that injection molding is extremely difficult when used alone. In order to improve such a defect, a material having a relatively well-balanced moldability, impact resistance and heat resistance was developed by blending styrene resin with PPE, and it was marketed as one of engineering plastics. ing. For example, US Pat.
No. 83435 discloses a composition of PPE and high impact polystyrene. However, although this product has poor solvent resistance and improved moldability, it cannot be said that the balance between heat resistance and impact resistance is sufficient.

Further, in JP-A-51-28659, PPE is blended with styrene resin and rubber or rubber-modified styrene resin, and the average particle diameter of the rubber is 0.5 to 2 μm.
By further improving the impact resistance of the composition,
JP-A-56-460 discloses a composition in which a styrene resin and a rubber or a rubber-modified styrene resin are blended with PPE and the gel fraction thereof is regulated. However, although these compositions have improved impact resistance and the like, they cannot be said to have a large amount of sink marks and warpage after molding and a sufficient surface impact strength which is a practical strength.

In the field where high rigidity is required, fibrous inorganic fillers such as glass fibers and carbon fibers and plate-like inorganic fillers such as talc and mica are filled, but in this case as well. The drawback of poor solvent resistance remains, and the drawback of poor moldability becomes more prominent.

On the other hand, crystalline resins are excellent in solvent resistance and moldability and are used in various fields. For example, olefin resins are widely used for automobile parts, home electric appliances, daily necessities, etc. because of their excellent organic solvent resistance and moldability. However,
Due to its poor heat resistance and lack of dimensional stability due to its large expansion coefficient, it cannot be used for large parts that require heat resistance, especially automobile fenders, wheel covers, etc., and its applications have been limited. In order to solve this, for example, studies have been made to add talc, which is an inorganic filler, but when talc is added, there is a problem that impact resistance is lowered. In order to improve the balance, a composition containing talc and ethylene-propylene rubber is disclosed in JP-A-60-
No. 3420, and a composition improved in appearance by further adding polyethylene is disclosed in JP-A-59-49252 and JP-A-59-49252.
No. 1-276840 and 63-65223, respectively. However, the molded products using these compositions are not always satisfactory in balance of mechanical strength, appearance of molded products, and dimensional stability, and have a problem of low surface hardness.

Further, in the field where high rigidity is required, fibrous inorganic fillers such as glass fiber and carbon fiber and plate-like inorganic fillers such as talc and mica are filled, but crystalline thermoplastic resin is used. When such an inorganic filler is filled in, the molded product has a big defect that it is warped.

On the other hand, a material having excellent heat resistance and mechanical properties of PPE which is an amorphous thermoplastic resin, and excellent solvent resistance and good moldability of an olefin resin which is a crystalline thermoplastic resin is used. For the purpose of obtaining, a composition in which both are blended has been proposed. For example, JP-A-42-7069 discloses a blend of PPE and an olefin resin,
Attempts have been made to improve solvent resistance and impact resistance. However, in this composition, since the amount of the olefin resin compounded is small, the matrix is substantially PPE.
Therefore, the effect of improving solvent resistance and moldability is not sufficient.
Further, if the blending amount of the olefin resin is increased, the compatibility of both resins is not sufficient, and there is a problem that the layered peeling of the molded product occurs and the mechanical properties deteriorate. As an attempt to improve the compatibility, a composition containing a styrene-butadiene block copolymer or a hydrogenated product thereof has been disclosed in, for example, Japanese Patent Application Laid-Open Publication No. Sho-6 (1994) -58.
3-225642, 63-245353, 64
No. -40556 and Japanese Patent Publication No. 1-93647.

However, these compositions also have a drawback that the characteristics of the olefin resin are not sufficiently exhibited because the matrix is substantially composed of PPE or a combination of the PPE and the styrene block copolymer.

On the other hand, a composition in which PPE having excellent heat resistance and dimensional stability is dispersed using an olefin resin as a matrix is also disclosed. For example, JP-A-2-18555
No. 3, gazette discloses that P in a matrix of propylene polymer.
A composition in which PE and rubber are dispersed in a specific size and which is excellent in moldability, impact resistance, and appearance of a molded article has been proposed. However, since the matrix is a propylene polymer, it is a composition in which the excellent rigidity and heat resistance of PPE are not sufficiently exhibited and the surface hardness is low, and it does not satisfy the recent high demands of the market. .

Further, a blend of PPE and an olefin resin loses the excellent flame retardancy inherent in PPE. Therefore, a large amount of flame retardant is required to make both blends flame retardant, but the obtained flame retardancy is not always satisfactory, and as a result of blending a large amount of flame retardant, mechanical There was a drawback that the strength was significantly impaired.

In the field where high rigidity is required, these blends are filled with a fibrous inorganic filler such as glass fiber or carbon fiber or a plate-like inorganic filler such as talc or mica. , In that case,
It was difficult to solve the problems such as warping of molded products, which is a defect of crystalline thermoplastic resins, and the problems of solvent resistance and moldability, which are defects of amorphous thermoplastic resins, and there were practical problems. .

[0013]

Under the circumstances, the present invention provides a composition comprising a crystalline thermoplastic resin and an amorphous thermoplastic resin, such as PPE, an olefin resin and a flame retardant. A material that has been reinforced with inorganic fillers and has both desirable properties, that is, a material that has excellent flame retardancy and moldability, and that has a good balance of mechanical strength, heat resistance, rigidity, chemical resistance, and dimensional stability. The purpose is to provide.

[0014]

Under the present circumstances, the present inventors believe that the resin forming the matrix in the composition mainly controls various characteristics, and it is considered that the resin in the prior art does not have such properties. A composition in which a crystalline thermoplastic resin such as PPE is a matrix or a crystalline thermoplastic resin such as an olefinic resin is a matrix, and a flame retardant is present in at least the crystalline thermoplastic resin. It has been considered that it is difficult to develop a desired material having the above-mentioned preferable properties with a material reinforced with an inorganic filler.

Then, as a result of intensive studies based on a completely new idea, as a result, an amorphous thermoplastic resin, for example, a morphological part in which PPE is a matrix, and a crystalline thermoplastic resin, for example, an olefin resin in a matrix are used. A certain morphological part is present in the same composition or the same molded body, and the inorganic filler is a resin composition in which the flame retardant is selectively present in the amorphous thermoplastic resin. A composition having excellent flame retardancy, moldability, mechanical strength, heat resistance, rigidity and dimensional characteristics that cannot be achieved by the conventional technique by strengthening and preferably including an inorganic filler in a specific phase. The present invention was discovered and the present invention was reached.

That is, the present invention comprises (a) an amorphous thermoplastic resin, (b) a crystalline thermoplastic resin, and (c) a flame retardant, wherein the component (a) forms a matrix, and the component A thermoplastic resin composition characterized in that (b) is present in a dispersed form with a morphological portion forming a matrix, and component (c) is selectively present in component (a). (D) A flame-retardant thermoplastic resin composition containing 5 to 60% by weight of a fibrous and / or plate-like inorganic filler in the entire composition, and a molded product thereof. Hereinafter, the present invention will be described in detail.

<Constituent> In the present invention, the amorphous thermoplastic resin (a) means a resin which generally has a glass-like property and shows only a glass transition temperature when heated.
An amorphous thermoplastic resin having a glass transition temperature of 50 ° C. or higher is preferable. Further, the amorphous thermoplastic resin shows that it does not have a definite melting point or measurable heat of fusion, but in the present invention, it includes those that show some crystallinity when slowly cooled, and the effect of the present invention is obtained. It also includes those exhibiting crystallinity within a range not significantly impaired. The glass transition temperature, melting point, and heat of fusion can be measured using a differential scanning calorimeter. An example is DSC-II manufactured by PERKIN-ELMER. Using this device, the heat of fusion can be measured at a heating rate of 10 ° C. per minute. The sample is heated to a temperature above the expected melting point, then the sample is cooled at a rate of 10 ° C per minute, cooled to 20 ° C, left for about 1 minute and then heated at a rate of 10 ° C per minute. It can be measured by As the heat of fusion, the one that has a constant value within the experimental error range is adopted even if it is measured in any of the temperature rising and cooling cycles after the beginning. The amorphous thermoplastic resin in the present invention is defined as one having a heat of fusion of less than 1 calorie / gram as measured by the above method.

The amorphous thermoplastic resin used as the component (a) of the present invention includes PPE, an aromatic vinyl compound polymer,
Examples thereof include rubber-modified aromatic vinyl compound polymer, polycarbonate, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, and the like. At least one amorphous thermoplastic resin selected from these groups is included. It is a composition. One of the suitable amorphous thermoplastic resins (a) is PPE. PPE
Is the following general formula (II)

[0019]

[Chemical 2]

(In the formula, Q ₁ , Q ₂ , Q ₃ and Q ₄ are each selected from the group consisting of a hydrogen atom, a halogen atom and a substituted or unsubstituted hydrocarbon group, and are the same as each other. Which may be different) is a homopolymer or a copolymer composed of structural units represented by

A specific example of this PPE is poly (2,
6-dimethyl-1,4-phenylene ether), poly (2,6-diethyl-1,4-phenylene ether),
Poly (2,6-dipropyl-1,4-phenylene ether), poly (2-methyl-6-isopropyl-1,4-)
Phenylene ether), poly (2,6-dimethoxy-
1,4-phenylene ether), poly (2,6-dichloromethyl-1,4-phenylene ether), poly (2,
6-diphenyl-1,4-phenylene ether), poly (2,6-dinitrile-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), poly (2,5- Dimethyl-1,4-phenylene ether) and the like. These may be used in combination.

Suitable homopolymers of PPE are, for example, those composed of 2,6-dimethyl-1,4-phenylene ether units. A preferable copolymer is a random copolymer composed of a combination of the above unit and 2,3,6-trimethyl-1,4-phenylene ether unit.

The PPE used here preferably has an intrinsic viscosity of 0.2 to 0.8 dl / g at 30 ° C. measured in chloroform. More preferably 0.2-0.5d
1 / g, and particularly preferably 0.25-
It is 0.45 dl / g. The aromatic vinyl compound polymer used as the amorphous thermoplastic resin (a) in the present invention has the following general formula (III):

[0024]

[Chemical 3]

(In the formula, R represents a hydrogen atom, a halogen atom or a lower alkyl group, Z represents a hydrogen atom, a lower alkyl group, a halogen atom or a vinyl group, and n represents an integer of 1 to 5.) It is a homopolymer or a copolymer having a structural unit represented by.

Examples of the aromatic vinyl compound include styrene, α-methylstyrene, α-methoxystyrene,
Methylstyrene, dimethylstyrene, 2,4,6-trimethylstyrene, chlorostyrene, dichlorostyrene,
Examples thereof include bromostyrene and t-butylstyrene, and among them, styrene, α-methylstyrene and methylstyrene are preferable. These may be used alone or in combination of two or more.

Examples of the polycarbonate used as the amorphous thermoplastic resin (a) in the present invention include aromatic polycarbonate, aliphatic polycarbonate, and aliphatic-aromatic polycarbonate. Among them, 2,2-bis (4-oxyphenyl) alkane-based, bis (4-oxyphenyl) ether-based, bis (4-oxyphenyl)
Aromatic polycarbonates composed of bisphenols such as sulfone, sulfide or sulfoxide are preferable. Further, a polycarbonate composed of bisphenols substituted with halogen as required can also be used.

Although there is no limitation on the molecular weight of polycarbonate, it is generally 10,000 or more, preferably 20,000 to
40,000. As other amorphous resin (a),
Acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, etc. can also be used.

In the present invention, the crystalline thermoplastic resin used as the component (b) on the other hand is one that can be melted by heating and has a non-glass-like characteristic having a clear crystal structure or molecular structure, It shows a clear melting point with a measurable heat of fusion. The melting point and the heat of fusion can be measured using a differential scanning calorimeter.
Examples include the device and measuring method described in the section of amorphous thermoplastic resin. The crystalline thermoplastic resin in the present invention is defined as one having a heat of fusion measured by this method of 1 calorie / gram or more.

Examples of the crystalline thermoplastic resin (b) used in the present invention include olefin resins, polyamides, polyesters, polyacetals, halogen-containing thermoplastic resins, polysulfones, polyphenylene sulfides, liquid crystal polymers, and the like. A composition comprising at least one crystalline thermoplastic resin selected from

The preferred crystalline resin (b), which is an olefin resin, is a homopolymer of α-olefin, a copolymer of these α-olefins, or a main component of these α-olefin (s). And a copolymer containing other unsaturated monomer (a plurality of kinds may be used) as a subcomponent, if necessary. Here, the copolymer may be any copolymer such as block, random or graft or a composite thereof. Further, it also includes modified products of these olefinic polymers by chlorination, sulfonation, carbonylation and the like.

Examples of the above α-olefins include ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, etc., which have 2 to 8 carbon atoms because of their simplicity. Those are preferable. Examples of the unsaturated monomer include unsaturated organic acids such as (meth) acrylic acid, (meth) acrylic acid ester, maleic acid, etc., or their anhydrides, and derivatives such as esters.

Specific examples of these olefin resins include low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, polybutene, ethylene-propylene block or random copolymer. These may be used in combination.

Among these, as the olefin resin, a crystalline olefin polymer, for example, a crystalline homopolymer of ethylene or propylene, or ethylene and / or propylene containing ethylene or propylene as a main constituent The crystalline copolymer with the ethylenically unsaturated monomer of is preferable. Among these, particularly preferable examples are low-, medium-, and high-density polyethylene, polypropylene, and ethylene-propylene block copolymers, and among them, high-density polyethylene, polypropylene, and ethylene-propylene block copolymers are the most preferable in terms of rigidity. preferable.

The melt flow rate (hereinafter referred to as “MFR”; 230 ° C., load 2.16 kg) of the olefin resin used in the present invention is preferably 0.01 to 250 g / 10 minutes, and 0.05 to 200 g / minute. The range of 10 minutes is more preferable, and the range of 0.1 to 100 g / 10 minutes is particularly preferable. When the MFR value is lower than this range, molding workability is difficult, and when it is higher than this range, the mechanical strength level is not preferable.

Further, in the present invention, a functional group-modified derivative of the olefin resin can be used as a part of the olefin resin. The functional group-modified derivative as used herein means an olefinic resin obtained by treating an unsaturated organic acid or an anhydride thereof (for example, acrylic acid, maleic acid, itaconic acid or an anhydride thereof) or an unsaturated organic silane compound (for example, vinyltriene). Methoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane, propenyltrimethoxysilane) or the like, or an olefin resin graft-modified with an organic acid or an anhydride thereof. Is an ionomer obtained by metal-ionizing a part of the carboxyl groups bonded to the graft chain of. Further, as the functional group-modified derivative of the olefinic resin, in addition to the specific examples listed here, those in which a hydrophilic group is introduced by a grafting, block or random copolymerization method, a substitution reaction, an oxidation reaction, or the like are also included. Can be used.

Polyamide, which is an example of the crystalline thermoplastic resin (b), has a --CO--NH-- bond in the polymer main chain and can be melted by heating. Typical examples are nylon-4, nylon-6, nylon-6, and
6, nylon-4,6, nylon-12, nylon-
6, 10 and the like, and other well-known aromatic diamines, low crystallinity and amorphous polyamides containing monomer components such as aromatic dicarboxylic acids, and the like can also be used.

Preferred polyamides are nylon-6 or nylon-6,6, with nylon-6 being especially preferred. The polyamide used in the present invention preferably has a relative viscosity of 2.0 to 8.0 (measured in 98% concentrated sulfuric acid at 25 ° C.).

The polyester which is an example of the crystalline thermoplastic resin (b) includes, for example, a dicarboxylic acid or a lower alkyl ester thereof, an acid halide or an acid anhydride derivative thereof, and a glycol or a dihydric phenol according to a conventional method. A thermoplastic polyester produced by condensing

Specific examples of the aromatic or aliphatic dicarboxylic acid suitable for producing the thermoplastic polyester include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid and sebacic acid. , Terephthalic acid, isophthalic acid, p, p'-dicarboxydiphenyl sulfone, p-carboxyphenoxyacetic acid, p-
Carboxyphenoxypropionic acid, p-carboxyphenoxybutyric acid, p-carboxyphenoxyvaleric acid, 2,
Examples thereof include 6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid and the like, or a mixture of these carboxylic acids.

As the aliphatic glycol suitable for producing the thermoplastic polyester, a linear alkylene glycol having 2 to 12 carbon atoms, for example, ethylene glycol, 1,3
-Propylene glycol, 1,4-butanediol,
Examples are 1,6-hexanediol and 1,12-dodecamethylene glycol. Moreover, p-xylylene glycol is illustrated as an aromatic glycol compound,
Examples of the dihydric phenol include pyrocatechol, resorcinol, hydroquinone, and alkyl-substituted derivatives of these compounds. Other suitable glycols include:
1,4-Cyclohexanedimethanol is also included.

Other preferable thermoplastic polyesters include polyesters obtained by ring-opening polymerization of lactone. For example, polypivalolactone, poly (ε-caprolactone) and the like. Further, as still another preferable thermoplastic polyester, a polymer (Thermotropic Liquid Cry) that forms a liquid crystal in a molten state is used.
There is a polyester as a stallPolymer (TLCP). Polyesters that fall into these categories include Eastman Kodak X7G and Dartco X.
Typical products are ydar, Sumitomo Chemical's Econor, and Celanese's Vectra.

Among the thermoplastic polyesters listed above, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), poly (1,4-cyclohexanedimethylene terephthalate) (PCT), or liquid crystallinity. Polyester and the like are thermoplastic polyesters suitable for the thermoplastic resin composition of the present invention.

The viscosity of the thermoplastic polyester used here is such that the intrinsic viscosity measured at 20 ° C. in a phenol / 1,1,2,2-tetrachloroethane = 60/40 wt% mixed solution is 0.5 to 5. A range of 0.0 dl / g is preferable. It is more preferably 1.0 to 4.0 dl / g, and most preferably 2.0 to 3.5 dl / g. Intrinsic viscosity is 0.5
If it is less than dl / g, the impact resistance is insufficient and 5.0 dl
If it exceeds / g, the moldability will be poor.

Examples of the polyacetal which is an example of the crystalline thermoplastic resin (b) include a high molecular weight polyacetal homopolymer produced by polymerizing formaldehyde or trioxane. Polyacetal produced from formaldehyde has a high molecular weight and has a structure represented by the following formula.

[0046]

Embedded image H—O— (CH ₂ —O—CH ₂ —O) _x —H

Wherein the terminal groups are derived from a controlled amount of water and x represents a formaldehyde unit (preferably about 1500) attached in the form of a head-to-tail bond. It is common practice to convert end groups to ester or ether groups in order to increase their chemical resistance. The term polyacetal also includes polyacetal copolymers. Examples of these copolymers are formaldehyde and monomers or prepolymers of other substances capable of providing active hydrogen, such as alkylene glycols, polythiols, vinyl acetate-acrylic acid copolymers or reduced butadiene. -Block copolymers with acrylonitrile polymers. Formaldehyde or trioxane can be copolymerized with other aldehydes, cyclic ethers, vinyl compounds, ketene, cyclic carbonates, epoxides, isocyanates or ethers.

Specific examples of these compounds include ethylene oxide, 1,3-dioxane, 1,3-dioxene,
Mention may be made of epichlorohydrin, propylene oxide, isobutylene oxide or styrene oxide.
Examples of the halogen-containing thermoplastic resin that can be used in the present invention as the crystalline thermoplastic resin (b) include polymers such as tetrafluoroethylene, chlorotrifluoroethylene, and vinylidene fluoride. In addition to this, a homopolymer or a copolymer derived from vinylidene chloride can also be used. Among them, the halogen-containing thermoplastic resin is preferably a vinylidene fluoride homopolymer or copolymer, or a crystalline vinylidene chloride copolymer. As the crystalline thermoplastic resin (b), polysulfone which can be used in the present invention has the following formula (IV):

[0049]

[Chemical 5]

(Wherein Y represents an oxygen, sulfur or aromatic diol residue) and has at least some repeating units represented by the following formulae.

[0051]

[Chemical 6]

Examples thereof include those having any of the repeating units represented by: As the other crystalline thermoplastic resin (b), polyphenylene sulfide, liquid crystal polymer and the like can be used. In the present invention, other components that can be added include a block copolymer comprising an aromatic vinyl compound polymer block A and a conjugated diene compound polymer block B and a hydrogenated product thereof. The block copolymer referred to here is an aromatic vinyl compound-conjugated diene block copolymer having a structure having at least one chain block A derived from a vinyl aromatic compound and at least one block B derived from a conjugated diene. The arrangement of blocks A and B includes those having a linear structure, a branched structure or a tapered structure. Also, in some of these structures,
A random chain derived from a random copolymer portion of an aromatic vinyl compound and a conjugated diene may be included. Of these, those having a linear structure are preferable, and those having a triblock structure are more preferable.

Further, the hydrogenated product of the block copolymer is a block copolymer in which the aliphatic unsaturated bond of the block B is reduced by hydrogenation, and the unsaturated bond of the unsaturated bond which remains without being hydrogenated. The ratio is preferably 20% or less,
10% or less is more preferable but not limited. Further, it may be used in combination with a non-hydrogenated block copolymer.

The aromatic vinyl compound is preferably styrene, α-methylstyrene, paramethylstyrene, vinyltoluene or vinylxylene, and particularly preferably styrene. The conjugated diene is preferably 1,3-butadiene, isoprene, 2-methyl-
It is 1,3 butadiene.

Specific examples of the block copolymer include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer and the like, and a plurality of these may be used. In the aromatic vinyl compound-conjugated diene block copolymer, the proportion of the repeating units derived from the aromatic vinyl compound is preferably in the range of 10 to 80% by weight, more preferably 15 to 65% by weight.

These block copolymers or hydrogenated products thereof preferably have a toluene solution viscosity value at 25 ° C. in the range of 30,000 to 10 cp, more preferably 10,000 to 30 as a measure of their molecular weight.
cp. When it exceeds 30,000 cp, the moldability of the final composition becomes difficult, and when it is less than 10 cp, the mechanical strength level is low, which is not preferable.

Next, the flame retardant (c) used in the present invention is not particularly limited, and may be an organic phosphorus compound, a compound containing a phosphorus-nitrogen bond, elemental phosphorus, a halogenated organic compound, an antimony compound or two or more of them. Mixtures may be used. Organic phosphorus compounds are preferable, and mono- or polyphosphate compounds represented by the following general formula (I) are more preferable.

[0058]

[Chemical 7]

(In the formula, Re represents a residue obtained by removing two hydroxyl groups from hydroquinone, resorcinol, biphenol, bisphenol A, bisphenol F or bisphenol S, and R ₁ , R ₂ , R ₃ and R ₄ are each hydrogen. Represents an atom or an alkyl group having 1 to 6 carbon atoms, R ₁ , R ₂ ,
When each of R ₃ and R ₄ is two or more, they may be different from each other. n represents an integer of 0 to 10,
m1, m2, m3 and m4 each represent an integer of 1 to 3. )

At least one of R ₁ , R ₂ , R ₃ and R _{4 in} the general formula (I) is preferably a methyl group, and more preferably a methyl group.
The preferable range of n in the general formula (I) is 0 to 5 from the viewpoint of heat resistance and workability. Further, the flame retardant of the general formula (I) may be a mixture of flame retardants having different n.

The compounds of the general formula (I) in which n is 1 or more have a specific bifunctional phenol as a bonding group and have an alkyl-substituted or unsubstituted monofunctional phenol at the end of the structure. The specific bifunctional phenol means hydroquinone, resorcinol, biphenol, bisphenol A, bisphenol F and bisphenol S. As the alkyl-substituted monofunctional phenol, monoalkylphenol,
Dialkylphenol and trialkylphenol can be used alone or in combination. Of these, cresol, dimethylphenol (mixed xylenol) and trimethylphenol are preferable.

In the compound of the general formula (I), one or more monophosphate ester compounds in which n is 0 can be used, and specifically, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate can be used. , Trixylenyl phosphate, xylenyl diphenyl phosphate, tri (isopropylphenyl)
Phosphate, isopropyl phenyl diphenyl phosphate, diisopropyl phenyl phenyl phosphate, tri (trimethylphenyl) phosphate,
Examples thereof include tri (t-butylphenyl) phosphate. Of these, triphenyl phosphate, tricresyl phosphate, and cresyl diphenyl phosphate are preferable.

It is also preferable to use those flame-retardants which have been surface-treated according to the resin used.
Next, as a method of selectively allowing the flame retardant (c) to be present in the amorphous thermoplastic resin (a), a method of using a flame retardant compatible with the amorphous thermoplastic resin and a flame retardant A method in which an amorphous thermoplastic resin is kneaded in advance, a method in which a functional group having an affinity for a flame retardant is introduced into the amorphous thermoplastic resin, and a functional group having an affinity for the amorphous thermoplastic resin is used as a flame retardant. And the like.

As the fibrous and / or plate-like inorganic filler (d) used in the present invention, various known ones can be used. From the viewpoint of reinforcing effect, the fibrous inorganic filler used in the present invention preferably has L / D represented by the ratio of the diameter (D) and the length (L) of the fiber of 5 or more. Examples thereof include glass fibers, carbon fibers, whiskers such as potassium titanate, wollastonite, and the like, and these may be used in combination of two or more kinds.

From the viewpoint of reinforcing effect, the plate-like inorganic filler used in the present invention has L '/ D' represented by the ratio of average plate thickness (D ') to average particle size (L') of 5 or more. It is preferable that mica, talc, glass flakes, etc. be mentioned as an example of such a plate-like inorganic filler, and these may be used in combination of two or more kinds. Also,
It is also preferable to use those inorganic fillers which have been surface-treated according to the resin used.

It is more preferable that the inorganic filler is selectively present in the amorphous thermoplastic resin (a). As a method of selectively presenting these inorganic fillers in the amorphous thermoplastic resin component, a method of previously kneading the inorganic filler and the amorphous thermoplastic resin, or an affinity for the amorphous thermoplastic resin with the inorganic filler A method of introducing a functional group showing As a method for introducing a functional group having an affinity for an inorganic filler into the amorphous thermoplastic resin, various known methods can be used. For example, a method of carrying out a Kraft reaction of a functionalized compound having an unsaturated group and a polar group in the same molecule as the resin in a solution state or a molten state in the presence or absence of a peroxide, or polymerizing these resins. And a method of copolymerizing a functionalized compound having a polar group.

These functionalized resins (amorphous thermoplastic resins having the above-mentioned functional groups introduced) may be used alone,
Although it may be mixed with an unfunctionalized resin, the proportion of the functionalized compound in the resin after mixing is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and particularly preferably Is 0.1% by weight or more.

Further, as other components which can be added to the composition of the present invention as required, for example, antioxidants, weather resistance improvers, nucleating agents, flame retardants, impact resistance improvers well known in thermoplastic resins, A plasticizer, a fluidity improver, etc. can be used. Further, an organic filler, an organic reinforcing agent, and an inorganic filler other than the component (c),
For example, the addition of calcium carbonate, silica, clay, etc.
Effective in improving rigidity, heat resistance, dimensional stability, etc. For practical use, various colorants and dispersants thereof may be known ones.

<Morphology of Composition and Molded Product> The present invention comprises an amorphous thermoplastic resin (a), a crystalline thermoplastic resin (b) and a flame retardant (c), and the component (a) is a matrix ( The morphological portion forming a continuous phase) and the morphological portion forming the matrix of the component (b) are present in a dispersed manner.

For example, the form in which the component (a) forms a matrix and the component (b) forms a domain (dispersed phase) [morphological part (A)], or the component (b) forms a matrix, A mode in which (a) forms a domain [morphological part (B)], a mode in which the component (a) and the component (b) mutually form a continuous phase [morphological part (c)] are considered, and the component (a)
The morphological part in which the matrix forms the matrix and the morphological part in which the component (b) forms the matrix are present in a dispersed state, and the morphological part (A) appears at various places in the composition and the molded article thereof. Or the appearance of the morphological part (B) or the appearance of the morphological part (C).

For example, in the vicinity of the surface layer of the molded body, the morphological portion (A) appears, and the morphological portion (B) appears inside thereof.
On the contrary, the morphological portion (B) is formed near the surface layer, and the morphological portion (A) is formed inside.
Of course, the form portions (A), (B), and (C) may appear twice or more in the thickness direction of the molded body. Further, a form part only of (C) is also conceivable.

Here, the form parts (A), (B),
The confirmation of (C) can be carried out by a method in which the composition or the molded body is dyed with ruthenium tetroxide, an ultrathin section is prepared, and observation is performed using a transmission electron microscope. Further, the component (c) is characterized in that it is selectively present in the component (a) in any of the morphological parts (A), (B) and (C).

<Melt Shear Viscosity Ratio of Components (a) and (b) and Shear Rate Dependence of Melt Shear Viscosity Ratio> Among two or more kinds of thermoplastic resins used in the present invention, one component is an amorphous thermoplastic resin. When the resin (a) and the other component are crystalline thermoplastic resins (b), the form in the composition of the present invention composed of two or more types of thermoplastic resin compositions is such that the component (a) forms a matrix. The morphological portion and the morphological portion in which the component (b) forms a matrix are dispersed.

The melt shear viscosities of the components (a) and (b) may basically take any value, but in order to more efficiently achieve the above-mentioned intended form, the component (a) ) / Component (b), the value (S) of the melt shear viscosity ratio at 280 ° C. and a shear rate of 30 sec ⁻¹ is 280 of the component (a) / component (b) in the sea-sea structure [morphological part (c)]. When the melt shear viscosity ratio (W1) at a temperature of 30 ° C. and a shear rate of 30 sec ⁻¹ is larger than the component (a) /
The value (T) of the melt shear viscosity ratio of the component (b) at 300 ° C. and the shear rate of 300 sec ⁻¹ is 300 ° C. of the component (a) / component (b) in the sea-sea structure [morphological part (c)].
Melt shear viscosity ratio (W2) at shear rate of 300 sec ^-1
Is smaller than W1, and when S is smaller than W1, T is preferably larger than W2.

Preferably, when the volume ratio of the components (a) and (b) is 5:95 to 95: 5 and S is larger than W1 and 100 or less, T is smaller than W2,
Alternatively, the volume ratio of the component (a) to the component (b) is 5: 95-9.
It is 5: 5, and when S is smaller than W1 and is 0.1 or more, it is satisfied that T is larger than W2.

More preferably, when the volume ratio of the components (a) and (b) is 30:70 to 90:10 and S is larger than W1 and 40 or less, T is smaller than W2, or Volume ratio of component (a) and component (b) is 30: 7
It is 0 to 90:10, and when S is smaller than W1 and 0.3 or more, it is satisfied that T is larger than W2.

The melt shear viscosity referred to here is the JIS.
The method described as a reference test of K7210, that is, the shear viscosity when a molten resin is extruded from a capillary at a constant speed, and as a specific device, a Koka type flow tester (Inst. Ron capillary rheometer). With this device, for example, the nozzle diameter is 1 mm and the nozzle length is 1 at various temperatures.
It can be measured by setting 0 mm and changing the extrusion speed.

<Composition Ratio of Constituent Components> The composition ratios of the components (a) and (b) described above are the same as those of the components (a) and (b).
The total amount of is set to 100% by volume and is as follows. Component (a): 5 to 95% by volume, more preferably 30 to 9
It is 0% by volume, particularly preferably 70 to 90% by volume. Component (b): 5 to 95% by volume, more preferably 10 to 7
0% by volume, particularly preferably 10 to 30% by volume,

When the content of the component (a) is less than 5% by volume, the component (a) is unlikely to form a matrix, and the advantages of the component (a), such as heat resistance and dimensional characteristics, are unsatisfactory. On the other hand, when the content of the component (b) is less than 5% by volume, the component (b) is less likely to form a matrix, and the advantages of the component (b), such as moldability,
Solvent resistance becomes unsatisfactory. The total amount of the component (a) and the component (b) is 100 parts by weight, and the component (c): 1 to 40 parts by weight, more preferably 3 to 35.
Parts by weight, particularly preferably 7 to 25 parts by weight.

When the amount of the component (c) is less than 1 part by weight, the flame retardancy is insufficient, and when it exceeds 40 parts by weight, the appearance and physical properties of the molded product are unsatisfactory. The content of component (d) is 5 to 60% by weight in the total composition.
Is more preferable, 7 to 60% by weight is more preferable, and 10 to 60% by weight is particularly preferable. When the content of the inorganic filler is less than 5% by weight, the reinforcing effect is small,
If it exceeds 60% by weight, the moldability is unsatisfactory.

<Manufacturing and Molding Method of Composition> As a method for obtaining the thermoplastic resin composition of the present invention, various kneading machines such as a uniaxial or multiaxial kneading machine, a Banbury mixer, a roll and a Brabender plastogram are used. After kneading the above components with, for example, a method of solidifying by cooling, a suitable solvent, for example, hexane, heptane, benzene, toluene, the above components are added to hydrocarbons or derivatives thereof such as xylene, or the components to be dissolved, or A solution mixing method in which a soluble component and an insoluble component are mixed in a suspended state is used. From the industrial cost, the melt kneading method is preferable, but not limited thereto. The molding method of the composition of the present invention is not particularly limited, molding methods generally used for thermoplastic resin compositions, for example, injection molding, blow molding, extrusion molding, sheet molding, thermoforming, rotational molding, A molding method such as lamination molding can be applied.

[0082]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these. Examples 1 to 6 and Comparative Examples 1 to 3 The following components were used as each component. (1) PPE: poly (2,6-dimethyl-1,4-phenylene ether) (Nippon Polyether Co., Ltd., intrinsic viscosity measured in chloroform at 30 ° C .: 0.41 dl / g,
Hereinafter abbreviated as "PPE")

(2) Polycarbonate: Mitsubishi Gas Chemical Company, Iupilon S2000, viscosity average molecular weight 2.5 × 1
0 ⁴ hereinafter referred to as "PC". (3) Polystyrene: HF77 manufactured by Mitsubishi Chemical Co., hereinafter abbreviated as "PS". (4) Maleic anhydride-modified PPE (hereinafter "M-PPE")
Abbreviated as)

It was manufactured by the following method. PPE100
After thoroughly mixing 1 part by weight of maleic anhydride (first-grade reagent) with a Henschel mixer, a cylinder temperature of 250 was obtained using a twin-screw extruder (manufactured by Japan Steel Works, Ltd.).
After melting and kneading at a temperature of 250 ° C. and a screw rotation speed of 250 rpm, maleic anhydride-modified PPE pellets were obtained after cooling. The grafted amount of maleic anhydride was 0.4% by weight as a result of measurement by infrared spectroscopy.

(5) Olefin-based resin: (5-1) High density polyethylene (Mitsubishi Chemical Corporation, Mitsubishi Polyethylene HD HY330B, abbreviated as "PE-1" hereinafter) (5-2) High density polyethylene (Mitsubishi Chemical (Mitsubishi Polyethylene HD EY40H, hereinafter abbreviated as "PE-2") (5-3) High density polyethylene (Mitsubishi Chemical Corporation, Mitsubishi Polyethylene HD JX20, hereinafter abbreviated as "PE-3")

(5-4) High-density polyethylene (Showa Denko KK, Shorex Super 4551H, hereinafter "PE
-4 ") (5-5) Maleic anhydride graft-modified high-density polyethylene (hereinafter abbreviated as" MM-HD ") It was produced by the following method.

With respect to 100 parts by weight of PE-2 above,
After thoroughly mixing 1 part by weight of maleic anhydride (first-grade reagent) with a Henschel mixer, melt-kneading with a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) at a cylinder temperature of 250 ° C. and a screw rotation speed of 250 rpm. After cooling, pellets of maleic anhydride graft-modified high-density polyethylene were obtained.
The grafted amount of maleic anhydride was 0.8% by weight as a result of measurement by infrared spectroscopy. (5-6) Polypropylene (Mitsubishi Chemical Corporation, Mitsubishi Polypro TA8, hereinafter abbreviated as "PP")

(6) Flame Retardant: (6-1) As aromatic phosphate ester-based flame retardant, triphenyl phosphate (hereinafter referred to as "P-1") manufactured by Daihachi Chemical Co., Ltd.
Abbreviated as). (6-2) Aromatic condensed phosphate ester flame retardant,
It is abbreviated as CR741C (hereinafter "P-2") manufactured by Daihachi Chemical Co., Ltd. having the following structure.

[0089]

[Chemical 8]

(6-3) As the red phosphorus coated with an inorganic compound, Nova Excel 140 (hereinafter referred to as "P
-3 "). (6-4) As a halogenated aromatic flame retardant, a brominated epoxy oligomer having the following structure Type: EP-100 manufactured by Dainippon Ink and Chemicals, Inc. (Molecular weight: about 10,000)
0 or less and abbreviated as "P-4") and S as a flame retardant aid.
b ₂ O ₃

[0091]

[Chemical 9]

(7) Fibrous inorganic filler: diameter 10 μ
m, glass fiber (8) plate-like inorganic filler having a length of 3 mm: average thickness 2 μm, average particle size 9
Kneading and molding of a 0 μm mica composition was carried out as follows.

Examples 1 to 6 and Comparative Examples 1 to 2 The amorphous thermoplastic resin component and the flame retardant component were mixed using a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) at a cylinder temperature of 230 ° C. and a screw rotation speed of 250 rpm. While melt-kneading with, the crystalline thermoplastic resin component and the fibrous and / or plate-like inorganic filler were added from a feed port provided in the middle of the cylinder to obtain a resin composition.

Comparative Example 3 A crystalline thermoplastic resin component and a flame retardant component were provided in the middle of a cylinder while being melt-kneaded using a twin-screw extruder (manufactured by Nippon Steel Co., Ltd.) at a cylinder temperature of 230 ° C. and a screw rotation speed of 250 rpm. The amorphous thermoplastic resin component and the fibrous or / and plate-like inorganic filler were added from the feed port to obtain a resin composition. Next, each of the above resin compositions and the above resin composition was injected by an injection molding machine (manufactured by Japan Steel Works, mold clamping force 100T).
Was used for injection molding at a cylinder temperature of 280 ° C. and a mold temperature of 60 ° C. to prepare a molded product.

Evaluation was carried out according to the following evaluation methods, and the results are shown in Table 1. Evaluation method (1) According to MFR JIS K7210, it was measured at 280 ° C. and a load of 5.0 kg. (2) Izod impact strength A notched Izod impact test was performed according to JIS K7110.

(3) Flexural Modulus A three-point bending test was performed according to the bending test method according to JIS K7203. (4) Heat distortion temperature According to JIS K7207, a load deflection test was performed with a load of 18.6 kg. (5) Warp amount In-line injection molding machine (manufactured by Japan Steel Works, mold clamping force 1
50T), cylinder temperature 280 ° C, mold temperature 60
The molded article shown in FIG. 1 was molded at ℃. Place this molded product on a flat table, measure the maximum displacement from the horizontal plane,
The amount of warpage was used.

(6) Coefficient of linear expansion Measurement was performed at 23 to 80 ° C. according to JIS K6714. (7) In accordance with the flammability standard of flame retardant UL94 plastic material,
Tested with 1/16 inch thick specimens.

(8) Morphological observation A molded piece obtained by injection molding was cut out, and was subjected to leveling operation parallel and perpendicular to the injection molding direction, and dyed with ruthenium tetroxide as follows. A sample and ruthenium tetroxide are placed in a container that can be sealed, stained at 50 ° C. for 1 hour, and an ultrathin section having a thickness of 0.1 μm is prepared by an ultrathin section microtome. This was observed with a transmission electron microscope (TEM: JEM100CX manufactured by JEOL Ltd.).

The location of the flame retardant was also confirmed by this method. The mixed type is a form in which the amorphous thermoplastic resin (a) forms a matrix and the crystalline thermoplastic resin (b) forms a domain in the vicinity of the surface of the molded product, that is, a morphological portion (A). The crystalline thermoplastic resin (b) is a matrix inside, and the amorphous thermoplastic resin (a) is a form forming a domain, that is, a morphological portion (B), P
The PE / PS matrix type is a form in which PPE / PS (a) is a matrix and the crystalline thermoplastic resin (b) forms a domain in all parts of the molded article, and the PO matrix type is All parts of the molded article are shown in which the olefin resin (b) is a matrix and the amorphous thermoplastic resin (a) is in a form of forming domains.

[0100]

[Table 1]

[0101]

From the results of the above-mentioned evaluation test, the morphological part comprising the amorphous thermoplastic resin (a), the crystalline thermoplastic resin (b) and the flame retardant (c), and the component (a) forms a matrix. And a morphological portion in which the component (b) forms a matrix are dispersed, and the flame retardant (c) is the component (a).
In the thermoplastic resin composition selectively present therein,
The flame-retardant thermoplastic resin composition of the present invention containing a specific amount of a fibrous or / and plate-like inorganic filler and a molded article thereof are composed of the component (a) forming a matrix and the component (b) forming a domain. When the thermoplastic resin composition is filled with an inorganic filler, or when the component (b) forms a matrix and the component (a) forms a domain, the thermoplastic resin composition is filled with an inorganic filler. It can be seen that the balance of mechanical strength, moldability, dimensional stability, solvent resistance, etc., is much better than that in the case of carrying out. Therefore, the thermoplastic resin composition of the present invention and the molded article thereof have a wide range of uses and can be industrially useful materials.

[Brief description of drawings]

1A and 1B are a plan view and a measurement view of a resin molded product whose warpage amount is measured in an example. Dimensions are in mm.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP 61-221244 (JP, A) JP 63-128076 (JP, A) JP 63-113075 (JP, A) JP 1- 98645 (JP, A) JP-A-2-103243 (JP, A) JP-A-2-248447 (JP, A) JP-A-6-57159 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08 C08J 5/00

Claims (14)

(57) [Claims] 1. A flame-retardant heat containing (a) an amorphous thermoplastic resin, (b) a crystalline thermoplastic resin, (c) a flame retardant, and (d) a fibrous and / or plate-like inorganic filler. A molded product comprising a plastic resin composition, wherein the component (a) forms a matrix, the component (b) forms a domain (A), and the component (b) forms a matrix. The component (a) has a morphological portion (B) forming a domain, and the vicinity of the surface layer of the molded body is the morphological portion (A), and the inside thereof is the morphological portion (B), Alternatively, the vicinity of the surface layer is the morphological portion (B), the inside is the morphological portion (A), the component (c) is selectively present in the component (a), and the component (d) is wholly contained. A molded product containing 5 to 60% by weight of the composition. 2. The molded product according to claim 1, wherein the component (a) is a mixture of a polyphenylene ether and an aromatic vinyl compound polymer, and the component (b) is an olefin resin. 3. The component (a) is 5 to 95% by volume and the component (b) is 95 to 5% by volume based on 100% by volume of the total of the components (a) and (b). Item 1. A molded article according to item 1 or 2. 4. The molded product according to claim 1, wherein the component (d) is selectively present in the component (a). 5. The component (c) has the following general formula (I): (In the formula, Re represents a residue obtained by removing two hydroxyl groups from hydroquinone, resorcinol, biphenol, bisphenol A, bisphenol F or bisphenol S,
R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom or a carbon number of 1 to
6 represents an alkyl group. When each of R ₁ , R ₂ , R ₃ and R ₄ is two or more, they may be different from each other. n represents an integer of 0 to 10, and m1, m2, m3 and m4 each represent an integer of 1 to 3. ) The molded product according to any one of claims 1 to 4, which is a flame retardant. 6. The molded article is an injection molded article.
The molded article according to any one of 1 to 5. 7. A flame-retardant heat containing (a) an amorphous thermoplastic resin, (b) a crystalline thermoplastic resin, (c) a flame retardant, and (d) a fibrous and / or plate-like inorganic filler. A plastic resin composition having the following formula (i) or (ii): (i) S> w ₁ and T <w ₂ , or (ii) S <w ₁ and T > W ₂ (where S is the melt shear viscosity ratio of component (a) to component (b) at 280 ° C. and shear rate 30 sec ⁻¹ , w ₁ is 280 ° C., shear rate 30 sec ^-1 is the melt shear viscosity ratio of component (a) to component (b) when in a sea-sea structure in which component (a) and component (b) are in continuous phase with each other, and T is 300 ° C., The melt shear viscosity ratio of the component (a) to the component (b) at a shear rate of 300 sec ^-1 , w ₂ is 300 ° C. and shear Satisfies the conditions of the melt shear viscosity ratio of the component (a) and the component (b) to the component (b) in a sea-sea structure in which the component (a) and the component (b) form a continuous phase with each other at a velocity of 300 sec ^−1. The component (c) is selectively present in the component (a),
A flame-retardant thermoplastic resin composition containing the component (d) in an amount of 5 to 60% by weight based on the whole composition. 8. The flame-retardant thermoplastic resin composition according to claim 7, wherein the component (a) is a polyphenylene ether and an aromatic vinyl compound polymer, and the component (b) is an olefin resin. 9. The component (a) is 5 to 95% by volume and the component (b) is 95 to 5% by volume with respect to a total of 100% by volume of the component (a) and the component (b). Item 7. A flame-retardant thermoplastic resin composition according to item 8. 10. The flame-retardant thermoplastic resin composition according to claim 7, wherein the component (d) is selectively present in the component (a). 11. The component (c) has the following general formula (I): (In the formula, Re represents a residue obtained by removing two hydroxyl groups from hydroquinone, resorcinol, biphenol, bisphenol A, bisphenol F or bisphenol S,
R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom or a carbon number of 1 to
6 represents an alkyl group. When each of R ₁ , R ₂ , R ₃ and R ₄ is two or more, they may be different from each other. n represents an integer of 0 to 10, and m1, m2, m3 and m4 each represent an integer of 1 to 3. ) The flame-retardant thermoplastic resin composition according to any one of claims 7 to 10, which is a flame retardant. 12. The flame-retardant thermoplastic resin composition according to claim 7, which is for injection molding. 13. A molded article made of the flame-retardant thermoplastic resin composition according to claim 7. 14. An injection-molded article made of the flame-retardant thermoplastic resin composition according to any one of claims 7 to 11.