JPH05140425A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To prepare the subject compsn. excellent in impact strength, resistance to heat and solvents, stiffness, etc., by compounding polyphenylene ether, a satd. polyester, an impact modifier, and a specific compd. in a specified ratio. CONSTITUTION:100 pts.wt. resin mixture comprising 5-60wt.% polyphenylene ether, 20-90wt.% satd. polyester (e.g. polybutylene terephthalate), and 1-35wt.% impact modifier (e.g. hydrogenated styrene-butadiene block copolymer) is compounded with 0.01-10 pts.wt. compd. of the formula (wherein Ar is a 9-20C arom. hydrocarbon group having at least one glycidyloxy group; R is H or CH3; and (n) is 1-4) having both a glycidyloxy group and a (meth)acrylamido group in the molecule.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic resin composition excellent in impact resistance, heat resistance, dimensional stability, solvent resistance and appearance of molded articles.

[0002]

2. Description of the Related Art Polyphenylene ether (hereinafter referred to as PPE
Is known as an engineering plastic having excellent heat resistance, dimensional stability, non-hygroscopicity and electrical characteristics, but it has poor melt flowability and is difficult to mold, and has a solvent resistance, It has the drawback of poor impact resistance.

On the other hand, saturated polyester is
As engineering plastics with excellent solvent resistance and mechanical strength, they are widely used in the fields of automobile parts and electric / electronic device parts. However, this resin has the drawbacks that the molding shrinkage rate and the linear expansion rate are large, and that the rigidity is greatly reduced at high temperatures. In order to improve this, a method of filling a reinforcing agent such as glass fiber has been proposed. However, since the appearance of the molded product is deteriorated, there is a problem that its use is limited depending on the required field.

Therefore, if a composition having both the good properties of PPE and saturated polyester and complementing the undesired properties can be obtained, it becomes possible to provide an excellent resin material having a wide range of fields of use, and its industrial significance is extremely high. Can be said to be large. Therefore, for the purpose of providing a molding material which complements the drawbacks without impairing the advantages of both, for example, a composition obtained by simply melt-mixing both resins is disclosed in JP-B-51-21664.
9-50050, 49-75662 and 59-
It is disclosed in each publication of No. 159847.

However, in such a simple blend system, since the PPE and the saturated polyester are inherently poor in compatibility, the adhesiveness at the interface of this two-phase structure is not good, and the two phases are uniform and uniform. It is difficult to form a fine shape, and when subjected to shear stress during molding processing such as injection molding, delamination is likely to occur, the appearance of the obtained molded product deteriorates, and the two-layer interface becomes a defective part. A composition having excellent mechanical properties such as dimensional accuracy, heat resistance and rigidity and physical properties such as solvent resistance cannot be obtained.

Therefore, some techniques for improving the compatibility of the two have been proposed. For example, a compound having (i) carbon-carbon double bond or carbon-carbon triple bond and (ii) one or more groups selected from carboxylic acid, acid anhydride, acid amide, epoxy group and hydroxyl group in the molecule. Using a modified PPE obtained by reacting (see JP-A-62-257)
No. 958, No. 63-54427, and Tokusho 63-50
No. 0803), alkoxysilyl group-modified PPE
(JP-A No. 63-503392) and a method using oxazoline-modified PPE (JP-A-2-187).
No. 453), a method of using polyester modified with hydroxyl- or carboxyl-terminated polystyrene (JP-A-2-170852), a method of blending oxycarboxylic acids (JP-A-2-129259), and the like. There is.

However, even if these methods are used, the PPE
In many cases, it is not sufficient to improve the compatibility between the saturated polyester and the saturated polyester, and the mechanical properties of the obtained composition are still insufficient, and further improvement is desired.

[0008]

DISCLOSURE OF THE INVENTION According to the present invention, the miscibility of PPE and saturated polyester is extremely excellent, and both components show a homogeneous and fine mixed state, whereby shear stress during molding such as injection molding is suppressed. To provide a thermoplastic resin composition that suppresses delamination when receiving, has excellent appearance of the obtained molded article, and has excellent impact resistance, solvent resistance, thermal rigidity, and mechanical strength balancing. To aim.

[0009]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a mixture of PPE, a saturated polyester and an impact resistance improver has a glycidyloxy group in the same molecule. It was found that a resin composition prepared by compounding a compound having both a base and a (meth) acrylamide group in a specific ratio is a composition having excellent impact resistance, heat resistance, dimensional stability, solvent resistance and molding appearance. The present invention has been reached.

That is, the present invention comprises the following components (a) to
A thermoplastic resin composition comprising (d) and a composition ratio. (A) Polyphenylene ether 5 to 60% by weight (b) Saturated polyester 20 to 90% by weight (c) Impact resistance improver 1 to 35% by weight (d) General formula (I)

[0011]

[Chemical 2]

(In the formula, Ar represents an aromatic hydrocarbon group having at least one glycidyloxy group and having 9 to 20 carbon atoms, R represents a hydrogen atom or a methyl group, and n represents 1 to 1).
A compound having a glycidyloxy group and a (meth) acrylamide group in the same molecule represented by the formula (4 is an integer of 4) 0.01 to 10 parts by weight based on 100 parts by weight of the total amount of the components (a) to (c).

The present invention will be described in detail below. <PPE (a)> The PPE used in the present invention has the general formula (II)

[0014]

[Chemical 3]

(Wherein Q ¹ represents a halogen atom, a primary or secondary alkyl group, a phenyl group, an aminoalkyl group, a hydrocarbonoxy group or a halohydrocarbonoxy group, and Q ² represents a hydrogen atom. , A halogen atom, a primary or secondary alkyl group, a phenyl group, a haloalkyl group, a hydrocarbon oxy group or a halohydrocarbon oxy group, and m represents a number of 10 or more). It is a polymer or a copolymer.

Preferable examples of the primary alkyl group for Q ¹ and Q ² include methyl, ethyl, n-propyl, n-butyl and n.
-Amyl, isoamyl, 2-methylbutyl, n-hexyl, 2,3-dimethylbutyl, 2-, 3- or 4-
Methyl pentyl or heptyl. Suitable examples of secondary alkyl groups include isopropyl, sec-butyl or 1-
It is ethylpropyl. In many cases, Q ¹ is an alkyl group or a phenyl group, especially an alkyl group having 1 to 4 carbon atoms, and Q ² is a hydrogen atom.

Suitable homopolymers of PPE are, for example, those composed of 2,6-dimethyl-1,4-phenylene ether units. A preferred copolymer is a random copolymer composed of a combination of the above units and 2,3,6-trimethyl-1,4-phenylene ether units. Many suitable homopolymers or random copolymers are described in the patent literature. Also suitable are PPEs that include molecular moieties that improve properties such as, for example, molecular weight, melt viscosity and / or impact strength.

The PPE used here has an intrinsic viscosity of 0.2 to 0.8 dl / g at 30 ° C. measured in chloroform.
Are preferred. The intrinsic viscosity is more preferably 0.2 to 0.5 dl / g, and particularly preferably the intrinsic viscosity is 0.25 to 0.4 dl / g. If the intrinsic viscosity is less than 0.2 dl / g, the impact resistance of the composition will be insufficient, and if it exceeds 0.8 dl / g, the moldability of the composition and the appearance of the molded article will be poor.

<Saturated Polyester (b)> As the saturated polyester used in the present invention, various saturated polyesters can be used. For example, one of them is a thermoplastic polyester produced by condensing a dicarboxylic acid or a lower alkyl ester thereof, an acid halide or an acid anhydride derivative, and a glycol or a dihydric phenol according to a usual method.

Specific examples of aromatic or aliphatic dicarboxylic acids suitable for producing this polyester include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and terephthalic acid. ,
Isophthalic acid, p, p'-dicarboxydiphenyl sulfone, p-carboxyphenoxyacetic acid, p-carboxyphenoxypropionic acid, p-carboxyphenoxybutyric acid, p-carboxyphenoxyvaleric acid, 2,6-naphthalene dicarboxylic acid or 2,7 -Naphthalene dicarboxylic acid and the like or a mixture of these carboxylic acids.

As the aliphatic glycol suitable for producing polyester, a linear alkylene glycol having 2 to 12 carbon atoms, for example, ethylene glycol, 1,3-propylene glycol, 1,4-butene glycol, 1,6-
Examples include hexene glycol and 1,12-dodecamethylene glycol. Further, p-xylylene glycol is exemplified as the aromatic glycol compound, and pyrocatechol, resorcinol,
Hydroquinones or alkyl-substituted derivatives of these compounds are mentioned. Other suitable glycols include 1,4
-Cyclohexanedimethanol is also mentioned.

Other preferable polyesters include polyesters obtained by ring-opening polymerization of lactone. For example, polypivalolactone, poly (ε-caprolactone)
Etc. Further, as still another preferable polyester, a polymer (Thermomo) that forms a liquid crystal in a molten state is used.
tropic Liquid Crystal Pol
There is polyester as a ymer; TLCP). Typical examples of polyesters that fall into these categories are Eastman Kodak's X7G, Dartco's Xyday (Zyder), Sumitomo Chemical's Econor, and Celanese's Vectra.

Among the saturated polyesters (b) listed above, polyethylene terephthalate (PET), polybutylene terephthalate (PET), polynaphthalene terephthalate (PEN), poly (1,4-cyclohexanedimethylene terephthalate) (PCT) or Liquid crystalline polyester and the like are saturated polyesters suitable for the thermoplastic resin composition of the present invention.

The viscosity of the saturated polyester (b) 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 0.1. A range of up to 5 dl / g is preferred. More preferably, 0.5 to 4 dl / g, and most preferably 1
~ 3.5 dl / g. If the intrinsic viscosity is less than 0.1 dl / g, the impact resistance is insufficient, and if it exceeds 5 dl / g,
Moldability is poor.

<Impact resistance improving material (c)> An elastomer is used as the impact resistance improving material. If the tensile modulus of elasticity of this elastomer is too high, it does not function sufficiently as an impact resistance improver, so that the tensile modulus of elasticity of the elastomer is 5000.
kg / cm ² (ASTM D 882) or less is preferable, and 3500 kg / cm ² or less is more preferable. Elastomers include natural rubbers or diene-based synthetic rubbers such as polybutadiene, polyisoprene or copolymers of such dienes with vinyl monomers such as vinyl aromatic monomers such as styrene.

Specifically, a styrene-butadiene-styrene terpolymer or a hydrogenated product thereof; polybutadiene, polychlorobutadiene such as neoprene; a copolymer of isobutylene and butadiene or isoprene; polyisoprene; ethylene and propylene. Copolymer with butadiene or copolymer with butadiene; siochol rubber; polysulfide rubber; acrylic rubber; polyurethane rubber; diene such as butadiene or isoprene and various monomers such as alkyl unsaturated ester A polymer may be mentioned.

Further, maleic acid, maleic acid monomethyl ester, maleic anhydride,
Α, β-unsaturated dicarboxylic acids such as itaconic acid, itaconic acid monomethyl ester, itaconic anhydride and fumaric acid,
Or an alicyclic carboxylic acid such as endo-bicyclo [2,2,1] -5-heptene-2,3-carboxylic acid or a derivative thereof; glycidyl methacrylate, 2-methylglycidyl methacrylate, 2-methacrylic acid Methyl-2,
Unsaturated epoxy compounds such as 3-epoxypropyl; those obtained by graft-polymerizing unsaturated hydroxy compounds such as hydroxyethyl methacrylate, polyethylene glycol methacrylate and hydroxyethyl acrylate using peroxide, ionizing radiation, ultraviolet rays, etc. May be used.

<Compound (d) having a glycidyloxy group and a (meth) acrylamide group in the same molecule> The compound having a glycidyloxy group and a (meth) acrylamide group in the same molecule used in the present invention is generally Formula (I)

[0029]

[Chemical 4]

(In the formula, Ar represents an aromatic hydrocarbon group having at least one glycidyloxy group and having 9 to 20 carbon atoms, R represents a hydrogen atom or a methyl group, and n is 1).
Is an integer of 4). Examples of such compounds include those of formula (III)

[0031]

[Chemical 5]

(Wherein R is the same as above), a compound of formula (IV)

[0033]

[Chemical 6]

(Wherein R is the same as above and p is 1 or 2) Formula (V)

[0035]

[Chemical 7]

(Where R is the same as above, q and r
Represents an integer of 0 to 2, and at least one of q and r is 1 or more). Among them, the compound represented by the formula (III), in which R in the formula is a hydrogen atom, is preferable. The compound having both a glycidyloxy group and a (meth) acrylamide group in the same molecule used in the present invention may be used alone or in combination of two or more.

As an example of such a compound having both a glycidyloxy group and a (meth) acrylamide group in the same molecule, Kaneka AXE manufactured by Kanegafuchi Chemical Industry Co., Ltd. (see JP-A-60-130580 for the production method) ) Is available as a product.

<Composition ratio of constituents> The composition ratio of the components (a) to (d) described above is as follows, with the total weight of (a) + (b) + (c) being 100% by weight. is there. Component (a): 5 to 60% by weight, preferably 10 to 50% by weight, particularly preferably 15 to 45% by weight.
When the component (a) is less than 5% by weight, heat resistance is unsatisfactory, and when it exceeds 60% by weight, solvent resistance and impact resistance are unsatisfactory. Component (b): 20 to 90% by weight, preferably 30 to 85
%, Particularly preferably 40 to 80% by weight. If the component (b) is less than 20% by weight, the solvent resistance and impact resistance are unsatisfactory, and if it exceeds 90% by weight, the heat resistance and rigidity are insufficient. Component (c): 1-35% by weight, preferably 3-32% by weight, particularly preferably 6-30% by weight. When the content of the component (c) is less than 1% by weight, the impact resistance is insufficient, and 3
If it exceeds 5% by weight, the heat resistance is unsatisfactory. The composition of component (d) is such that the total amount of (a) to (c) is 100 parts by weight, and the amount added as an external number is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight. Parts by weight, particularly preferably 1 to 4 parts by weight. If the amount of the component (d) is less than 0.01 part by weight, impact resistance is insufficient,
If it exceeds 10 parts by weight, the appearance of the molded product will be poor.

<Additional component> Other additional components can be added to the thermoplastic resin composition according to the present invention.
For example, well-known antioxidants such as saturated polyesters, weather resistance improvers, nucleating agents, flame retardants, and other additives; and well known PPE antioxidants, weather resistance improvers, plasticizers, flow improvers, etc. Can be used as an additional ingredient. Further, addition of organic / inorganic fillers and reinforcing agents, particularly glass fiber, mica, talc, wollastonite, potassium titanate, calcium carbonate, silica and the like is effective for improving rigidity, heat resistance, dimensional accuracy and the like. For practical use, various known colorants and their dispersants can be used.

<Manufacturing and Molding Method of Composition> The melt kneading method for obtaining the thermoplastic resin composition of the present invention includes:
A kneading method generally used for thermoplastic resins can be applied. For example, if necessary, the powdery or granular components, together with the additives described in the additional components section, are uniformly mixed by a Henschel mixer, a ribbon blender, a V-type blender, etc., and then uniaxial or multiaxial. A kneading extruder, a roll, a Banbury mixer or the like is used for kneading.

The order of kneading may be such that all the components may be kneaded at the same time, or a blended product preliminarily kneaded may be used for kneading. Further, each component may be sequentially fed and kneaded from the middle of the extruder. Further, it is desirable to carry out kneading while sequentially degassing in vacuum from the middle of the kneading machine.

The method for molding the thermoplastic resin composition of the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, that is, injection molding, blow molding, extrusion molding, sheet molding, and heat molding. Molding methods such as molding, rotational molding, laminated molding and press molding can be applied.

[0043]

EXAMPLES The present invention will be described in detail below with reference to examples. Examples 1 to 4 The components used are as follows. Component (a) PPE: Poly (2,6-dimethyl-1,4-phenylene ether) produced by Japan Polyether Co., Ltd., and has an intrinsic viscosity [η] of 0.31 dl / measured in chloroform at 30 ° C. The one of g was used.

Component (b), saturated polyester: Polybutylene terephthalate (PBT) (trade name: PB, manufactured by Kanebo Co., Ltd.)
T128) (phenol / 1,1,2,2-tetrachloroethane = 20 ° C. measured in a 60/40 wt% mixture)
Intrinsic viscosity of 2.8 dl / g) was used. Component (c) impact resistance improver: Hydrogenated styrene-butadiene block copolymer (SEBS) manufactured by Shell Co. (trade name:
Clayton G1652) was used.

A compound having a glycidyloxy group and a (meth) acrylamide group in the same molecule of the component (d):
An epoxidized acrylamide compound (trade name: Kaneka AXE) manufactured by Kanegafuchi Chemical Industry Co., Ltd. was used.

The above-mentioned component (a) at the compounding ratio shown in Table 1,
(C) and (d) were thoroughly mixed and stirred with a super mixer. Then, using a TEX44 twin-screw extruder manufactured by Japan Steel Works, this was set at a temperature of 230 ° C. and the screw rotation speed was 3
At the same time as the melt kneading at 50 rpm, the component (b) was quantitatively added from the intermediate hopper of the extruder, and melt kneading was carried out in the latter stage while successively performing vacuum deaeration to prepare a composition and then pelletized.

From the pellets of the above resin composition, an in-line screw type injection molding machine (IS-
90B type), injection molding was performed at a cylinder temperature of 260 ° C. and a mold cooling temperature of 80 ° C. to prepare a test piece.

In the injection molding, a vacuum drier was used immediately before the injection molding under the conditions of 0.1 mmHg and 80 ° C.
It was dried for 8 hours. In addition, the injection molded test piece is
Immediately after molding, it was placed in a desiccator and allowed to stand at 23 ° C. for 4 to 6 days, and then an evaluation test was conducted. The results are shown in Table 1.

Each physical property value and various characteristics were measured by the following methods. (1) Flexural modulus ISO R178-1974 Procedure 1
According to 2 (JIS K 7203), the measurement was performed using an Instron tester. (2) Izod impact strength ISO R180-1969 (JIS K 7110)
According to the notched Izod impact strength, the measurement was performed using an Izod impact tester manufactured by Toyo Seiki Seisakusho. (3) Heat distortion temperature Using an HDT tester manufactured by Toyo Seiki Seisakusho, JIS
Evaluation was performed according to K 7207 under a load of 4.6 kg.

[0050]

[Table 1]

Comparative Example 1 The procedure of Example 1 was repeated except that the compound (d) having both a glycidyloxy group and a (meth) acrylamide group in the same molecule was not added. The results are shown in Table 1.

Comparative Example 2 Commercially available glycidyl methacrylate, which is a compound having an epoxy group but not a (meth) acrylamide group in place of the compound (d) having both a glycidyloxy group and a (meth) acrylamide group in the same molecule. Example 1 was repeated except that (GMA) was used. The results are shown in Table 1.
Shown in.

COMPARATIVE EXAMPLE 3 Instead of the compound (d) having a glycidyloxy group and a (meth) acrylamide group in the same molecule, a compound having an epoxy group but not a (meth) acrylamide group, manufactured by ADEKA ARGUS CORPORATION The same procedure as in Example 1 was performed except that the epoxidized liquid polybutadiene (trade name: BF-1000) having an oxirane oxygen content of 7.5% by weight and a molecular weight of about 1000 was used. The results are shown in Table 1.

[0054]

As described above, the impact resistance of the thermoplastic resin composition of the present invention is remarkably improved, whereby the thermoplastic resin composition of the present invention has heat resistance, rigidity and impact strength. The balance is excellent, its use is wide, and it can be an industrially useful material.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yoshihiro Kurasawa 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Petrochemical Co., Ltd. Yokkaichi Research Institute

Claims (1)

[Claims] 1. A thermoplastic resin composition comprising the following components (a) to (d) and a composition ratio. (A) Polyphenylene ether 5 to 60% by weight (b) Saturated polyester 20 to 90% by weight (c) Impact resistance improver 1 to 35% by weight (d) General formula (I) (In the formula, Ar represents an aromatic hydrocarbon group having at least one glycidyloxy group and having 9 to 20 carbon atoms, and R represents
Represents a hydrogen atom or a methyl group. n is an integer of 1 to 4) A compound having both a glycidyloxy group and a (meth) acrylamide group in the same molecule, represented by the formula (0) based on 100 parts by weight of the total amount of the components (a) to (c). 01-10 parts by weight