JP2890669B2 - Thermoplastic resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having improved weld strength based on an aromatic polycarbonate and a polyamide, which has mechanical properties, solvent resistance and the like. And is usefully used as a molding material.

[Conventional technology and its problems]

Thermoplastic resin compositions in which various polyamides are blended with an aromatic polycarbonate resin are known. For example, JP-A-48-28044 discloses an adhesive composition, and JP-B-48-13944 discloses a glass fiber-containing molding material. And compositions of an aromatic polycarbonate resin and various polyamides are known.

As an improvement over the disadvantages of this known composition, JP-B-52-43667 discloses that a composition with up to 20% by weight of nylon 12 improves the thermal stability which is a disadvantage of a composition with nylon 6 or the like. JP-A-62-257960 discloses that a composition having excellent tracking resistance is obtained.
JP-A-62-257961 is an isocyanate, JP-A-63-2756
No. 30 can be used in combination with one or more compounds such as acid chloride, isocyanate, carboxylic acid and its acid anhydride, and by blocking terminal amino groups of the polyamide resin, a composition having improved heat stability can be obtained. It is disclosed that.

However, according to studies by the present inventors, a composition comprising an aromatic polycarbonate resin and a polyamide resin has a serious problem that weld strength generated during injection molding is low. For this reason, it was unsuitable to use these compositions for the production of molded articles using large molds in which many welds occur.

[Problems to be solved by the invention]

An object of the present invention is to provide a composition based on an aromatic polycarbonate and a polyamide resin, which has improved weld strength and a good balance of heat resistance, mechanical properties, solvent resistance and the like.

To solve this problem, the present inventors have studied from various aspects. As a result, surprisingly, it was found that by selecting an inorganic acid, not only the thermal stability was further improved, but also the weld strength was greatly improved, and the present invention was reached.

[Means for solving the problem]

That is, the present invention is a thermoplastic resin composition comprising A. an aromatic polycarbonate resin, B. a polyamide resin, and C. an inorganic acid, wherein the weight ratio of the components A and B is
1/9 to 9/1, the compounding amount of the inorganic acid of the component C is 0.00
The thermoplastic resin composition is characterized in that the content is in the range of 5 to 2% by weight and the inorganic acid is boric acid.

 Hereinafter, the configuration of the present invention will be described.

First, the aromatic polycarbonate resin A, which is the base resin of the present invention, is a homopolymer of an aromatic polycarbonate produced by a conventionally known method using a dihydric phenol, phosgene or a carbonic acid diester and a terminal stopper.
Alternatively, it is a copolymer.

Here, as the dihydric phenol, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl)
Ether, bis (4-hydroxyphenyl) sulfone,
Bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) ) Propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxy-3 , 5-Dibromophenyl) propane, 4,4'-
Dihydroxy-3,3 ', 5,5'-tetrabromodiphenyl sulfide, 2,2- (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-
Bromophenyl) propane, bis (4-hydroxy-3)
-Chlorophenyl) methane, bis (4-hydroxy-3,
5-dichlorophenyl) methane and the like.

In addition, a terminal terminator (molecular weight regulator) may be octyl phenol, nonyl phenol, octyl phenol, nonyl phenol, or the like in addition to ordinary phenol, pt-butyl phenol, tribromophenol, and the like.
Long-chain alkyl-substituted phenols such as lauryl phenol, palmityl phenol and stearyl phenol; octyl hydroxybenzoate, lauryl hydroxybenzoate,
Long-chain alkyl esters of hydroxybenzoic acid such as nonyl hydroxybenzoate and stearyl hydroxybenzoate; octyl ether phenol (= octyloxyphenol), nonyl ether phenol, lauryl ether phenol, palmityl ether phenol, octadecyloxyphenol, dodecyloxy Long-chain alkyloxyphenols such as phenol; and aliphatic acid chlorides such as capric acid chloride, lauric acid chloride, myristic acid chloride, palmitic acid chloride, stearic acid chloride, and cerotic acid chloride.
A branched polycarbonate may be used in combination with a branching agent in an amount of 0.01 to 3 mol, particularly 0.1 to 1.0 mol, per 100 mol of the above dihydric phenol compound.
Such branching agents include phloroglysin, 2,6-
Dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3,4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2,1,3,5-tri ( 4-hydroxyphenyl) benzol, 1,1,1-tri (4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, α,
α ', α "-tri (4-hydroxyphenyl) -1,3,5
-Polyhydroxy compounds exemplified by triisopropylbenzene and the like, and 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol);
Examples thereof include 5-chlorisatin, 5,7-dichlorisatin, and 5-bromoisatin.

The average molecular weight of these aromatic polycarbonate resins is
1,000-100,000, preferably 12,000-50,000, especially 18,0
00-35,000.

The polyamide resin of the B component of the present invention is a thermoplastic resin having a main chain formed by an amide bond (-CONH-) generally called nylon, and is generally represented by the following (1) to (1).
It is manufactured by (3).

In the above, R ¹ is an alkylene group having 5 to 11 carbon atoms, R ²
Is an alkylene group having 5 to 18 carbon atoms, R ³ is an alkylene group which may have an aromatic ring having 5 to 11 carbon atoms, R ⁴ is 3 to
It is an alkylene group which may have 40 aromatic rings. Representative polyamide resins include nylon-6 obtained by ring-opening polymerization of ε-caprolactam, nylon-12 obtained by ring-opening polymerization of ω-laurolactam, and similarly γ-butyrolactam, δ-valerolactam, and ξ- From enantholactam or η-caprylactam; nylon-11 obtained by heating and polycondensing 11-aminoundecanoic acid; similarly, from 7-aminoheptanoic acid, 9-aminononanoic acid, etc .; hexamethylene With diamines such as diamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, meta-xylylenediamine, terephthalic acid, isophthalic acid, adipic acid,
Nylon-4, 6, 7, 8, 11, 12, 6, 6, 6, 9, 6, 10, or 6 obtained by polycondensing dicarboxylic acids such as sebacic acid, dodecane dibasic acid and glutaric acid. , 1
1, 6, 12, 6T, 6/12, 6/6, 6, 6 / 6T, 6I / 6T and the like.

The molecular weight of these polyamide resins is generally 10,000 or more, preferably 13,000 to 50,000, particularly preferably 15,000 to 30,000, and the degree of polymerization is 100 or more, 130 to 500, particularly 150 to 300.
Is preferred.

The polyamide resin of the present invention preferably does not contain a carbonate of a metal or an amphoteric metal, and includes, for example, an alkali metal such as lithium, sodium and potassium; and an alkaline earth such as magnesium, calcium, barium and strontium. Metals; amphoteric metals such as chromium, manganese, aluminum, zinc, tin, and lead; carbonates such as transition metals such as iron, cobalt, nickel, copper, palladium, and cadmium;
It is included as a component of a release agent and a crystal nucleating agent. Further, the terminal group amount of the polyamide resin is preferably appropriately stabilized by reacting with a molar ratio of diamine and dibasic acid during polymerization and acid anhydride, acid chlorand, isocyanate compound, and other terminal blocking agents. In general, the amino group is preferably 60 g-meq / kg or less, particularly 30 g-meq / kg or less.
A meq / kg or less is suitable.

The resin composition of the present invention is a composition having not only improved thermal stability but also improved weld strength by incorporating C. an inorganic acid based on the above components.

Known inorganic acids can be used, such as phosphoric acid, phosphorous acid, hypophosphorous acid, tripolyphosphoric acid, phosphoric anhydride, boron, boric anhydride, hydrochloric acid, nitric acid, sulfuric acid, etc., and further monomethyl phosphate,
Phosphate esters such as dimethyl phosphate, monoethyl phosphate, diethyl phosphate, isopropyl phosphate, diisopropyl phosphate, propyl phosphate, dipropyl phosphate, heptyl phosphate, diheptyl phosphate, octyl phosphate, and phenyl phosphate such as phenyl phosphate, diphenyl phosphate, cresyl phosphate, dicresyl phosphate Esters, monomethyl borate, dimethyl borate, monoethyl borate, diethyl borate, isopropyl borate, diisopropyl borate, propyl borate, dipropyl borate, heptyl borate, diheptyl borate, octyl borate, etc., phenyl borate, cresyl borate, dicresyl borate, etc. Boric acid phenyl esters. Boric acid, phosphorous acid, diethyl phosphate, diphenyl phosphate, diethyl borate, diphenyl borate are preferred, and boric acid is particularly preferred.

The mixing ratio of the above components A, B, and C of the present invention is generally not particularly limited, but A / B = 1/9 to 9/1 by weight ratio, and the C component is
It is in the range of 0.005 to 2% by weight. If the amount of the inorganic acid as the component C is too small, the effect of improving the weld strength is small.

The resin composition having excellent weld strength of the present invention is one that requires the above components, but in preparing the composition,
Resins such as polystyrene resins, polyesters, polyphenylene oxides, maleated polyphenylene oxides, and polysulfones; thermoplastic elastomers and rubbers; stabilizers such as sterically hindered phenols and phosphite compounds; benzotriazoles;
Other ultraviolet absorbers: phenol, cresol, a mixture of isopropylphenol and phenol, benzohydroquinone, various phosphates produced using bisphenol A, etc., decabromobiphenyl, pentabromotoluene, decabromophenyl ether, hexabromobenzene, Flame retardants consisting of brominated compounds such as brominated polystyrene and brominated polycarbonate, nitrogen-containing compounds such as melamine derivatives, and compounds other than carbonates such as antimony, boron, zinc and iron; titanium oxide, zinc sulfide, zinc oxide and carbon Pigments exemplified by black and the like; various kinds of fibers such as glass fiber, glass milled fiber, glass beads, carbon fiber, wholly aromatic polyamide fiber, and stainless steel fiber; It can be blended pressurized agents.

Here, the thermoplastic elastomer or rubber is effective for imparting higher impact resistance, and specifically, ABA ′ comprising a diene compound (B) and a vinyl aromatic compound (A). Block copolymer or hydrogenated product thereof, butyl graft polyethylene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer,
Polyester elastomer, polyamide elastomer (polyether block polyamide), grafted product of butyl rubber and polyethylene, polybutadiene, polyisoprene, styrene-butadiene copolymer, nitrile rubber, thiochol rubber, polyurethane rubber, butyl rubber,
0.1 to 0.1% for acrylic rubbers and these various copolymers
5% by weight of α, β unsaturated carboxylic acid such as maleic anhydride added; core-shell type MAS, MBS, MEBS,
Mainly made of acrylic rubber core and MMA (meta)
Examples thereof include those having a shell made of an acrylic acid ester polymer, and can be used alone or in combination as appropriate.In particular, maleated ethylene-propylene,
Maleated propylene, MBS and the like are preferred.

The method of adjusting the composition is not particularly limited as long as it is a method of uniformly mixing, but usually, a method of mixing each component in powder and then melt-kneading is preferable, for example, A, B, C
A method of mixing the components and further mixing other additives;
A method using a master batch in which additives are blended at a high concentration; other methods may be appropriately selected.

〔Example〕

Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples. In the Examples and Comparative Examples, “%” and “parts” are on a weight basis unless otherwise specified, and physical property values are described below.

・ Σ _Tb (tensile breaking strength): kg / cm ² .・ Ε _T (〃 elongation): Unit%. Measured in accordance with ASTM D-638.

・ W _Tb (weld strength): unit kg / cm ² .・ Ε _W (〃 elongation): Unit%. Using a test piece having a weld line at the center formed by a mold having gates at both ends of a dumbbell test piece, tensile strength and elongation were measured according to ASTM D-638.

Examples 1 and 2 and Comparative Examples 1 and 2 Aromatic polycarbonate resin (trade name; Iupilone E)
-1000, manufactured by Mitsubishi Gas Chemical Co., Ltd.) 55.8 parts, nylon-6
(Product name: Novamide 1010J, manufactured by Mitsubishi Chemical Corporation) 37.2
Part, maleated ethylene-propylene rubber (trade name; Exa
lor XX1301, 6 parts by Exxon) and MBS resin (trade name: KM
As shown in Table 1, 0.2 parts of boric acid in Example 1, 0.2 parts of phosphorous acid in Example 2, and 0.2 parts of benzoyl chloride in Comparative Example 1 as shown in Table 1. After dry blending, in Comparative Example 2, dry blending was performed without adding an acid, and the mixture was melt-kneaded at 260 ° C. using a vented twin-screw extruder at 260 ° C. while vacuum suctioning the vent to form pellets.

Using the obtained pellets, injection molding was performed at a cylinder temperature of 255 ° C. using an injection molding machine to produce test pieces, and the physical properties shown in Table 1 were measured.

 The results are shown in Table 1.

Examples 3 to 5 In Example 1, the amount of boric acid added was changed (Example 3), and diphenyl borate (Example 4) or diphenyl phosphite (Example 5) was used instead of boric acid. Table 2 shows the same results except that the amounts described in Table 2 were blended.

[Function and Effect of the Invention] As described above, the composition of the present invention is based on an aromatic polycarbonate resin and a polyamide resin, and a composition obtained by blending an inorganic acid with the composition has improved strength and weld strength. This is extremely useful especially in large-sized molded articles.

────────────────────────────────────────────────── (5) References JP-A-3-229754 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 69/00 C08L 77/00-77 / 12

Claims (3)

(57) [Claims] 1. A thermoplastic resin composition comprising: A. an aromatic polycarbonate resin, B. a polyamide resin, and C. an inorganic acid, wherein the weight ratio of the components A and B is 1/9 to 9/1. Stuff. 2. The thermoplastic resin composition according to claim 1, wherein the amount of the inorganic acid of component C is in the range of 0.005 to 2% by weight. 3. The thermoplastic resin composition according to claim 2, wherein said inorganic acid is boric acid.