JPS62119256A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:A thermoplastic resin composition, consisting of a specific amorphous polyether ester amide and transparent graft copolymer having a specific value or less of difference in refractive index between both and having improved permanent antistatic properties, impact resistance and transparency. CONSTITUTION:A thermoplastic resin composition, consisting of (A) an amorphous polyether ester amide consisting of (A1) 2-90wt% salt of a >=6C diamine with isophthalic acid, (A2) 0-88wt% >=6C aminocarboxylic acid or lactam and (A3) 10-90wt% total of a poly(alkylene oxide)glycol having 200-6,000 number-average molecular weight and isophthalic acid in an equimolar amount with the poly(alkylene oxide)glycol and (B) a copolymer prepared by graft copolymerizing (B2) 99-20pts.wt. mixture [of composition to give <=0.02 refractive index difference between a polymer consisting only of a component (B2) and a component (B1)] consisting of an acrylic acid or methacrylic acid ester monomer and another copolymerizable vinyl based monomer in the presence of (B1) 1-80pts.wt. rubber-like polymer and prepared by blending the component (A) in an amount within 1-99pts.wt. range with the component (B) in an amount within 99-1pts.wt. range. The difference in refractive index between the components (A) and (B) is <=0.02.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermoplastic resin composition having excellent permanent band prevention properties, impact resistance and transparency.

[Conventional technology]

A resin in which the refractive index of the rubbery polymer substantially matches that of the matrix resin, such as methacrylic tvm methyl-butadiene-styrene copolymer (IVf BS resin) or methyl methacrylate-1-crylonitrile-1 Butadiene-styrene copolymer (MABS resin) is used in a wide range of fields as a resin having excellent impact resistance and transparency. If these resins are provided with antistatic properties in addition to their mechanical strength and optical properties, their uses can be further expanded.

In other words, it becomes possible to develop applications such as IC carrying cases and OA equipment covers that want to prevent damage caused by static electricity, and various employment-prevention parts.

A method for imparting antistatic properties to a transparent resin is to use a hydrophilic rubber-like polymer obtained by copolymerizing a conjugated diene or/and acrylic acid 7-kyl ester and a vinyl monomer having 1-kylene oxide group. There is a method of graft polymerizing a vinyl monomer whose refractive index substantially matches that of the above (Japanese Unexamined Patent Publication No. 55-36237), which achieves practical antistatic properties.

[Problem that the invention seeks to solve]

Conventional antistatic resins use special hydrophilic rubber-like polymers, which have the drawbacks of complicated manufacturing methods and poor mechanical properties such as impact resistance and elastic modulus of the resulting resins. Yes, but it is not completely satisfactory.

The inventors of the present invention conducted extensive studies with the aim of providing an antistatic resin with excellent permanent antistatic properties, impact resistance, and transparency. In the presence of a satisfying rubbery polymer (
We have discovered that the above objective can be efficiently achieved by mixing a transparent graft copolymer obtained by graft polymerizing a vinyl monomer mixture containing a meth)acrylic acid ester monomer as an essential component. We have arrived at the present invention.

[Means for solving problems]

That is, the present invention consists of (1) (2 to 90% by weight of a salt of a diamine having 6 or more carbon atoms and isophthalic acid, (b) 0 to 88% by weight of an aminocarboxylic acid or lactam having 66 or more carbon atoms, and fC1
1 to 99 ffifi parts of an amorphous polyether μ ester amide composed of a poly(alkylene oquindo) glycol having a number average molecular weight of 200 to 6,000 and a total of 10 to 90% by weight of this and equimolar isophthalic acid,! :(81t
A monomer mixture 99-20 consisting of (b) a (meth)acrylic acid ester monomer and another vinyl monomer copolymerizable therewith in the presence of 1-80 parts by weight of a + rubbery polymer;
When graft polymerizing parts by weight, the difference between the refractive index of the polymer obtained by polymerizing only the monomer mixture (To) and the refractive index of the [al rubbery polymer] should be 0.02 or less (bl monomer mixture). Graft copolymer 9 that allows the composition of the mixture to be selectively obtained
9 to 1 part by weight, and the difference in refractive index between (B) the amorphous tl polyether ester amide and (B) the graft copolymer is 0.02 or less. be.

The present invention will be specifically explained below.

The composition of the present invention comprises a transparent graft copolymer in which the difference in refractive index between N amorphous rd riether ester amide and (Bl amorphous a! riether ester amide) is 0.02 or less.

(a) Salts of diamines having 6 or more atoms and isophthalic acid, which are amorphous polyether ester μamide components in the present invention, include hexamethylene diamine isophthalate, octamethylene diamine Isophthalate, decamethylenediamine-isophthalate, undecamethylenediamine-isophthalate, dodecamethylenediamine-isophthalate, etc. are used, and hexamethylenediamine-isophthalate is particularly preferably used. (false) diamines with 6 or more carbon atoms and isophtha/l/
If the proportion of the acid salt is less than 2% by weight, an amorphous polyether ester amide cannot be obtained, and if it exceeds 90% by weight, the antistatic properties will be insufficient, which is not preferable.

(A) It is a groove component of amorphous polyether ester amide (bl aminocarboxylic acids or lactams having 6 or more carbon atoms include ω-7 minocaderonic acid, ω-aminoenanthanoic acid, ω-amizukaguri/L' acid) , ω-aminopergonic acid, ω-aminocagliic acid and aminocarboxylic acids such as 11-aminoundecanoic acid, 12-7 minododecanoic acid or lactams such as cabrooctam, enanthuoctam, cabrioμoctam and laurolactam are used, especially ω-aminocaproic acid. is preferably used. If the proportion of (b) 7-minocarboxylic acid or lactam having 6 or more carbon atoms exceeds 88% by weight, an amorphous polyetheresteramide cannot be obtained and cannot be used.

(5) Examples of the (Cl poly (alkylene oxide) glycol) that is a constituent component of the amorphous polyether ester amide include polyethylene glycol, poly (L, 2-propylene oxide) glycol, poly (1,3-propylene oxide) glyco -p1 Poly (tetofumethylene oxide) glycol, poly (hexamethylene oxide) glycol, block or random copolymers of ethylene oxide and propylene oxide, and block or random copolymers of ethylene oxide and tetrahydrofufurine, etc. are used. Among them, polyethylene glycol is particularly preferably used because of its antistatic property of 4N.The number average molecular weight of poly(purkylene oxide) glycol is 200 to 6.000, and 250 to 2.
If the number average molecular weight is less than 200, the mechanical properties of the obtained polyetheresteramide will be poor, and if the number average molecular weight exceeds 6.000, antistatic properties will be insufficient, which is not preferred.

If the total proportion of poly(alkylene oxide) glycol (C) and isophthalic acid in equimolar amount is less than 10% by weight, the antistatic property will be poor; if it exceeds 90% by weight, B
) It cannot be used because it has poor affinity with graft copolymers and causes delamination, which impairs the appearance of molded products.

(A) The polymerization method of the amorphous polyether ester amide is not particularly limited. For example, (al diamine having 6 or more carbon atoms and salt of isophtha/L' acid) Minocarboxylic acid or lactam and FCL poly(alkylene oxide) glycol and about the same amount of isophthalic acid are charged as reactive species, heated at high temperature,
A known method can be used, such as a method in which a preliminary reaction is carried out while flowing a window element under normal pressure, and then polymerization is carried out under vacuum.

Next, the rubbery polymer (a) which is a constituent component of the graft copolymer (B) in the present invention has a glass transition temperature of 0.
℃ or less, specifically polybutadiene, polystyrene-butadiene, polyacrylonitrile-
diene rubbers such as butadiene, polyisoprene,
Examples include acrylic rubbers such as polychloroprene, polyacrylic A/butyl acid, and ethylene-globylene-diene monomer terpolymers. These are (AHI'
The difference in refractive index with polyetherester 7mid is 0.
02 or less.

Here, the difference in refractive index between the two is 0. If it exceeds 02, the transparency of the composition decreases and it cannot be used.

(B) The (b) (meth)acrylic acid ester type gas which is a constituent component of the graft copolymer includes acrylic/L/acid and methacrylic acid methyl, ethyl, propyl, n-
Examples include varnish/chill compounds such as butyl and i-butyl. In addition, other vinyl monomers that can be copolymerized with this include styrene, α-methylstyrene, vinyltoluene (D aromatic vinylμ monomer, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile). maleimide, maleimide monomers such as N-methylmaleimide, N-ethylmaleimide, and N-phenylmaleimide, N-vinylpyrrolidone, acrylic/L/7mide, maleic anhydride, acrylic acid, methacrylic acid, etc. The proportion of these monomers that can be copolymerized with the (meth)acrylic/L'#1 ester monomer is in the range of 1 to 99% by weight based on the total monomers. used within.

These vinyl monomer mixtures are prepared so that the difference in refractive index between the rubbery polymer and the polymer obtained by polymerizing only the vinyl monomer mixture is 0.02 or less. Made by selecting a vinyl monomer.

If the difference in refractive index between the two exceeds 0.02, the transparency of the graft copolymer will decrease, which is not preferable.

The refractive index of a matrix resin made only of a monomer mixture can be determined by calculation from a theoretical formula or by measuring the refractive index of a resin obtained by polymerizing a monomer mixture having the same composition in advance.

[F]) In the graft copolymer, (meth)acrylic/
99 to 20 parts by weight of a monomer mixture consisting of L' acid ester 1v phosphor and other vinyl monomers copolymerizable with it;
Preferably, 90 to 40 parts by weight is added by a known polymerization method, such as a method in which a monomer mixture, a polymerization initiator, and an emulsifier are continuously fed in the presence of a rubbery polymer latex to form an emulsion graft. Obtainable.

If the proportion of the rubbery polymer in the Q31 graft copolymer tsm is less than 1 part by weight, a composition with insufficient impact resistance will be obtained, and if it exceeds 80 parts by weight, the grafting rate will be low and the proportion of the rubbery polymer will deteriorate. It is not preferable because it has poor dispersion and reduces transparency and impact resistance.

This (Bl graft copolymer) is prepared by blending other vinyl polymers such as styrene-acrylonitrile-methyl methacrylate copolymer, styrene-methyl methacrylate copolymer, etc. to dilute the concentration of the rubbery polymer. However, it is preferable that the refractive index of the vinyl polymer used here has a difference of 0.02 or less from the refractive index of B) the graft copolymer.

(A) 1 to 99 parts by weight, particularly preferably 5 to 70 parts by weight, of the amorphous polyether ester ρ amide and (8) 99 to 1 part by weight, particularly preferably 95 to 1 part by weight, of the transparent graft copolymer thus obtained. It is blended within a range of 30 parts by weight.

(A) 1 part by weight of amorphous polyetheresteramide i
With S-mat, the antistatic properties of the resin composition are insufficient.

99 parts by weight IJiL5-tkl-, rg The resin composition becomes flexible and the mechanical properties are poor, which is not preferred.

There are no particular limitations on the method for producing the resin composition of the present invention, such as Banbury mixer, roll, Ext A/
- N amorphous polyether ester amide and (
B) It is manufactured by kneading a transparent graft copolymer.

It is also possible to further improve the antistatic property by adding an antistatic agent such as a metal salt of sulfonic acid or an anionic or cationic surfactant within a range that does not impair the transparency of the resin composition. Furthermore, various stabilizers such as antioxidants and ultraviolet absorbers, pigments, dyes, lubricants, and plasticizers can also be added as required.

[Effect]

In the present invention, an amorphous polyether ester amide obtained by copolymerizing a specific amount of a diamine having 6 or more carbon atoms and a salt of isophthalic acid, and a transparent graft copolymer having a refractive index difference of 0.02 or less A resin blended with the above has excellent permanent antistatic properties and transparency, and exhibits high mechanical properties.

This phenomenon occurs when a specific amount of (meth)acrylic/L' is added to a rubbery polymer that has no affinity with amorphous polyetheresteramide.
It is presumed that this is because the affinity between the amorphous polyether ester amide and the graft copolymer increases due to the fact that the R ester is grafted.

〔Example〕

EXAMPLES In order to explain the present invention more specifically, Examples and Comparative Examples will be given below. The resin composition finally obtained was molded by injection molding, and then various physical properties were measured using the following test methods.

Izotsu impact strength ASTM 0256-56A
Tensile strength ASTM 0638 flexural modulus
ASTM D790 Volume Resistivity 2 x 4
The measurement was carried out using a 0φ disk (room temperature: 23'C, humidity: 50% RH). For the first measurement, a super insulation resistance tester SM-LOE model manufactured by Toa Denpa Kogyo Co., Ltd. was used.

Light Transmittance Total light transmittance was measured using a 2xtoφ disk. A direct reading haze meter manufactured by Toyo Seiki Co., Ltd. was used for the measurement.

The appearance of the molded product was determined by visual inspection of the test piece, and the criteria for evaluation were ◎: extremely good appearance, O: good, and ×: defective due to damage to the surface of the molded product.

Further, parts and % in the examples indicate parts by weight and % by weight.

Reference Example (1) (A) Preparation of amorphous polyether ester amide A-, -1: Pre-prepared salt of hexamethylene diamine and isophthalic acid (IPA) (nylon 6I salt) 9.2
parts, 32 parts of ε-cabrotam, number average molecular weight 600
49.3 parts of polyethylene glycol/L', IPAI
3.9 parts of Irganox"1098 (antioxidant)
0.2 part and 0.1 part of antimony dioxide (SBO) catalyst
The mixture was placed in a reaction vessel equipped with a helical ribbon stirring blade, followed by straight displacement, heated and stirred at 240°C for 60 minutes to obtain a transparent homogeneous solution, and then polymerized for 5 hours at 260°C and below 0.5 mHg. A viscous and transparent polymer was obtained. Polyether ester amide (A-1) in the form of pellets was prepared by discharging the polymer in chunks onto a cooling bed and pelletizing it. This polyether ester amide remained crystal-free and transparent even after being left at room temperature for 200 days.

A-2 = 6.9 parts of nylon 6I salt, 24 parts of ε-carblock tam, polyethylene glycol/I/6 with a number average molecular weight of 1000: Same as A-1 except that 9 parts of L and 0.5 parts of IPAI were used. Polyether ester amide (A
-2) was adjusted. This polyether ester amide was confirmed to be amorphous in the same manner as A-1.

A-3: 40 parts of ε-cabrotam, number average molecular weight is 6
Polyether ester amide (A-3) was prepared under the same conditions as A-1 except that 49.3 parts of polyethylene glycol and 13.0 parts of adipic acid were used. When the amorphous nature of this polyether diamide was confirmed in the same manner as A-1, it was found that crystallization progressed and the transparency deteriorated significantly.

(A) #3) Graft copolymer hair styling s-1: methyl methacrylate 72%, styrene in the presence of 30 parts (solid content) of polybutadiene latex (rubber particle size 0.25μ, gel content 80%) 24%, acrylonitrile 4
70 parts of a monomer mixture consisting of: The obtained graft copolymer latex was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered, and dried to prepare a powdery graft copolymer (B-1).

B-2: Methymethacrylic acid tv 60.4 in the presence of 50 parts (solid content) of styrene-butadiene copolymer latex (styrene copolymerization %, rubber particle size 0.25μ, gel content 78%) After emulsion polymerization of 50 parts of a monomer mixture consisting of 39.6% styrene and 39.6% styrene, a powdery graft copolymer (B-2) was prepared in the same manner as B-1.

B-32 Polybutadiene latex 9 used in B-1
Methyl methacrylate 1v in the presence of 0 parts (solid content)
After emulsion polymerization of 10 parts of a monomer mixture consisting of 72% styrene, 24% styrene, and 4% acrylonitrile/I/I, a powdery graft copolymer (B-3) was prepared in the same manner as B-1.

(3) Preparation of fC1 copolymer C-t: 72 parts of methi methacrylate, 24 parts of styrene,
A copolymer (C-
t) was prepared.

C-2=60.4 parts of methyl methacrylate, 39 parts of styrene
．． 6 parts were copolymerized to prepare a copolymer <C-2).

C-3: methacrylate/I/acid methoxy/L 150 parts, styrene 7
A copolymer (C-3) was prepared by copolymerizing 50 parts.

Example-1 N polyether ester amide prepared in Reference Example and [F
]) Graft copolymer and C) copolymer were mixed at the blending ratio shown in Table 11, and a 40m tube with a vent was prepared. Pellets were produced by melt-kneading and extruding at a resin temperature of 220° C. using a 1φ extruder. Next, a test piece was molded using an injection molding machine at a cylinder temperature of 230°C and a mold temperature of 60°C, and each physical property was measured.

The specific volume resistivity was determined using an injection molded disk with a thickness of 2 mm.
Measurements were made under the following conditions.

(1) Immediately after molding, wash with an aqueous solution of detergent 11 Mama Lemon 11 (manufactured by Lion Yushi Co., Ltd.), then thoroughly wash with distilled water, remove surface moisture, and store at 50% RH and 23°C for 24 hours. The humidity was adjusted for a period of time and measured.

(A) After molding, it was left at 50% RH and 23°C for 200 days, washed with a detergent solution of Mama Lemon II, and then thoroughly washed with distilled water to remove surface moisture, and then 50% The humidity was adjusted at RH and 23° C. for 24 hours. The measurement results are shown in Table 1.

Comparative Example-1 N polyether ester amide prepared in Reference Example and (B
The I-graft copolymer and C) copolymer were mixed at the blending ratios shown in Table It, and their physical properties were measured in the same manner as in Example 1.

The following is clear from the results in Table 1. The resin compositions (41 to 6) of the present invention all have excellent mechanical properties such as transparency and impact strength, and have low specific volume resistivity. Furthermore, the resistance value hardly changes even after surface cleaning or changes over time, and it exhibits excellent permanent antistatic properties. Moreover, the appearance of the molded product is also extremely good.

That is, the resin composition of the present invention is a composition that has both excellent mechanical properties and permanent antistatic properties, and gives a molded article with an extremely good appearance.

On the other hand, when the amount of amorphous polyether ester amide N is 1 part by weight (&7), the antistatic property (resistivity) is poor, and when the amount is 99 parts by weight (&8.15), the tensile yield stress is and the flexural modulus is inferior.

When the amount of graft copolymer (6) is 1 part by weight Higashiura (f9), the impact strength is inferior to 99 parts by weight! j3) In case (414, 16), the antistatic property is poor.

When using a graft copolymer (13) in which the proportion of the rubber R polymer is 80 parts by weight (&10), the dispersion of the graft copolymer is poor and the appearance of the molded product is impaired. When a crystalline polyether ester copolymer is used, the difference in refractive index between the amorphous polyether ester amide (A) and the graft copolymer [F]) and copolymer C) is 0.
．． In the case of OI μL 3 (&11 to 13), transparency is significantly impaired, which is not preferable.

〔Effect of the invention〕

The present invention has made it possible to efficiently obtain a thermoplastic resin composition that has transparency and permanent antistatic properties, as well as excellent impact resistance and bending elasticity.

Claims (1)

Scope of Claims: (A) (a) 2 to 90% by weight of a salt of a diamine having 6 or more carbon atoms and isophthalic acid, (b) 0 to 88% by weight of an aminocarboxylic acid or lactam having 6 or more carbon atoms, and (c) Number average molecular weight 200-60
00 poly(alkylene oxide) glycol and 1 to 99 parts by weight of an amorphous polyether ester amide consisting of 10 to 90 parts by weight of the same molar amount of isophthalic acid; In the presence of 1 to 80 parts by weight of combined (
b) When graft polymerizing 99 to 20 parts by weight of a monomer mixture consisting of a (meth)acrylic acid ester monomer and another vinyl monomer copolymerizable with it, (b) only the monomer mixture Graft copolymer obtained by selecting the composition of (b) monomer mixture so that the difference between the refractive index of the polymer obtained by polymerizing and the refractive index of (a) rubbery polymer is 0.02 or less Union 99-1
parts by weight, and the difference in refractive index between (A) the amorphous polyether ester amide and (B) the graft copolymer is 0.0.
2 or less.