JPH07216134A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject compsn. which is excellent 10 weatherability, antistatic properties, coated appearance of welds, adhesion to a coating film, etc., and suitable esp. for a molding subjected to a posttreatment such as partial coating or partial plating. CONSTITUTION:This resin compsn. comprises 100 pts.wt. thermoplastic resin, 0.1-20 pts. wt. org. compd. having a 7-value calculated by the general formula: lngammaV<1/3>= 0.3853lndelta<2>+0.0082) (wherein A is 0.3853, V is the molar vol.; and deltais the SP value) of 40 or higher, and up to 20 pts.wt. antistatic compd.

Description

Detailed Description of the Invention

[0001]

The present invention relates to weather resistance, antistatic property,
The present invention relates to a thermoplastic resin composition that is used as a molding material for a molded product having excellent coating appearance of a weld portion, adhesion of a coating film, and the like.

[0002]

2. Description of the Related Art Thermoplastic resins are used for interior and exterior parts of automobiles, housing materials for household electrical appliances, structural materials, etc. because they are excellent in molding processability and secondary processability such as painting and plating. Has been done. However, recently, the number of molded products for which partial coating or partial plating is carried out has increased depending on the use, and the weather resistance of the unpainted or unplated part and the coating appearance of the welded part have become problems. As a method to improve the weather resistance of unpainted or unplated parts,
Addition of a known anti-aging agent can be expected to improve to some extent, but eventually discolors. Further, as a method of improving the coating appearance of the weld portion, it is considered to improve chemical resistance, and it is disclosed in JP-A-54-94547, JP-B-63-60953, or JP-A-3-2155.
Japanese Patent No. 47 discloses such a technique, but the adhesion of the coating film is poor.

[0003]

The present invention has been made against the background of the above-mentioned problems of the prior art, and is excellent in weather resistance, antistatic property, coating appearance of weld portion, adhesion of coating film, and the like. It is an object of the present invention to provide a thermoplastic resin composition suitable as a molding material for a molded product to be secondarily processed such as partial coating and partial plating.

[0004]

[In the general formula (I), V represents a molar volume, δ represents an SP value, A and B are constants, and A=0.3853 and B=0.0082. ]

Particularly, in the thermoplastic resin composition of the present invention, a hydrophilic group-containing unsaturated compound is used as a copolymerization component in an amount of 0.
It is preferable to use the thermoplastic resin (A) containing 01 to 20% by weight.

As the thermoplastic resin as the component (A),
Examples thereof include maleimide copolymers, vinyl resins such as acrylic resins and styrene resins, polycarbonates, polyamides, and thermoplastic polyesters, and styrene resins are preferable. Examples of the styrene resin include AS resin and polystyrene/styrene-MMA.
Examples of the copolymer include a styrene-based copolymer, a styrene-maleimide-based copolymer, a styrene-maleic anhydride-based copolymer, and a rubber-modified styrene-based resin, and a rubber-modified styrene-based resin is particularly preferable.

As the rubber-modified styrene resin,
Rubber-modified styrenic resin itself, or rubber-modified styrene-based resin and styrene-based resin (not rubber-modified)
And a rubbery polymer contained in a specific styrene resin for the purpose of obtaining a high degree of impact resistance. The content may be a simple mechanical blending method, but in order to obtain good compatibility, the so-called graft copolymerization is carried out by graft-copolymerizing a styrene-based monomer or the like in the presence of a rubbery polymer. The one obtained by the polymerization method is more preferable. Further, a rubber-modified styrene resin (graft copolymer) obtained by this method
In addition, it is also preferable to use a resin obtained by a so-called graft-blending method in which a styrene resin obtained by a separate method is mixed. The graft ratio with respect to the rubbery polymer is preferably 10 to 150% by weight, more preferably 20 to 120% by weight.

Examples of the rubbery polymer include polybutadiene rubber, diene rubber such as styrene-butadiene rubber, styrene-butadiene block copolymer,
Examples thereof include block copolymers such as styrene-isoprene block copolymers and hydrogenated products thereof, ethylene-propylene-(diene) copolymer rubbers, acrylic rubbers, silicone rubbers and the like. The amount of the rubbery polymer in the component (A) is preferably 3 to 60% by weight, more preferably 5 to 50% by weight. Further, examples of the styrene-based monomer include styrene, α-methylstyrene, bromostyrene, and the like. Among these, styrene is optimally used.

If necessary, it is possible to copolymerize the styrene-based monomer with another monomer copolymerizable with the styrene-based monomer. Examples of the other monomer include acrylonitrile, methacrylonitrile, methyl methacrylate, N-phenylmaleimide, N-cyclohexylmaleimide and the like. In the rubber-modified styrenic resin, impact resistance is difficult to develop when the styrenic monomer is used alone, so it is preferable to copolymerize acrylonitrile. Further, in order to improve heat resistance, it is preferable to copolymerize N-phenylmaleimide.

Specific examples of the rubber-modified styrene resin include acrylonitrile-butadiene-styrene resin (A
BS resin), acrylonitrile-ethylene/propylene-styrene resin (AES resin), methyl methacrylate-
Butadiene-styrene resin (MBS resin), acrylonitrile-butadiene-methyl methacrylate-styrene resin, acrylonitrile-n-butyl acrylate-styrene resin (AAS resin), rubber modified polystyrene (high impact polystyrene; HIPS), α-methylstyrene The heat-resistant rubber-modified styrene resin used and the like can be mentioned.

The thermoplastic resin which is the component (A) of the present invention is preferably a vinyl resin, more preferably a vinyl resin containing a hydrophilic group-containing unsaturated compound as a copolymerization component, and particularly preferably a hydrophilic group-containing resin. A rubber-modified styrenic resin containing an unsaturated compound as a copolymerization component. The method of incorporating the hydrophilic group-containing unsaturated compound as a copolymerization component into the thermoplastic resin as the component (A) is not particularly limited, but for example, a hydrophilic group-containing unsaturated compound may be added during polymerization of the thermoplastic resin. It is achieved by coexisting and copolymerizing. For example, a rubber-modified styrene-based resin will be described as an example. (a) A method of copolymerizing a hydrophilic group-containing unsaturated compound as a copolymerization component during the polymerization of the rubber-modified styrene-based resin, or In the case of a mixture of a base resin and a styrene resin, there may be mentioned a method of copolymerizing a hydrophilic group-containing unsaturated compound in the presence of at least one of them. Preferably,
(B) is a method of copolymerizing a styrene resin with a hydrophilic group-containing unsaturated compound.

Here, the unsaturated compound containing a hydrophilic group has at least one unsaturated bond (double bond, triple bond) and contains a hydrophilic group such as a hydroxyl group, a carboxyl group or an amino group. A compound, preferably a compound containing a hydroxyl group. Typical examples thereof include an alcohol having a double bond, an alcohol having a triple bond, an ester of a monovalent or divalent unsaturated carboxylic acid and an unsubstituted dihydric alcohol, and an unsubstituted trivalent unsaturated carboxylic acid. Examples thereof include esters with polyhydric alcohols, esters with unsubstituted tetrahydric alcohols, and esters with unsubstituted pentavalent or higher alcohols.

Of the hydroxyl group-containing unsaturated compounds used in the present invention, suitable representative examples include 3-
Hydroxy-1-propane, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4
-Hydroxy-2-butene, 3-hydroxy-2-methyl-1-propene, cis-5-hydroxy-2-pentene, trans-5-hydroxy-2-pentene, cis-
1,4-dihydroxy-2-butene, trans-1,4
-Dihydroxy-2-butene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3
-Hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxyethyl crotonate, 2,3,4,5,6-pentahydroxyhexyl acrylate, 2,3,4,5,6-pentahydroxyhexyl methacrylate, 2, Examples include 3,4,5-tetrahydroxypentyl acrylate and 2,3,4,5-tetrahydroxypentyl methacrylate.
Among these, it is preferable to use 2-hydroxyethyl methacrylate. These hydrophilic group-containing unsaturated compounds may be used alone or in combination of two or more.

The copolymerization content of the unsaturated compound containing a hydrophilic group in the thermoplastic resin as the component (A) is preferably 0.
The amount is 01 to 20% by weight, more preferably 0.2 to 5% by weight, particularly preferably 0.3 to 2% by weight, and most preferably 0.3 to 1% by weight. When the copolymerization content of the hydrophilic compound containing a hydrophilic group is 0.01% by weight or more, the adhesiveness between the obtained composition and the coating film is further excellent. On the other hand, 20% by weight
If it exceeds, the molding heat stability and the molding processability are deteriorated, which is not preferable.

Next, in the organic compound which is the component (B), the γ value calculated by the Hildebrand-Scott relational formula represented by the following general formula (I) is 40 (dyn/ cm) or more, preferably 40 to 80 (dyn/cm). lnγV ^1/3 =Aln δ ² +B... General formula (I) [In the general formula (I), V is a molar volume, δ is an SP value,
A and B are constants, A=0.3853, B=0.0082
Is. ] Here, the γ value is 40 (dyn/cm)
If it is less than this, the adhesion of the coating film becomes poor, which is not preferable.

Examples of the component (B) used in the present invention include (b-1) bis(2,2',6,6'-tetramethyl-4-piperidyl) sebacate and (b-2)2. , 2
-Methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol] and the like. Above (b-1)
Is a compound represented by the following structural formula (I), and the γ value calculated from the Hildebrand-Scott relational formula represented by the general formula (I) is 42. In addition, the above (b-
2) is a compound represented by the following structural formula (II), and the γ value calculated from the Hildebrand-Scott relational formula represented by the general formula (I) is 52.

[0017]

[Chemical 1]

[0018]

[Chemical 2]

The amount of the organic compound (B) used is (A)
0.1-20 parts by weight, preferably 0.2-10 parts by weight, more preferably 0.3-
5 parts by weight. If the amount of the component (B) used is less than 0.1 parts by weight, the weld appearance after coating, the adhesion of the coating film and the weather resistance will be poor, while if it exceeds 20 parts by weight the impact resistance and heat resistance will be poor. Become.

Next, the component (C) used in the present invention is
It is a compound having an antistatic property such as anionic property, cationic property and nonionic property. Specific examples of the component (C) include
N,N'-dipolyoxyalkylene-N-alkyl (or alkenyl)amine, N,N'-bishydroxyalkyl-N-alkylamine, N,N'-dialkyl-
Cationic antistatic agents such as N-alkyl (or alkenyl) amines, anionic antistatic agents such as sodium alkylbenzene sulfonate, nonionic antistatic agents such as mono-, di- or triglycerides, polyoxyalkylene alkyl phenyl ethers, etc. Be done.
These (C) antistatic compounds may be used alone or in combination of two or more.

The amount of component (C) used is 100 parts of component (A).
20 parts by weight or less, preferably 0.05
-5 parts by weight, more preferably 0.1-3 parts by weight. If the amount of component (C) used exceeds 20 parts by weight, the adhesion, impact resistance, and heat resistance of the coating film will deteriorate. Further, when the environmental humidity is less than 10%, it is preferable to use the component (C) because sufficient antistatic properties cannot be obtained only with the components (A) and (B).

The composition of the present invention can be obtained by mixing the components (A) to (C) using a conventional mixing method. For example, each component is mixed with a mixer, and then melt-kneaded with an extruder at 180 to 230° C. to granulate.
Further, each component can be simply melt-kneaded and molded in a molding machine.

[0023]

EXAMPLES The present invention will be described in more detail below with reference to examples. In the examples, parts and% are based on weight unless otherwise specified. The evaluation of physical properties is as follows. Weld appearance after painting The weld is on the center line, and the thickness is 3.2 mm ×
Using a 7 mm×15 mm test piece, a paint [High Urethane #5000 manufactured by NOF CORPORATION] was applied using an air spray gun (film thickness=25 μm). The coated surface of the welded portion after this coating was visually evaluated. ○: Weld line is not visible. △: It is clear that the weld line is seen carefully. ×: Weld line is clearly visible.

Adhesion of coating film The width of the coated surface of the test piece whose weld appearance was evaluated was 2 mm wide.
mm squares were cut to make 100 squares, and a peeling test was performed using a water jet with a water pressure of 20 kg/cm ² . 100/100 means that 100 of the 100 squares remain, and 50/100 means that of the 100 squares, 50 squares remain.

[0025] Izod impact strength ASTM D256 (1/4 ", 23 ℃ , notched) Heat distortion temperature ASTM D648 (18.6kg / cm ²⁾ light resistance sunshine weather meter (black panel temperature 6
After accelerated light resistance for 400 hours at 3° C. and a rain cycle of 10 minutes/120 minutes), the color difference ΔE from before light resistance was evaluated. Antistatic property Test piece with a thickness of 3.2 mm × 7 mm × 15 mm
After conditioning for 8 hours at 50° C. and 50% humidity, the surface resistivity was measured.

Examples 1 to 4 and Comparative Examples 1 to 5 Preparation of Component (A) The following components were used as the component (A). Rubber-modified styrene resin (a-1); 40 parts of polybutadiene rubber latex in terms of solid content, ion-exchanged water 65 in a reactor equipped with a reflux condenser, a thermometer and a stirrer.
Parts, 0.35 parts of rosin acid soap, 15 parts of styrene and 5 parts of acrylonitrile, then 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate heptahydrate and 0.4 parts of glucose are ionized. It was added to a solution dissolved in 20 parts of exchanged water.

Then, 0.07 part of cumene hydroperoxide was added to start the polymerization, and the polymerization was carried out for 1 hour. After that, 45 parts of ion-exchanged water and 0.7 part of rosin acid soap were added.
30 parts of styrene, 10 parts of acrylonitrile and 0.01 part of cumene hydroperoxide were continuously added over 2 hours, and the reaction was completed by further polymerizing for 1 hour. Sulfuric acid was added to the obtained copolymer latex for coagulation, and the content of residual organic acid and/or metal salt was 0.
It was washed with water and dried to 5% or less to obtain a rubber-modified styrene resin (a-1).

Styrene resin (a-2); reflux condenser,
In a reactor equipped with a thermometer and a stirrer, ion-exchanged water 2
50 parts, potassium rosinate 3.0 parts, styrene 70 parts,
Add 30 parts acrylonitrile and 0.1 part t-dodecyl mercaptan, then 0.05 parts sodium ethylenediaminetetraacetate, 0.002 parts ferrous sulfate heptahydrate and 0.1 parts sodium formaldehyde sulfoxylate.
Parts were added to a solution prepared by dissolving 8 parts of ion-exchanged water. Then, 0.1 part of diisopropylbenzene hydroperoxide was added to start the polymerization, and the polymerization was carried out for about 1 hour to complete the reaction. Sulfuric acid was added to the obtained copolymer latex for coagulation, washed with water until the residual organic acid and/or metal salt content was 0.5% or less, and dried to obtain a styrene resin (a-2). It was

Hydroxyl group-containing styrenic resin (a-
3); in a reactor equipped with a reflux condenser, a thermometer and a stirrer, 250 parts of ion-exchanged water, 1.0 part of sodium dodecylbenzenesulfonate, 70 parts of styrene, 20 parts of acrylonitrile, 10 parts of 2-hydroxyethyl methacrylate.
And 0.1 part of t-dodecyl mercaptan were added, and then 0.16 part of sodium persulfate was added to a solution prepared by dissolving 8 parts of ion-exchanged water. The reaction was completed by polymerizing for about 1 hour. Calcium chloride was added to the obtained copolymer latex for coagulation, washed with water until the content of residual organic acid and/or metal salt was 0.5% or less, and dried to obtain a hydroxyl group-containing styrene resin. ..

Preparation of Component (B) As the component (B), (b-1) bis(2,2′,6,6)
6'-tetramethyl-4-piperidyl) sebacate [MARK LA-77 manufactured by Asahi Denka Co., Ltd.], (b-
2) 2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol] [Asahi Denka Kogyo KK, MA
RK LA-31] and (b-3) stearic acid [manufactured by NOF CORPORATION] were used.

Preparation of component (C) As the component (C), (c-1) N,N′-dipolyoxyalkylene-N-alkenylamine (manufactured by Kao Corporation, Electrostripper EA) was used.

Production of Thermoplastic Resin Composition The components shown in Tables 1 and 2 were melt-kneaded at a temperature of 190 to 240° C. using an extruder having an inner diameter of 50 mm to prepare pellets. The obtained pellets were molded at a molding temperature of 200 to 240° C. using a 5 oz injection molding machine to prepare test pieces, and the physical properties thereof were evaluated. The results are shown in Tables 1-2.

[0033]

[Table 1]

[0034]

[Table 2]

As is apparent from Table 1, the compositions of the present invention of Examples 1 to 4 have been obtained as the object of the present invention. On the other hand, Comparative Examples 1 and 2 are compositions lacking the component (B) which is an essential component of the present invention, and are inferior in weld appearance after coating, adhesion of coating film, and light resistance. The composition of Comparative Example 3 had a γ value of 38 (b) as the component (B).
-3) This is an example using stearic acid (manufactured by NOF CORPORATION), and the adhesion of the coating film is poor. The compositions of Comparative Examples 4 to 5 are examples in which the amount of the component (B) used in the present invention is outside the range of the present invention. That is, in Comparative Example 4, since the component (B) was too small, the weld appearance after coating, the adhesion of the coating film, and the light resistance were poor, and in Comparative Example 5, the component (B) was too large.
Poor impact resistance and heat resistance.

[0036]

INDUSTRIAL APPLICABILITY The thermoplastic resin composition of the present invention is excellent in weather resistance, antistatic property, weld appearance after coating, adhesion of coating film and the like, and is particularly subjected to secondary processing such as partial coating and partial plating. It is suitable as a molding material for molded articles.

Claims (2)

[Claims] 1. The γ value calculated by the following general formula (I) is 40 with respect to 100 parts by weight of the thermoplastic resin (A).
A thermoplastic resin composition comprising 0.1 to 20 parts by weight of an organic compound having a (dyn/cm) or more and (C) 20 parts by weight or less of a compound having an antistatic property. lnγV ^1/3 =Aln δ ² +B... General formula (I) [In the general formula (I), V is a molar volume, δ is an SP value,
A and B are constants, A=0.3853, B=0.0082
Is. ] 2. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin (A) contains 0.01 to 20% by weight of a hydrophilic group-containing unsaturated compound as a copolymerization component.