JPH09249788A - Resin composition for urethane coating and molding coated with urethane coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition which can give moldings excellent in adhesion of films of urethane coating materials by mixing a composition comprising a saturated polyester resin and a rubberreinforced styrene resin with glass fibers and a polyamide elastomer. SOLUTION: This composition comprises 100 pts.wt. composition comprising 5-80wt.% saturated polyester resin (A) and 95-20wt.% rubber-reinforced styrene resin (B), 1-50 pts.wt. glass fibers (C) and 1-50 pts.wt. polyamide elastomer (D). A molding obtained by molding the composition is coated with a urethane coating material to form a urethane-coated molding. The order of mixing components A to D and the state of the mixture are not particularly limited. The method for molding the composition is also not particularly limited.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a urethane coating resin composition which is obtained by blending a polyamide elastomer and glass fibers in a saturated polyester resin-based molding material and which has excellent coating film adhesion during urethane-based paint coating. .

[0002]

2. Description of the Related Art Saturated polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) are already known as polymers having excellent chemical resistance.
Due to its poor heat resistance, it has been proposed to blend a saturated polyester resin with a rubber-reinforced styrene resin such as ABS resin or glass fiber (Japanese Patent Publication Nos. 47-30421 and 51-25261). Such an improved saturated polyester resin-based molding material is widely used in the fields of vehicles, electric / electronics, machinery and daily necessities. However, in the urethane coating performed for decoration and weather resistance improvement, there is a problem that the adhesive force between the coating film made of the urethane coating material and the resin is not sufficient.

[0003]

Means for Solving the Problems As a result of diligent studies on the above-mentioned problems in a saturated polyester resin-based molding material, the present inventors have found that a composition comprising a saturated polyester resin and a rubber-reinforced styrene-based resin has a specific amount of The present inventors have found that a resin composition having improved coating film adhesion at the time of coating a urethane-based paint can be obtained by blending a polyamide elastomer and glass fiber, and arrived at the present invention.

That is, according to the present invention, 1 to 100 parts by weight of a composition composed of 5 to 80% by weight of a saturated polyester resin (A) and 95 to 20% by weight of a rubber-reinforced styrene resin (B) is used. The present invention provides a resin composition for urethane coating, which comprises 50 parts by weight and 1 to 50 parts by weight of a polyamide elastomer (D).

The present invention will be described in detail below. Examples of the saturated polyester resin (A) in the present invention include polyethylene terephthalate, polybutylene terephthalate, and polyester-ether block polymers having a polyester hard segment and a polyether soft segment, and these may be used alone or in combination of two or more. Can be used. Particularly preferred is polybutylene terephthalate.

The rubber-reinforced styrene resin (B) in the present invention is a diene rubber such as polybutadiene, butadiene-styrene rubber or butadiene-acrylonitrile rubber, non-conjugated diene component such as ethylene-propylene rubber, ethylidene norbornene or dicyclopentadiene. Ethylene-propylene-containing rubber such as ethylene-propylene-non-conjugated rubber, acrylate-based copolymer,
In the presence of at least one rubber component selected from chlorinated polyethylene and the like, a monomer composed of an aromatic vinyl monomer and a vinyl cyanide monomer and / or another copolymerizable vinyl monomer is used. It is a resin produced by polymerizing a monomer.

The rubber component is produced by emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization or the like. The particle size and gel content of the rubber-like polymer in the case of production by emulsion polymerization are not particularly limited, but the average particle size is 0.
It is desirable that it is 1-1 μm and the gel content is 0-95%.

Aromatic vinyl monomers include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, α-methylvinyltoluene, dimethylstyrene,
Chlorostyrene, dichlorostyrene, bromostyrene,
Examples thereof include dibromostyrene and vinylnaphthalene, and one kind or two or more kinds can be used. Particularly preferred are styrene and α-methylstyrene.

Examples of the vinyl cyanide-based monomer include acrylonitrile, methacrylonitrile, fumaronitrile and the like, and one kind or two or more kinds can be used. Acrylonitrile is particularly preferred.

Other copolymerizable monomers include unsaturated carboxylic acid alkyl esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate and 2-ethylhexyl methacrylate. Examples of the monomer include imide-based monomers such as a system monomer, maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide, and one kind or two or more kinds can be used. Methyl methacrylate and N-phenylmaleimide are particularly preferable.

There are no particular restrictions on the composition ratio of the rubber component, the aromatic vinyl monomer and the vinyl cyanide monomer and / or other copolymerizable vinyl monomer in the rubber-reinforced styrene resin. Is 10 to 40% by weight of rubber, 40 to 70% by weight of aromatic vinyl monomer and 20 to 50% by weight of vinyl cyanide monomer and / or other copolymerizable vinyl monomer. . Further, it is not necessary that all of the aromatic vinyl-based monomer, the vinyl cyanide-based monomer, and / or another copolymerizable vinyl-based monomer be bonded on the rubber, and the rubber does not need to have these monomers. In the form of a mixture of a graft polymer formed by bonding with an aromatic vinyl-based monomer, a vinyl cyanide-based monomer and / or a copolymer of other vinyl-based copolymerizable monomers. Also includes.

The graft polymer and copolymer can be produced by known emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization or a combination thereof. Also,
The rubber-reinforced styrene resin (B) may be a mixture of polymers obtained by different polymerization methods, such as a mixture of an emulsion graft polymer and a block copolymer.

The compounding ratio of the saturated polyester resin (A) and the rubber-reinforced styrene resin (B) in the present invention is
The saturated polyester resin (A) is 5 to 80% by weight and the rubber-reinforced styrene resin (B) is 95 to 20% by weight. When the saturated polyester resin is less than 5% by weight (the rubber-reinforced styrene-based resin exceeds 95% by weight), the heat resistance and the chemical resistance are poor, and when it exceeds 80% by weight (the rubber-reinforced styrene-based resin is less than 20% by weight). The impact resistance and adhesion tend to be poor. From the viewpoint of heat resistance, chemical resistance and adhesion, saturated polyester resin is preferably 20 to 80% by weight and rubber-reinforced styrene resin is 80 to 20% by weight.

As the glass fibers (C), known glass fibers can be used. There is no limitation on the sizing agent and the surface treatment agent, and glass fibers that have been subjected to a converging treatment with an acrylic resin, an epoxy resin, a urethane resin or the like and / or a surface treatment with a silane coupling agent or the like can also be used. Further, the shape of the fiber diameter and the fiber length is not limited at all, but the fiber diameter of 0.2 to 20 μm and the fiber length of 1 to 30 mm are preferable.

The glass fiber (C) is blended in an amount of 1 to 50 parts by weight per 100 parts by weight of the composition comprising the saturated polyester resin (A) and the rubber-reinforced styrene resin (B). 1
If it is less than 50 parts by weight, the rigidity and adhesion are poor, and if it exceeds 50 parts by weight, the fluidity and impact resistance of the final composition are lowered. From the aspects of fluidity, impact resistance, heat resistance and shrinkage of the composition, 5 to 30 parts by weight is preferable.

The polyamide elastomer (D) means an aminocarboxylic acid having 6 or more carbon atoms as a hard segment, a lactam, or nylon mn having m + n ≧ 12.
A salt (X) and a polyol as a soft segment, for example, poly (alkylene oxide) glycol (Y), and the proportion of the component (X) in the elastomer is 95 to 10% by weight, preferably 9.
0 to 20% by weight. If the proportion of the component (X) in the elastomer exceeds 95% by weight, the flexibility becomes 1.
If it is less than 0% by weight, the chemical resistance tends to be poor.

Aminocarboxylic acid having 6 or more carbon atoms or lactam or nylon mn salt (X) having m + n ≧ 12
As, ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminobergonic acid, ω
-Aminocapric acid, 11-aminoundecanoic acid, 12
-Aminocarboxylic acids such as aminododecanoic acid or lactams such as caprolactam and laurolactam, and nylons 6.6, 610, 612, 11.6, 11.1
Nylon salts such as 0, 11.12, 12.6, 12.10, 12.12.

As the poly (alkylene oxide) glycol (Y), polyethylene glycol, poly (1,
2 and 1,3 propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, a block or random copolymer of ethylene oxide and propylene oxide,
Examples include a block or random copolymer of ethylene oxide and tetrahydrofuran. Their average molecular weight is 500 to 3000.

The bond between the component (X) and the component (Y) may be an ester bond or an amide bond depending on the terminal group of the elastomer component. A third component such as a dicarboxylic acid or a diamine can be used depending on the bond.

The dicarboxylic acid has 4 to 20 carbon atoms, and examples thereof include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4, Aromatic dicarboxylic acids such as 4-dicarboxylic acid, diphenoxyethanedicaric acid, sodium 3-sulfoisophthalate, 1,
Alicyclic dicarboxylic acids such as 4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,4-dicarboxylic acid, and succinic acid, oxalic acid, adipic acid, and dicarboxylic acid.

Examples of the diamine include aromatic, alicyclic, and aliphatic diamine (hexamethylenediamine).

Polyamide elastomer is also called polyether ester amide, and is disclosed in JP-A-62-232.
450, JP-A-63-33456, JP-A-63-952
51, JP-A-01-60647, and JP-A-01-2405.
53, JP-A-03-97751, JP-A-04-3095
47, JP-A-04-314741, JP-A-04-348
150, JP 05-230365, JP 05-26
2971, JP 05-287161 A, JP 05-2
95191, Japanese Patent Laid-Open No. 05-320497, Japanese Patent Laid-Open No. 06-
313079, JP-A-07-10989, JP-A-07-
145368, JP07-188475, JP07
The substances described in 188476 and the like are used.

The polyamide elastomer (D) is a saturated polyester resin (A) and a rubber-reinforced styrene resin (B).
1 to 50 parts by weight per 100 parts by weight of the composition consisting of If it is less than 1 part by weight, the adhesion of the final composition will not be improved, and if it exceeds 50 parts by weight, the rigidity will decrease. From the viewpoint of mechanical properties including adhesiveness and rigidity of the composition,
30 parts by weight are preferred.

There is no limitation on the order of mixing the saturated polyester resin (A), the rubber-reinforced styrene resin (B), the glass fiber (C) and the polyamide elastomer (D) and the state thereof, such as pellets, beads and powder. Examples include a simultaneous simultaneous mixing of the four components (A), (B), (C) and (D) according to the form, and a method of mixing the remaining components after premixing the specific components. As a mixing method,
Known methods such as Banbury mixer, roll, and extruder can be adopted. In addition, at the time of mixing, if necessary, an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, a lubricant,
Additives such as dyes, pigments, plasticizers, flame retardants, mold release agents, metal fibers, carbon fibers, metal flakes, reinforcing materials, and fillers can be added. Further, a thermoplastic resin such as polyacetal, polycarbonate, polyamide, polyphenylene oxide, polymethylmethacrylate, or polyvinyl chloride can be appropriately blended.

The method of molding the resin composition of the present invention is not particularly limited, and it may be molded by a known method such as injection molding, extrusion molding, compression molding, blow molding and the like. The molding temperature at this time is preferably in the range of 230 to 290 ° C. In the present invention, the method for applying urethane coating to the molded product is not particularly limited, and the urethane coating can be applied by means such as brush coating, spraying, roll coating, dipping or the like.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, the number of parts and the percentage are all shown on a weight basis.

Saturated polyester resin (A) A-1: polybutylene terephthalate (PBT) N-1000 manufactured by Mitsubishi Rayon Co., Ltd.

Rubber-Reinforced Styrene Resin (B) B-1: Copolymerized with 15 parts of acrylonitrile and 35 parts of styrene by emulsion polymerization in the presence of 50 parts (solid content) of polybutadiene rubber latex having a weight average particle diameter of 0.43 μm. This was polymerized to prepare an ABS graft copolymer latex (graft ratio: 50%, free acrylonitrile-styrene copolymer intrinsic viscosity: 0.63). Separately, in a reactor purged with nitrogen, 120 parts of pure water and potassium persulfate of 0.
After charging 3 parts, the temperature was raised to 65 ° C. with stirring. Then, 30 parts of acrylonitrile, 70 parts of styrene and 30 parts of an emulsifier aqueous solution containing 2 parts of sodium dodecyl sulfonate and a mixed monomer solution consisting of 0.25 of t-dodecyl mercaptan were continuously added over 5 hours, and then the polymerization system was heated to 70 ° C. The temperature was raised and aged for 3 hours to complete the polymerization, to produce a styrene-acrylonitrile copolymer having an intrinsic viscosity of 0.58. After mixing 30 parts of ABS graft copolymer latex (solid content) and 70 parts of styrene-acrylonitrile copolymer latex (solid content), 1 part of Sumilizer NW and Trisnonyl as an antioxidant per 100 parts of total solid content of the copolymer. Phenylphosphite 2
Parts were added, and after salting out with magnesium sulfate, separation and recovery, a rubber-reinforced styrene resin (B) having a rubber content of about 15% was obtained.

Glass fiber (C) C-1: Fiber diameter 10 μm, fiber length 3.0 mm, glass fiber treated with epoxy type sizing agent, aminosilane type surface treatment agent (RES 03-TP31 manufactured by Nippon Glass Fiber Co., Ltd.)

Polyamide elastomer (D) D-1: Polyether ester amide (manufactured by Sanyo Kasei Co., Ltd.,
Pelestat IOS-6321) D-2: Polyether ester amide (Toray Industries, Inc., Bepax 4011MA)

Talc: Hayashi Kasei, Micron White #
5000S

Examples and Comparative Examples Saturated polyester resin (A), rubber-reinforced styrenic resin (B), glass fiber (C), polyamide elastomer (D) and talc were mixed in the composition shown in Table 1 and 4
Using a 0 mm twin-screw extruder, the mixture was melt mixed at 250 ° C. and pelletized. Various test pieces were prepared using the obtained pellet-shaped thermoplastic resin composition, and mechanical and thermal characteristics and adhesion were measured by the following methods. The results are shown in Table 1.

Impact resistance : Izod impact strength with notch,
ASTM D-256 (23 ° C) Fluidity : According to ASTM D-1238 (240 ° C, 1
0 kg). Rigidity : Based on ASTM D-790. Heat resistance : Compliant with ASTM D-648 (1/4 inch,
18.6 kg / cm ² load).

Molding shrinkage : engraving size 150 mm × 9
A mold having a thickness of 0 mm × 3 mm was used and injection molding was performed at a molding temperature of 260 ° C. to obtain a molded product. After molding, leave at room temperature for 72 hours, and then measure the size of the molded product using a caliper to 0.01 mm.
Was measured and calculated by the following formula.

Adhesion : Using a mold having a thickness of 80 mm × 60 mm × 3 mm, injection molding was performed at a molding temperature of 260 ° C. to obtain a molded product. A urethane paint (R-230, manufactured by Nippon Bee Chemical Co., Ltd.) was applied to the molded product using an air spray gun and dried (80 ° C., 30 minutes) to obtain a urethane coated molded product. Hold the cutting edge of a single-edged razor at about 30 degrees with respect to the coated surface, and reach 100 squares of 1 mm (10
X10) was prepared, a cellophane adhesive tape of 24 cm width was completely adhered on the cross-cut, and immediately one end of the tape was kept perpendicular to the effective surface and momentarily separated, and the number of peeled pieces / the number of tests (100) Represent The following two measurements were performed while changing the environmental conditions after coating. Condition 1; Adhesion after leaving at room temperature for 48 hours Condition 2; Adhesion after warm water immersion (40 ° C, 240 hours)

[0036]

[Table 1]

[0037]

INDUSTRIAL APPLICABILITY The present invention is excellent in mechanical and thermal characteristics such as heat resistance, impact resistance, rigidity, fluidity, and dimensional stability (molding shrinkage rate), and also in coating film adhesion at the time of coating urethane coating. It is intended to provide an excellent thermoplastic resin composition and has extremely high practical value as a vehicle part such as a motorcycle or an automobile to which urethane coating is applied.

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Claims (2)

[Claims] 1. 1 to 50 parts by weight of a glass fiber (C) and 100 parts by weight of a composition consisting of 5 to 80% by weight of a saturated polyester resin (A) and 95 to 20% by weight of a rubber-reinforced styrene resin (B). A resin composition for urethane coating, comprising 1 to 50 parts by weight of a polyamide elastomer (D). 2. A urethane-coated molded article obtained by coating the molded article obtained by molding the resin composition according to claim 1 with urethane.