JPH04103640A - painted molded body - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Background of the Invention] <Industrial Application Field> The present invention relates to a coated molded body formed from an olefin resin material and whose surface is coated.

More specifically, it is formed from a resin composition consisting of an olefinic resin, a copolymer of ethylene and an unsaturated compound containing a hydroxyl group, and a copolymer of ethylene and an unsaturated compound containing a carboxyl group (including an acid anhydride group). The present invention relates to a molded body and a coated molded body in which the surface of the molded body formed from a resin composition obtained by adding an elastomer component to each of these components is directly coated.

<Prior art> JP-A-63-275656 discloses a propylene polymer, a copolymer of ethylene and an unsaturated compound containing a carboxyl group (including an acid anhydride group), and a copolymer of ethylene and an unsaturated compound containing a hydroxyl group. The invention relates to a propylene polymer composition comprising a copolymer with.

However, this invention was developed in order to improve heat resistance, to improve the shortcomings of the previous technology that when vacuum forming a propylene polymer sheet, the sheet sagged and a good product could not be obtained.
The purpose is to provide a composition with excellent vacuum formability, and in addition, it is a copolymer of ethylene and an unsaturated compound containing a carboxyl group, and a copolymer of ethylene and an unsaturated compound containing a hydroxyl group. The blending amount of the polymer can vary widely, and by crosslinking the hydroxyl groups and carboxyl groups in the composition, the heat resistance and vacuum formability are improved.

Therefore, in the invention of the composition, there is no recognition of a resin composition that can improve paintability, and there is no description suggesting this. Furthermore, the range of the amount of the ethylene copolymer containing the polar group is as follows:
The range is too wide to be aimed at as a paintable resin composition, and includes a range in which the purpose cannot be achieved.

That is, in the entire range of particularly preferred formulations of the invention in this prior art, it is not possible to obtain satisfactory paint adhesion even if the paint is applied directly (Comparative Example)
(See 3). Therefore, it was necessary to newly consider a composition with good paintability from a different perspective than the invention in the prior art.

<Problems to be Solved by the Invention> Generally, polyolefin resins do not have polar groups in their structures and are highly crystalline, so it is known that paints do not adhere very well to them and their paintability is poor. ing. Therefore, in order to improve this poor adhesion, the surface of the polyolefin resin is modified by applying a primer or plasma treatment in advance to improve the paintability and then the paint is applied. Ta.

However, such coating methods have conventionally had the following problems.

In other words, the brimer application method has disadvantages such as the need to use an expensive brimer and the increased number of painting steps, which increases the coating cost. The work environment was not only bad because of the need to do this, but also there was a safety problem due to the risk of fire.

On the other hand, plasma processing requires a high degree of vacuum, so expensive equipment must be installed.
Moreover, since it is a batch process, an increase in cost cannot be avoided. Furthermore, the surface after plasma treatment is unstable;
Contact with foreign matter reduces the adhesion of the paint, which can lead to variations in coating film performance, making handling extremely inconvenient.

Therefore, if it is possible to omit the steps of applying the brusher and plasma treatment, the painting process can be simplified.
Since it is possible to improve the work environment, reduce costs, etc., many studies have been conducted to solve these problems.

However, in the end, this goal has not yet been achieved, and with polyolefin resin materials, it is not possible to omit such treatments such as brimer FFI and plasma treatment, and if painting is applied after such treatment. There are many.

On the other hand, without applying treatments such as coating the resin molding with brimer,
It is also known that when directly applying a paint, additives such as light stabilizers, antioxidants, and lubricants added to the resin composition may reduce the canal properties of the paint.

[Summary of the invention]

Summary> As a result of intensive research in view of the above problems, the present inventors have discovered that
The present invention was completed based on the finding that the above problems can be solved by using a specific resin composition for the object to be coated.

That is, the molded article of the present invention contains an olefin resin, 0.01 to 30 parts by weight of a copolymer of ethylene and a hydroxyl group-containing unsaturated compound per 100ffiE1 part of the olefin resin, and 0.01 to 30 parts by weight of a copolymer of ethylene and a carboxyl group (acid anhydride group). A molded article formed from a resin composition containing 0.01 to 20 parts by weight of a copolymer with an unsaturated compound containing (including 1 to 200 parts of an elastomer component). This molded article is characterized by having a paint coated directly on its surface.

Effect> By using specific components in the resin composition forming the coated molded body of the present invention, the coated molded body of the present invention has the advantage that it is impossible to directly coat olefin resin, which is impossible in the past. By overturning common sense, we applied a primer to the molded object.
Good paint adhesion can be exhibited even when the paint is directly applied without prior surface modification treatment such as plasma treatment.

In addition, even if additives such as commonly used resin light stabilizers, antioxidants, and lubricants are added to the resin composition, the adhesion of the paint will not be reduced, and the paint will have a good quality. It exhibits adhesive properties and is extremely useful industrially.

[Detailed description of the invention]

(I) Resin composition (1) Constituent components The resin composition forming the molded article of the present invention includes the following (a) to
It is basically formed from the constituent components shown in (c).

(a) Olefin resin The olefin resin used in the present invention includes:
Ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, 1-
Homopolymers of α-olefins such as pentene,
Or a copolymer of these α-olefins,
Moreover, the bending elastic modulus measured in accordance with J Is-7203 is 1,000 to 20. 000 kg/c4, preferably 2,000 to 18,000 kg/cd, particularly preferably 3,000 to 15.00 kg/cd. 000 kg/cd. The melt flow rate (MFR) of this copolymer resin is not particularly limited, but the value measured in accordance with ASTM-D1238 is usually 0.01 to 200 g/10 minutes, preferably 0. 1~
Optimally it is within the range of 100g/10 minutes.

Specifically, for example, polyethylene resins such as so-called low-pressure polyethylene, medium-pressure polyethylene, high-pressure polyethylene, linear low-density polyethylene, stereoregular polypropylene, stereoregular poly-1-butene, stereoregular poly-4 -Stereoregular poly-α- such as methyl-1-pentene
Examples include olefin resins. Among these olefin resins, stereoregular polypropylene (hereinafter simply referred to as "propylene resin") is preferred. Among these propylene resins, propylene and other α-
Copolymers with olefins are preferred, and copolymers with ethylene are particularly preferred. The copolymer may be a random copolymer or a block copolymer, but a block copolymer is particularly preferred.

These olefin resins can be used alone or as a mixture of two or more of the above resins, and usually,
An appropriate resin can be selected and used from commercially available resins.

(b) Copolymer of ethylene and hydroxyl group-containing unsaturated compound The copolymer of ethylene and hydroxyl group-containing unsaturated compound used in the molded article of the present invention is, from a structural standpoint,
Refers to all compounds having a structure in which hydroxyl group-containing unsaturated compounds are copolymerized with ethylene in a branched or linear carbon chain in an irregular or regular manner.

Specifically, the content of hydroxyl group a unsaturated compound is 0.1
~50% by weight, preferably Iio, 5-45% by weight,
Particularly preferably 1 to 40% 2 parts, J
In accordance with IS-6760? rlj determined melt flow rate (VFR) is 0.1 to 1.000g/10
minutes, preferably 0.5 to 700 g to 10 minutes, particularly preferably 1 to 500 g and 710 minutes, and includes polymers that are liquid, semisolid, or solid at room temperature.

Such a copolymer of ethylene and a hydroxyl group-containing unsaturated compound can be produced by a well-known method such as a high-pressure radical polymerization method using ethylene and a hydroxyl group-containing unsaturated compound as raw materials. In the case of production by the high-pressure radical polymerization method, ethylene, a hydroxyl group-containing unsaturated compound, and a radical polymerization initiator are heated at a pressure of, for example, 1000 to 3,000 yen.
In a reaction zone maintained at 0 atm and temperature between 90 and 300°C,
The ratio of ethylone: hydroxyl group-containing unsaturated compound is 1:0.0
Continuously supply I7 so that the ratio is 001 to 1:0.1,
It is produced by producing an ethylene copolymer at a conversion rate of 3 to 20% and continuously removing the copolymer from the reaction zone.

Examples of such hydroxyl group-containing unsaturated compounds include:
Examples include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, and poly(ethylene glycol) monomethacrylate.

In addition to the above-mentioned ethylene and hydroxyl group-containing unsaturated compound components, third copolymerization monomer components include unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, and methyl methacrylate; styrene, α-methylstyrene, and vinyltoluene. Vinyl aromatic compounds such as: Nitrile compounds such as acrylonitrile and methacrylaterile; Vinyl pyridines such as 2-vinylpyridine and 4-vinylpyridine; Vinyl ethers such as methyl vinyl ether and 2-chloroethyl vinyl ether; Vinyl ethers such as vinyl chloride and vinyl bromide; Examples include vinyl chloride: vinyl esters such as vinyl acetate, acrylamide, etc., and it is also possible to use them as ternary or multicomponent copolymers.

These copolymers can be used alone or as a mixture of multiple types.

(C) A copolymer of ethylene and an unsaturated compound containing a carboxyl group (including an acid anhydride group) used in the molded article of the basic invention is a branched copolymer from a structural standpoint. Alternatively, it refers to any type of carbon having a structure in which unsaturated compounds containing carboxyl groups (including acid anhydride groups) are copolymerized with ethylene in a linear carbon chain, either irregularly or regularly.

Specifically, the content of unsaturated compounds containing carboxyl groups (including acid anhydride groups) is 0.1 to 40, preferably 0. 5-35 weight 06, particularly preferably 1-3
0% by weight, and the melt flow rate (MFR) determined by M1 according to JIS-K 6760 is 0% by weight.
．． 1-1,0OOK/10 minutes, preferably 0°5-7
00 g/10 minutes, particularly preferably 1-500 g/10 minutes, and includes polymers that are liquid, semi-solid, or solid at room temperature.

This ethylene carboxyl 2! The 4i-containing unsaturated compound copolymer (containing an acid anhydride group) is produced by a well-known method such as a high-pressure radical polymerization method using ethylene and an unsaturated compound containing a carboxyl group (containing an acid anhydride group) as raw materials. can be manufactured.

In the case of production by the high-pressure radical polymerization method, ethylene, an unsaturated compound containing a carboxyl group (including an acid anhydride group), and a radical polymerization initiator are heated at a pressure of, for example, 1,000 to 3,000 yen.
In a reaction zone maintained at 000 atmospheres and a temperature of 90 to 300°C, the ratio of ethylene to unsaturated compounds containing carboxyl groups (including acid anhydride groups) is 1:0.0001 to 1:0.1.
The ethylene copolymer is produced by continuously supplying the ethylene copolymer under conditions such that the conversion rate is 3 to 20%, and then continuously taking out the copolymer from the reaction zone.

Carboxyl 2 like this! Examples of unsaturated compounds (containing acid anhydride groups) include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, norbornene-5,6-
Examples include unsaturated carboxylic acids such as dicarboxylic acids and anhydrides thereof, and acid anhydrides thereof. Among these specific examples, acrylic acid and methacrylic acid are
preferable.

In addition to the unsaturated compound components containing ethylene and carboxyl groups (including acid anhydride groups), unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, and methyl methacrylate can be used as a third copolymer component. ; Vinyl aromatic compounds such as styrene, α-methylstyrene, and vinyltoluene; Nitrile compounds such as acrylonitrile and methacrylonitrile;
Vinyl pyridine such as 2-vinylpyridine and 4-vinylpyridine; Vinyl ether such as methyl vinyl ether and 2-chloroethyl vinyl ether; Vinyl chloride, vinyl bromide, etc.; Vinyl ester such as vinyl acetate; Acrylamide, etc. can be mentioned, ternary system,
It is also possible to use it as a multicomponent copolymer.

These copolymers can be used alone or as a mixture of multiple types.

(d) Elastomer component As the elastomer component used in the preferred molded article of the present invention, at least one type of elastomer selected from styrene-based and olefin-based elastomers is optimal.

■ Styrenic elastomer The above styrene elastomer includes styrene, α-
These are elastomeric random or block copolymers of styrene compounds such as methylstyrene and conjugated dienes such as 1,3-butadiene and isoprene, and hydrogenated products of these copolymers. Among these styrene-based elastomers, block copolymers of a styrene-based compound and a conjugated diene are preferred, and those block copolymers whose general formula is represented by the following formula are optimal.

General formula % Formula % (In the above formula, A is a polymer block made of a styrene compound, B is a conjugated diene polymer block, and n is 1 to
An integer of 20, the proportion of A block in the entire molecule is 1
~50% by weight. ) The average molecular weight of these copolymers is 10,000 to 1.000,000, preferably 50,
000 to 250.000.

Specific examples of these styrene-based elastomers include styrene/butadiene random copolymer, styrene/isoprene random copolymer, styrene/butadiene/styrene triblock copolymer, styrene/isoprene/styrene triblock copolymer, and polystyrene. Styrene such as styrene φ butadiene radial block copolymer with block terminals, styrene/isoprene radial block copolymer with polystyrene block terminals, styrene/butadiene multi-block copolymer, styrene/isoprene block copolymer, etc. - Conjugated diene block copolymers and hydrogenated products of these can be mentioned.

Preferred among these styrene elastomers are hydrogenated styrene/conjugated diene block copolymers.

■ Olefin elastomer The olefin elastomer mentioned above may be a copolymer of α-olefins such as ethylene, propylene, 1-butene, 1-hexene, or a copolymer of these with a non-conjugated diene, or 1-hexene. A homopolymer of higher α-olefin, which is an elastomeric polymer, and has a Mooney viscosity ML1+4 measured at 100° C., usually in the range of 1 to 200, preferably 5 to 150, particularly preferably 7 to 100. belongs to.

Among these olefin elastomers, ethylene elastomers are particularly preferred in terms of quality and stability.

Specifically, ethylene propylene copolymer rubber (EPM)
, ethylene/1-butene copolymer rubber, ethylene/propylene/1-butene copolymer rubber, ethylene/propylene/
Non-conjugated diene copolymer rubber (EPDM), ethylene/1-
There are butene/non-conjugated diene copolymer rubber, ethylene/propylene/1-butene/non-conjugated diene copolymer rubber, etc.

Specific examples of the non-conjugated diene include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, dicyclooctadiene, methylene norbornene, 5-
Examples include ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 5-methyl-1,4-hexadiene, and 7-methyl-1,6-octadiene.

Among these elastomer components, olefin elastomers are particularly preferred because they are less likely to cause surface roughening of the molded article.

(e) Additional components In the resin composition forming the molded article of the present invention, the above-mentioned essential components (a) to (C) or (a) to (d) may be added to the extent that the effects of the present invention are not significantly impaired. In addition to the ingredients, additional ingredients such as those shown below can be included.

Examples of the additional components include inorganic fillers, specifically natural silica such as quartz, synthetic silica produced by wet or dry methods, natural silicates such as kaolin, mica, talc, and asbestos, calcium silicate, and aluminum silicate. synthetic silicates such as magnesium hydroxide, metal hydroxides such as aluminum hydroxide, metal acid compounds such as alumina and titania, metal powders such as calcium carbonate, aluminum, bronze, carbon black, glass fiber, carbon fiber, titanium There are whiskers such as potassium acid, calcium sulfate, zinc oxide, silicon nitride, sapphire, beryllia, boron carbide, and silicon carbide. Also included are lubricants, plasticizers or fluidity improvers, and other additives, such as colorants, stabilizers, dispersion aids, molecular weight regulators, crosslinking agents, and nucleating agents.

(2) Quantitative ratio The quantitative ratio of the above-mentioned components constituting the resin composition used in the present invention is usually 100 parts by weight of the olefin resin as the component (a) to ethylene as the component (b). The copolymer with the hydroxyl group-containing unsaturated compound is 0.01 to 30 parts by weight, preferably 0.05 to 25 parts by weight, particularly preferably 0.01 to 30 parts by weight. 1 to 20 parts by weight, and the copolymer of ethylene and a carboxyl group (including acid anhydride group)-containing unsaturated compound as component (C) is preferably 0.01 to 20 parts by weight, preferably 0.01 to 20 parts by weight. 0.05 to 10 parts by weight, particularly preferably 0.1
-7 parts by weight.

If the amount of the copolymer of component (b) ethylene and hydroxyl group-containing unsaturated compound is less than the above range, it is undesirable because the reproducibility of the paint adhesion may be poor or the adhesion strength of the paint may be weak. . On the other hand, if the above range is exceeded, the amount of the expensive polymer added increases, resulting in a high cost as a resin composition, and the polymer tends to delaminate or bleed out, reducing the adhesion of the paint. This is not desirable because it causes

Additionally, if the copolymer of component (C), ethylene and an unsaturated compound containing carboxyl groups (including acid anhydride groups), is less than the above range, the adhesion strength may be extremely weak depending on the paint being applied. This is not desirable. On the other hand, when the amount exceeds the above range, not only does the cost of the resin composition increase due to the large amount of the expensive polymer added, but also the effect proportional to the amount of the polymer added cannot be obtained. In addition, the crosslinking density of the polymer increases due to delamination or the reaction with the above-mentioned copolymer of ethylene and the unsaturated compound containing a hydroxyl group, resulting in decreased paintability, poor painted appearance, and poor moldability. This is not preferable because it lowers the temperature.

In addition, a resin composition consisting of the blending ratio of the above constituent components,
Furthermore, blending the elastomer component of component (d),
This is convenient because rigidity, impact resistance, etc. can be adjusted. Therefore, from the viewpoint of mechanical strength, the elastomer component should be 1 to 20 parts by weight per 100 parts by weight of the olefin resin.
It is preferable to use 0 parts by weight, preferably 11 parts by weight of 5 to 150 ff, particularly preferably 10 to 100 parts by weight.

(3) Mixing The resin composition for forming the molded article of the present invention is produced by mixing the above-mentioned components.

There is no particular restriction on the mixing order of each of these components, and any method can be used, such as mixing the above components at the same time, mixing any two components in advance, and then mixing the remaining components. Good too.

As for the mixing method, any conventionally known kneading machine can be used, such as a Brabender blastograph, a -screw or twin-screw extruder, a strong cascade kneading machine, a Banbury mixer, a kneader, a roll, etc. be able to.

[II) Molded object The molded object of the present invention can be obtained by molding the resin composition described above using various molding methods.

Molding can be carried out by conventional methods.

That is, any molding method such as injection molding, compression molding, extrusion molding (sheet molding, blow molding), etc. may be used.

It is particularly effective for molded articles injection molded into complex shapes.

[■] Coating As a coating method for forming the coated molded article of the present invention, a conventional coating process excluding surface modification processes such as brimer application and plasma treatment can be adopted. That is, a coating material is applied to a molded article obtained by forming and processing the resin composition either directly or after degreasing treatment if necessary.

In the present invention, "direct coating" means coating without applying the conventionally performed brimer coating or plasma treatment, and unless it deviates from the technical idea of the present invention, some surface treatment must be performed before applying the paint. This does not exclude the use of

One example of such surface treatment is degreasing treatment.

Such degreasing is a normal operation that is generally performed just before applying paint, and it removes hand grime that inevitably adheres to the surface of the molded product during the process from molding the resin composition to painting. It is possible to wash and remove machine oil, etc. Specifically, there are cleaning methods using organic solvents or their vapors, water, steam, acids, alkaline aqueous solutions, surfactant aqueous solutions, etc. Among these, cleaning methods using organic solvent vapors and various aqueous solutions are preferably used.

Further, as means for applying the paint, there are methods such as spraying, brushing, and roller application, and any of these methods can be employed.

As the paint that can be used in the main painting process, commonly used paints such as acrylic paints, epoxy paints, polyester paints, urethane paints, alkyd paints, etc. can be used. Among these, acrylic paints and urethane paints are preferred, and acrylic paints are particularly preferred.

[IV) Painted resin molded body The molded body painted in this way generally contains 1 coat of paint.
It is coated with a thickness of 0 to 100 μm, preferably about 20 to 70 μm, and the coating is strongly adhered, so it can be used for various industrial parts, such as automobile bumpers, mudguards, side moldings, wheel caps, and spoilers. Automotive exterior parts such as instrument panels, levers, knobs 1, interior linings, etc., electrical products such as pots, vacuum cleaners, washing machines, refrigerators, lighting equipment, audio equipment, etc., color boxes, storage cases, etc. It can be used as daily necessities.

[Experiment example]

EXAMPLES The present invention will be explained in more detail below with reference to Examples and Comparative Examples.

The molding conditions and test methods for obtaining test samples from the resin compositions produced in each experimental example are as shown below. Note that "parts" in the experimental examples are parts by weight.

Molding conditions〉 8 molding machines Injection molding machine manufactured by Seisakusho M40A-8J Molding degree 230℃ Molded product flat plate (65 mm x 6 5 mm x 2 * u +) Three-point bending modulus test piece (90 + n x 10 m x 4 mm) Flexural modulus JIS K Measured in accordance with -7203.

MFR Measured in accordance with ASTM D-1238.

<Painting> Painting was performed using a one-component acrylic paint and a one-component urethane paint.

Coating method Each paint was prepared and spray coated using an air spray gun so that the coating thickness was about 40 μm in the stone grain test and about 100 μm in the peel strength test. Thereafter, the acrylic paint was baked at 100°C for 60 minutes, and the urethane paint was baked at 120°C for 60 minutes to dry.

Evaluation of paint adhesion> Substrate test: Using a single-edged razor, make 100 substrate openings by making 11 vertical and horizontal lines perpendicular to the surface of the test piece, with 1 perforation at 2×1 intervals. On top of that, add 6 cellophane tapes (J Is Z1
522) was sufficiently crimped, maintained at about 30 degrees to the coating surface, and peeled off at once toward the viewer.The state of the portion surrounded by the base grains was observed, and the number of base grains that did not peel off was recorded.

The upper half of the peel strength test piece was treated to prevent the paint from adhering to it, and then each paint was applied to the lower half to a film thickness of 100 μm, and baked-on was dried.

Cellophane adhesive tape (example: 24m width made by Nichiban) on the test piece
Apply m) to the entire surface and make a 1 cm wide cut extending vertically into the substrate. Peel off the side with no paint film attached by hand, attach it to a tensile tester and test it in a 180 degree direction with 5C1++■/
The load when peeled off at a speed of 1 minute was recorded. In addition, when the coating film was broken, it was described as broken.

Examples 1 to 22 and Comparative Examples 1 to 13 Production of resin molded bodies The components shown in Tables 1 and 2 were blended and melt-kneaded at 200°C using a twin-screw extruder to form pellets.

Using this pellet, a flat plate and a test piece for three-point bending modulus measurement were injection molded.

The ingredients in Tables 1 and 2 are as follows.

Olefin resin = (a) component> Block PP (1): Ethylene content is 8. 2ffi
Q96, flexural modulus is 10. 000kg/cd, a propylene/ethylene block copolymer with a KaMFR of 33g/10min.

Block pp (2): ethylene content 13% by weight, flexural modulus 6. 000kg/cd MFR is 30g
/10 minutes of propylene ψ ethylene block copolymer.

Random PP, ethylene content 3.4% by weight, flexural modulus 10. 500kg/c-gag MFR is 15g/1
Propylene/ethylene random copolymer with 0 minutes.

+11. German PP has a bending modulus of 13. 000kg/c
- Polypropylene with an MFR of 25 g/10 min.

HDPE: Flexural modulus is 9. 000kg/cF, high density polyethylene with a MFR of 20g/10min.

Copolymer with ethylene/hydroxyl group-containing unsaturated phase compound:
(b) Component > (MFR+, iJIS-67
60) EHM (1): Obtained by high-pressure radical polymerization method, 2-hydroxyl methacrylate content 10% by weight, MFR 7
g/10 min of ethylene-2-hydroxyethyl methacrylate copolymer.

EHM (2): Obtained by high-pressure radical polymerization method, 2-hydroxyethyl methacrylate content 10% by weight, methyl acrylate content 10% by weight, MFR Kami 3 g
/ 1.0 minute ethylene-2-hydroxyethyl methacrylate/methyl acrylate terpolymer.

EHM (3): Obtained by high-pressure radical polymerization, 2-hydroxyethyl methacrylate content 10% by weight, methyl acrylate content 10% by weight, MFR 100g/1
0 minute ethylene/2-hydroxyethyl methacrylate/methyl acrylate copolymer.

<Copolymer of ethylene and unsaturated compound containing carboxyl group (including acid anhydride group) = component (C)> (MFR is J
Measured according to IS-6760.

FAA (1): Ethylene-acrylic acid copolymer obtained by high-pressure radical polymerization, having an acrylic acid content of 13% by weight and an MFR of 7 g/10 minutes.

EAA (2): Ethylene-acrylic acid copolymer obtained by high-pressure radical polymerization, having an acrylic acid content of 20% by weight and an MFR of 300 g/10 minutes.

Elastomer component: (d) component> EPM (1): Mooney viscosity ML (100°C) 1
Ethylene, propylene, with +4 of 70 and specific gravity of 0.86.
Copolymer rubber.

EPM (2): Mooney viscosity ML (100°C) 1
Ethylene-propylene copolymer rubber with +4 of 24 and specific gravity of 0.86.

EPDM: Mooney viscosity ML (100°C) is 1+
4 47, ethylene-propylene-ethylidene norbornene copolymer rubber with a specific gravity of 0.86.

5EBS: Number average molecular weight is 70,000, specific gravity is 0.
91, a hydrogenated product of styrene-butadiene block copolymer rubber.

Additives: (e) Component> Phenolic antioxidant: Ciba Geigy [Irganox 101. OJ (tetrakis[methylene-3-(3
, 5-di-t-butyl-4-hydroxyphenyl)propionate comethane).

HALS (-hindered amine light stabilizer) "Sanol 770J (bis-2,2,6,6-tetramethyl-4-piperidinyl sebacate)" manufactured by Nisankyo Co., Ltd.

Lubricant: "Neutron" (oleic acid amide) manufactured by Nippon Kuka Co., Ltd. Painting of resin moldings After degreasing the flat plate molded by the above resin molding process with trichloroethane vapor for 30 seconds, paint was applied using an air gun. was applied. Baking is done after drying, 4
The substrate was left at room temperature for 8 hours, and then a substrate test was performed.

The results of the elastic modulus and paint adhesion of the obtained resin composition were
Shown in Table and Table 2.

The composition shown in Comparative Example 3 was so soft that the flexural modulus could not be measured using a measuring method based on JIS-720B.

Furthermore, during painting, baking after application of the paint could not be evaluated because the flat plate of the test piece was severely deformed during drying and the surface of the flat plate was also uneven.

Also, from the formulations of Comparative Examples 4 to 7 in Tables 1 and 2,
It can be seen that the paint adhesion was good without the additive component (e), but when the additive was added, the paint adhesion decreased rapidly. However, compared to these, in the formulations of Examples 16 and 20-22, (e)
It can be seen that despite the addition of component additives, it shows fairly strong paint adhesion.

hand Continued Supplementary Positive book Heisei 41' Heisei Patent application number name of investigation painted molded body N-1 name to correct Relationship with 44i'1 ((io5) special language applicant Hishiura Ka 13th type company by compensation [Number of item items Target of correction Month vinegar Nine Day 7 Contents of amendment (1) Amend the claims as shown in the attached sheet.

(2) Page 5, line 13 of the specification "Avoid rising" Corrected to "avoid rising".

(3) Page 6 lines 7-8 of the specification “Painting is often applied after this type of treatment.

” to ``Painting is often applied after this type of treatment.''
Correct.

(4) Same page, line 20 "The molded article of the present invention is" Please note that "the coated molded article of the present invention is".

(5) Page 7, line 9 of the specification "It is a molded object with characteristics." Corrected to ``It is a painted molded object with characteristics.''

(6) "Molded article of the present invention" on page 8, line 7 of the specification, page 10, line 8, and page 13, line 3 of the specification is corrected to "coated molded article of the present invention."

(7) In specification picture 14 t'i, line 16, "as an unsaturated compound" is corrected to "as a specific example of an unsaturated compound".

(8) "Preferred molded article of the present invention" on page 16, line 3 of the specification is changed to "U suitable molded article of the present invention!";! ! Corrected to ``A molded object with a molded body.''

(9) Page 19, line 16 of the specification "The molded article of the present invention" "The coated molded article of the present invention" is subjected to f pressure.

(10) Specification 8, page 24, lines 2-3 "As a painting method," Stop at ``As for the painting method.''

(11) In lines 1 and 11 of the same page, change ``to apply without applying,'' to ``to apply without applying,'' to iJ.

(12) r (Measured based on 67601:'P on MFRI; MFR is corrected to J (measured in accordance with JIS-6760).

Scope of claims 1. Olefin resin, said olefin resin 100f
0.01 to 30 parts by weight of a copolymer of ethylene and an unsaturated compound containing a hydroxyl group and 0.01 part of a copolymer of ethylene and an unsaturated compound containing a carboxyl group (including acid anhydride) to the flffi part. A coated molded article, characterized in that the paint is directly applied onto the surface of a molded article formed from a resin composition containing ~20 parts by weight.

2. Olefin resin, containing 0.01 to 30 parts by weight of a copolymer of ethylene and a hydroxyl group-containing unsaturated compound per 100 parts by weight of the olefin resin, containing ethylene and carboxyl groups (including acid anhydrides). -J- Paint is applied directly to the surface of a molded article formed from a resin composition containing 0.01 to 20 parts by weight of a copolymer with an unsaturated compound and 1 to 200 parts by weight of an elastomer component. A painted molded object characterized by being painted.

Claims (1)

[Claims] 1. Olefin resin, 0.01 to 30 parts by weight of a copolymer of ethylene and a hydroxyl group-containing unsaturated compound per 100 parts by weight of the olefin resin, and a copolymer of ethylene and a carboxyl group (acid anhydride). A paint is applied directly to the surface of a molded article formed from a resin composition containing 0.01 to 20 parts by weight of a copolymer with an unsaturated compound (containing groups). A molded object. 2. Olefin resin, 0.01 to 30 parts by weight of a copolymer of ethylene and an unsaturated compound containing a hydroxyl group per 100 parts by weight of the olefin resin; 0.01 to 20 parts by weight of a copolymer with a saturated compound and 1 to 20 parts by weight of an elastomer component
A coated molded article, characterized in that the paint is directly applied to the surface of a molded article formed from a resin composition containing 200 parts by weight.