JPH04272938A - Molded article and coated molded article - Google Patents

Abstract

PURPOSE:To provide a coated molding which shows a good adhesion between the molded surface and a coating material even when it is directly applied to the surface without any surface pretreatment such as priming or plasma treatment. CONSTITUTION:A molded article which is prepd. from a resin compsn. comprising a polyolefin resin, a diene polymer having terminal hydroxyl groups or a hydrogenation product thereof, an organotin compd. and/or a tert. amine compd., and optionally an elastomer, and a coated molded article prepd. by directly coating the surface of the molded article.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded article made of an olefin resin material suitable for coating the surface thereof, and a coated molded article having the surface of the molded article coated. More specifically, a molded article formed from a resin composition consisting of an olefinic resin, a diene polymer having a hydroxyl group at the end or a hydrogenated product thereof, an organic tin compound and/or a tertiary amine compound, and A molded body formed from a resin composition further containing an elastomer component, and the surface of the molded body,
This invention relates to a coated molded body that has been directly coated.

0002

BACKGROUND OF THE INVENTION Conventionally, it has been known that polyolefin resins have no polar groups in their structure and are highly crystalline, resulting in extremely poor paint adhesion and poor paintability. 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.
The paint was applied after improving the paintability.

0003

[Problems to be Solved by the Invention] However, such coating methods have conventionally had the following problems. In other words, the primer application method requires the use of expensive primers,
There are drawbacks such as higher painting costs due to the increased number of painting steps, but there are also disadvantages such as the need to activate the solvent in the primer, which creates a poor working environment and poses a risk of fire, making it safer. There were also problems with sexuality. On the other hand, in the plasma processing method, since a high degree of vacuum is required, expensive equipment must be installed, and furthermore, since it is a batch method, an increase in cost cannot be avoided. Furthermore, the surface after plasma treatment is unstable, and the adhesion of the paint decreases when it comes into contact with foreign matter, which can lead to variations in coating film performance, making handling very inconvenient. Therefore, if such primer application and plasma treatment processes could be omitted, it would be possible to simplify the painting process, improve the working environment, and reduce costs. Many studies have been conducted to try to improve these problems. However, in the end, this goal has not yet been achieved, and with polyolefin resin materials, such primer application and plasma treatment cannot be omitted, and if painting is applied after such treatment, There are many.

0004

[Means for Solving the Problems] [Summary of the Invention] As a result of intensive research in view of the above problems, the present inventors have solved the above problems by using a specific resin composition for the object to be coated. The present invention was completed based on the knowledge that the present invention can be obtained. That is, the molded article of the present invention contains 100 parts by weight of an olefin resin, 0.01 to 20 parts by weight of a diene polymer having a hydroxyl group at the end or a hydrogenated product thereof, 0.01 to 5 parts by weight of an organotin compound, and/or Or, it is characterized by being formed from a resin composition containing 0.01 to 20 parts by weight of a tertiary amine compound (in addition, 1 to 200 parts by weight of an elastomer component may be blended). It is. In addition, the coated molded body, which is another invention of the present invention, has an olefin resin 100%
To parts by weight, 0.01 to 20 parts by weight of a diene polymer having a hydroxyl group at the end or its hydrogenated product, 0.01 to 5 parts by weight of an organic tin compound, and/or 0.01 to 20 parts by weight of a tertiary amine compound. % (and may further contain 1 to 200 parts by weight of an elastomer component), and is characterized by being directly coated on the surface of a molded body formed from a resin composition. It is.

[Specific 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 (d). (a) Component: 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
- A homopolymer of α-olefins such as pentene, or a copolymer of these α-olefins, and has a flexural modulus of 1,000 to 20, as measured in accordance with JIS-K7203. 000 kg/cm2, preferably 2,000 to 18,000 kg/cm2, particularly preferably 3,000 to 15,000 kg/cm2
The following resins can be mentioned. Further, the methane 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 min, preferably 0.
The optimum range is 1 to 100 g/10 minutes. Examples of the olefin resin include polyethylene resins such as so-called low-pressure polyethylene, medium-pressure polyethylene, high-pressure polyethylene, and linear low-density polyethylene, stereoregular polypropylene, stereoregular poly-1-butene, and stereoregular polyethylene. Examples include stereoregular poly-α-olefin resins such as poly-4-methyl-1-pentene. Among these olefin resins, stereoregular polypropylene (hereinafter simply referred to as "propylene resin") is preferred. Among these propylene-based resins, copolymers of propylene and other olefins are preferred;
In particular, copolymers with ethylene are 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 can usually be appropriately selected from commercially available resins.

Component (b): Diene polymer having a hydroxyl group at the end or its hydrogenated product ■ Diene polymer having a hydroxyl group at the end Diene polymer having a hydroxyl group at the end or its hydrogenated product used in the molded article of the present invention Examples of the diene polymer having a hydroxyl group at the end include polyhydroxybutadiene. Specifically, it has at least one hydroxyl group at the end and has a molecular weight of 200 to 100,000,
Preferably 500 to 50,000, particularly preferably 80
0 to 10,000, and includes polymers that are liquid, semisolid, or solid at room temperature. The average number of hydroxyl groups per molecule is generally 1 to 10, particularly preferably 1.5 to 5, and the hydroxyl value is generally 15 to 250, preferably 25 to 125 (KO
Hmg/g) is particularly preferred. A diene polymer having a hydroxyl group at the end can be produced by a well-known method such as a radical polymerization method or an anionic polymerization method using 1,3-diene as a raw material. Specifically, for example, the method described in JP-A-51-71391 can be mentioned. When produced by the above-mentioned radical polymerization, it can be easily obtained by polymerizing a diene monomer using, for example, hydrogen peroxide as a polymerization initiator. In addition, when producing by the above-mentioned anionic polymerization, a conjugated diene is polymerized using an anionic polymerization catalyst such as an alkali metal or an organic alkali metal compound according to a well-known method. For example, a monoepoxy compound, formaldehyde, acetaldehyde, acetone, halogenoalkylene oxide, or polyepoxide may be reacted with a living polymer having a structure in which a metal is bonded. At least one type of conjugated diene monomer is used as a raw material monomer for these polymers. Conjugated diene monomers include 1,3-butadiene, 1,3-pentadiene,
Isoprene, chloroprene, 2,3-dimethyl-1,3
-butadiene, 1-phenyl-1,3-butadiene, and the like.

[0007] Hydrogenation of a diene polymer having a hydroxyl group at the end Further, as a hydrogenation product of a diene polymer having a hydroxyl group at the end, the above-mentioned diene polymer having a hydroxyl group at the end can be prepared by a conventional method, for example, in JP-A-Sho. It is obtained by hydrogenation by the method described in Japanese Patent No. 51-71391. Regarding the degree of hydrogenation, the double bonds contained in the polymer may be completely or partially hydrogenated, but in particular, the iodine value is usually 0 to 2.
0, especially 0 to 5 (g/100g). These diene polymers having a hydroxyl group at their terminals and hydrogenated products thereof can be used alone or as a mixture of two or more types.

Component (c): Organic tin compound Examples of the organic tin compound used in the present invention include those represented by the following formula.

[0009]

[Formula 1] (R1, R2, R3, and R4 in the above formula are each a saturated hydrocarbon group having 1 to 12 carbon atoms, and each may be the same or different, preferably having 3 to 12 carbon atoms.
is a saturated hydrocarbon group. Further, Y1 and Y2 are each a fatty acid residue, a maleic acid derivative residue, a mercaptan residue, a mercapto acid residue, etc., and they may be the same or different, and are preferably fatty acid residues or maleic acid derivatives. It is a residue. Further, X1 is an oxygen atom, a sulfur atom, a maleic acid residue, etc., and preferably an oxygen atom or a maleic acid residue. Also, m is 0 or 1 to 30
, preferably 0 or an integer of 1 to 25, particularly preferably 0 or an integer of 1 to 20. ) Specific examples of these organic tin compounds include monobutyl tin trimethyl maleate, monobutyl tin trioctyl maleate, dibutyl tin dilaurate, dibutyl tin laurate methyl maleate, and dibutyl tin dioleyl maleate. , dibutyl tin dimethyl malate, dibutyl tin malate, dibutyl tin methoxymethyl malate, dibutyl tin dioctyl maleate, dibutyl tin dioctyl thiocreate, dibutyl tin lauryl mercaptite, tribenzyl - Tin octyl maleate, tribenzyl tin trimethyl maleate, etc. can be mentioned. Among these, it is preferable to use dialkyl tin compounds. These organic tin compounds can be used alone or as a mixture of a plurality of them, and can usually be appropriately selected from commercially available compounds.

Component (d): Tertiary amine compound The tertiary amine compound used in the molded article of the present invention includes from low molecular weight compounds to high molecular weight compounds having a tertiary amine structure. (2) Low-molecular compound having a tertiary amine structure A low-molecular compound having a tertiary amine structure refers to a compound having a molecular weight of 100 to less than about 1,000. Specific examples include triethylenediamine, dimethylaminopropylamine, diethylaminopropylamine, tetraguanidine, 1,8-diazabicyclo(5.4.0)
-7-undecene, N,N-bis(2-hydroxyethyl)laurylamine, and tetrakis(N-methyl-2,2,6,6-tetramethyl-4-piperidyl)1
, 2,3,4-butanetetracarboxylate and the like. These materials can be appropriately selected from commercially available products.

■ Polymer compounds having a tertiary amine structure In addition, polymer compounds having a tertiary amine structure have a molecular weight of 1,000 or more, are liquid at room temperature,
Includes semi-solid, solid, polymers with molecular weights up to about 100,000. Examples of such polymeric compounds having a tertiary amine structure include modified olefin polymers containing tertiary amino groups. From a structural standpoint, such modified olefin polymers containing tertiary amino groups are those in which unsaturated compounds containing tertiary amino groups are randomly or regularly arranged in branched or linear carbon chains. Refers to all compounds having a structure in which they are copolymerized or grafted with a side chain having a tertiary amine structure. in particular,
Content of tertiary amino group-containing unsaturated compound is 0.1 to 50
% by weight, preferably 0.5 to 45% by weight, particularly preferably 1 to 40% by weight, and conforms to JIS-K676
The melt flow rate (MFR) measured in accordance with 0.0 is preferably 0.1 to 1,000 g/10 minutes, particularly preferably 0.5 to 700 g/10 minutes. This modified olefin polymer containing a tertiary amino group can be produced by a well-known method using an unsaturated compound containing a tertiary amino group. For example, in the case of production by a high-pressure radical polymerization method, ethylene, an unsaturated compound containing a tertiary amino group, and a radical polymerization initiator are
In a reaction zone maintained at ,000 to 3,000 atm and temperature of 90 to 300°C, the ratio of ethylene to tertiary amino group-containing unsaturated compound was 1:0.0001 to 1:0.1. The ethylene copolymer is produced by continuously supplying the ethylene copolymer at a conversion rate of 3 to 20%, and continuously removing the copolymer from the reaction zone. In addition, in the case of production by the impregnation graft polymerization method, the tertiary amino group-containing unsaturated compound and the radical polymerization initiator to be reacted with the olefin polymer pellets are suspended in an aqueous solvent, and the tertiary amino group It is produced by impregnating olefinic polymer pellets with the unsaturated compound and initiator, then heating to the decomposition temperature of the initiator to cause a graft reaction within the pellets, resulting in modification.

[0012] Such an unsaturated compound containing a tertiary amino group is represented by the following formula.

[0013]

[Formula 2] (R5 in the above formula is hydrogen or a saturated hydrocarbon group having 1 to 4 carbon atoms, preferably a hydrogen atom or a saturated hydrocarbon group having 1 to 4 carbon atoms.
~2 saturated hydrocarbon groups. R6 is a saturated hydrocarbon group having 2 to 12 carbon atoms, preferably a saturated hydrocarbon group having 2 to 6 carbon atoms. R7 and R8 are saturated hydrocarbon groups having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms. Moreover, R7 and R8 may be the same or different here. X2 is an oxygen atom, -NR9-, or a sulfur atom, preferably an oxygen atom or -NR9-. R9 is a hydrogen atom or a saturated hydrocarbon group having 1 to 12 carbon atoms, preferably a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms. ) Specific examples of these tertiary amino group-containing unsaturated compounds include 2-(dimethylamino)ethyl acrylate,
2-(diethylamino)ethyl acrylate, 2-(dimethylamino)ethyl methacrylate, 2-(diethylamino)ethyl methacrylate, 2-[di(t-butyl)amino]ethyl acrylate, 2-[di(t-butyl)amino] Examples include ethyl methacrylate, 3-(dimethylamino)-propylacrylamide, and 3-(dimethylamino)-propylmethacrylamide. In addition, as the olefin monomer component when copolymerizing with the above-mentioned tertiary amino group-containing unsaturated compound,
Examples include α-olefins such as ethylene, propylene, and 1-butene, and among these, ethylene is particularly preferred. In addition, when the above-mentioned tertiary amino group-containing unsaturated compound is grafted, the olefin-based polymer component as the backbone polymer is the above-mentioned olefin-based resin ((
a) component) and the olefin elastomer ((
(e)-(2) component), etc. Among these, it is preferable to use polyethylene resins, polypropylene resins, and ethylene elastomers. In addition, when producing a tertiary amino group-containing modified olefin polymer, monomer components that can be copolymerized with the above-mentioned tertiary amino group-containing unsaturated compound include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, Unsaturated carboxylic acid esters such as acrylates; vinyl aromatic compounds such as styrene, α-methylstyrene, and vinyltoluene; nitrile compounds such as acrylonitrile and methacrylonitrile; vinylpyridines such as 2-vinylpyridine and 4-vinylpyridine; methyl vinyl ether, 2
- Vinyl ethers such as chloroethyl vinyl ether; vinyl halides such as vinyl chloride and vinyl bromide; vinyl esters such as vinyl acetate; acrylamide; It is also possible to use it as a polyolefin. These modified polyolefins can be used alone or as a mixture of multiple types. Among the above-mentioned tertiary amine compounds, it is preferable to use a modified olefin polymer containing a tertiary amino group, which is difficult to bleed out when used.

Component (e): 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 (A-B)n+1, or A-(B-A)n, or B-(A-B)n+1 (A in the above formula is a polymer block made of a styrene compound, and B is a conjugated diene polymer. block, where 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 1,00
0,000, preferably 50,000-250,000
It is. 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 block copolymer. styrene-butadiene radial block copolymer with terminals, styrene-isoprene radial block copolymer with polystyrene block terminals,
Examples include styrene/conjugated diene block copolymers such as butadiene multiblock copolymers, styrene/isoprene multiblock copolymers, and products obtained by hydrogenating these. Preferred among these styrene elastomers are hydrogenated styrene/conjugated diene block copolymers.

■ Olefin elastomer The above olefin elastomer 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; - A homopolymer of higher α-olefin such as hexene, which is an elastomeric polymer, and has a content of 10
Mooney viscosity ML1+4 measured at 0°C is usually 1~
200, preferably 5-150, particularly preferably 7-1
00 range. 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-nonconjugated diene copolymer rubber (EP
DM), ethylene/1-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, methylenenorbornene, 5-ethylidene-2-norbornene,
5-vinyl-2-norbornene, 5-methylene-2-norbornene, 5-methyl-1,4-hexadiene, 7-
Examples include 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.

Component (f): Additional components The resin composition forming the molded article of the present invention may contain the above-mentioned components (a) to (d) or (a) to the extent that the effects of the present invention are not significantly impaired. In addition to the essential components of component (e), additional components as shown below may 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 silicic acid. Synthetic silicates such as aluminum,
Metal hydroxides such as magnesium hydroxide and aluminum hydroxide, metal acid compounds such as alumina and titania, metal powders such as calcium carbonate, aluminum and bronze, carbon black, glass fiber, carbon fiber, potassium titanate,
Whiskers include calcium sulfate, zinc oxide, silicon nitride, sapphire, beryllia, boron carbide, and silicon carbide. Further examples include plasticizers or fluidity improvers, and other additives, such as colorants, stabilizers, dispersion aids, molecular weight regulators, crosslinking agents, and nucleating agents.

(2) Amount Ratio As for the amount ratio of the above-mentioned components constituting the resin composition used in the molded article of the present invention, the amount ratio is usually as follows, based on 100 parts by weight of the olefin resin as component (a): (b) The diene polymer having a hydroxyl group at the terminal or its hydrogenated product is 0.01 to 20 parts by weight, preferably 0.05 to 17 parts by weight.
Parts by weight, particularly preferably from 0.1 to 15 parts by weight, and component (c), the organotin compound, is from 0.01 to 5 parts by weight, preferably from 0.05 to 4 parts by weight, particularly preferably from 0.01 to 5 parts by weight. is 0.1 to 3 parts by weight, and the tertiary amine compound as component (d) is 0.01 to 20 parts by weight, preferably 0.05 to 3 parts by weight.
18 parts by weight, particularly preferably in the range from 0.1 to 17 parts by weight. (b) If the blending amount of the diene polymer having a hydroxyl group at the end of the component or its hydrogenated product is less than the above range, it is not preferable 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 is large;
The cost of the resin composition increases, and the polymer tends to delaminate or bleed out.
This is not preferable because it reduces the adhesion of the paint. Also,
When the organic tin compound of component (c) is less than the above range, the adhesion strength may become very weak depending on the paint to be applied, which is not preferable. On the other hand, even if the above range is exceeded, an effect proportional to the amount added cannot be obtained;
In fact, it is not preferable because it may accelerate the deterioration of the polyolefin. In addition, when the tertiary amine compound of component (d) is less than the above range, depending on the paint to be applied,
The adhesion strength may become very weak, which is not preferable. 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. Furthermore, it is advantageous to further blend the elastomer component (e) into the resin composition having the above-mentioned blending ratio of the constituent components, since rigidity, impact resistance, etc. can be adjusted. Therefore, from the point of view of mechanical strength, the elastomer component is 100% olefin resin.
1 to 200 parts by weight, preferably 5 to 18 parts by weight
It is good to use 0 parts by weight, particularly preferably 10 to 150 parts by weight.

(3) Compounding 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 a mixing method, any conventionally known kneading machine can be used, such as a Brabender blastograph, single-screw or twin-screw extruder, high-power screw kneader, Banbury mixer, kneader, roll, and the like.

[II] Molded object The molded object of the present invention can be obtained by molding the above resin composition by 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.

[III] Painting As the coating method for forming the coated molded body of the present invention, a process that removes surface modification processes such as primer application and plasma treatment from the conventional painting process can be adopted. Can be done. 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, "directly painted" means that the paint is applied without applying the conventional primer application or plasma treatment.
Unless it deviates from the technical idea of the present invention, it is not excluded that some kind of surface treatment be performed before applying the paint. 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. In addition, methods of applying paint include spraying, brushing, and roller application.
Either method can be adopted. As the paint that can be used in the painting process, commonly used paints such as acrylic paints, epoxy paints, polyester paints, urethane paints, and alkyd paints can be used. Among these, urethane paints are preferred, and two-component urethane paints are particularly preferred.

[IV] Painted resin molded article The paint is generally 10 to 100%
The coating is applied to a thickness of μm, preferably about 20 to 70 μm, and the coating is strongly adhered to, so it can be used for various industrial parts such as automobile bumpers, mudguards, side moldings, wheel caps, spoilers, etc. Automotive exterior parts, instrument panels, levers, knobs, interior linings and other automotive interior parts, pots, vacuum cleaners, washing machines, refrigerators, lighting equipment, audio equipment and other electrical products, color boxes, storage cases and other miscellaneous goods. It can be used as a product.

[Experimental Examples] The present invention will be explained in more detail with reference to Examples and Comparative Examples below. 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> Injection molding machine manufactured by Molding Machine Meiki Seisakusho M40A-SJ Molding temperature 230°C Molded product flat plate (65 mm x 65 mm x 2 mm) Three-point bending modulus test piece (90 mm x 10 mm x 4 mm) Flexural modulus JIS K Measured in accordance with -7203. MFR Measured in accordance with ASTM D-1238.

<Painting> Paint Painting was carried out using a two-component urethane paint. Painting method: Mix the paint and use an air spray gun to obtain a coating thickness of approximately 40 μm in the grid test and approximately 1 μm in the peel strength test.
It was spray coated to a thickness of 00 μm. After that, 8
It was baked and dried at 5°C for 30 minutes.

<Evaluation of paint adhesion> Cross-cut test Using a single-edged razor, 11 vertical and horizontal parallel lines perpendicular to the surface of the test piece were drawn at 2 mm intervals to form 100 cross-cuts. Apply cellophane adhesive tape (JIS Z1522) on top of it, hold it at about 30 degrees to the coating surface, and peel it off at once toward you. Observe the condition of the area surrounded by a grid pattern. The number was recorded. After treating the upper half of the peel strength test piece to prevent paint from adhering, each paint was applied to a film thickness of 100 μm and baked and dried. Apply cellophane adhesive tape (e.g.
Apply a Nichiban product (width 24 mm) to the entire surface and make a 1 cm wide cut vertically reaching the base material. The side to which the coating film was not attached was peeled off by hand, and the sample was attached to a tensile testing machine and the load was recorded when the sample was peeled off in a 180 degree direction at a speed of 50 mm/min. In addition, when the coating film was broken, it was described as broken.

Experimental Examples 1 to 25 and Comparative Examples 1 to 8 (1)
Production of resin moldings The components shown in Tables 1, 2, and 3 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, 2, and 3 are as follows. <Olefin resin: (a) component> Block PP (1)
: Ethylene content is 4% by weight, flexural modulus measured in accordance with JIS-K7203 is 14,000kg/cm2
, and MFR measured in accordance with ASTM-D1238
is 60g/10min of propylene/ethylene block copolymer. Block PP (2): ethylene content 13% by weight, JI
Flexural modulus measured in accordance with S-K7203 is 6.0
A propylene/ethylene block copolymer with an MFR of 30 g/10 min measured in accordance with ASTM-D1238. Random PP: ethylene content 3.4% by weight, JIS-K
Flexural modulus measured in accordance with 7203 is 10,500
A propylene/ethylene random copolymer with an MFR of 15 g/10 min measured in accordance with ASTM-D1238. Single PP: Flexural modulus measured in accordance with JIS-K7203 is 13,000 kg/cm2, and ASTM-
Polypropylene with an MFR of 25 g/10 min measured according to D1238. HDPE: Flexural modulus measured in accordance with ASTM-D747 is 10,500 kg/cm2, and JIS-K
Low-pressure polyethylene (high-density polyethylene) with an MFR of 20 g/10 minutes as measured in accordance with 6760.

<Diene polymer having a hydroxyl group at the end or its hydrogenated product: component (b)> Synthesis of a diene polymer having a hydroxyl group at the end In an autoclave with a capacity of 500 ml, 100 g of 1,3-butadiene, 70 g of isopropyl alcohol, and 60 g of isopropyl alcohol were added.
90% in an argon atmosphere using 10g of hydrogen peroxide solution.
Polymerization was carried out at ℃ for 5 hours. After the reaction was completed, unreacted monomers were removed and the resulting diene polymer was dried. The molecular weight of the obtained polymer was approximately 2,900, and the hydroxyl value was approximately 88.
(KOHmg/g). Synthesis of hydrogenated product of diene polymer having a hydroxyl group at the end 50 g of the diene polymer obtained in the above synthesis of the diene polymer having a hydroxyl group at the end, 50 g of cyclohexane,
5 wt % carbon-supported ruthenium catalyst, 5 g, capacity 20
After charging into a 0 ml autoclave and replacing the inside of the system with argon gas, hydrogen gas was introduced until the pressure reached 50 kg/cm2. The temperature was raised to 100℃, and the total pressure was 50kg.
/cm2 while supplying hydrogen gas to keep it at 10
A time reaction was performed. After the reaction was completed, hydrogen was removed and the catalyst was removed by filtration, and the resulting hydrogenated product was precipitated in methanol, separated from the sieve, and dried to obtain the desired product. The iodine value of the obtained diene polymer hydrogenate was 1.5 (g/
100g), and the hydrogen value was 87.8 (KOHmg/g). Diene polymer: A diene polymer obtained by synthesizing the diene polymer having a hydroxyl group at the terminal. Diene polymer hydrogenated product (1): A diene polymer hydrogenated product having a hydroxyl group in the hydrogenated product of the diene polymer having a hydroxyl group at the terminal. Diene polymer hydrogenated product (2): Iodine value 0.5 (g
/100g), butadiene polymer hydrogenated product with a hydroxyl value of 46.9 (KOHmg/g)

<Organotin compound: component (c)> DBTD
L: Dibutyltin dilaurate DOTDL: Dioctyltin dilaurate

[0028]
<Tertiary amine compound: component (d)> EDMA (1):
2-(dimethylamino)ethyl methacrylate content is 30% by weight, obtained by high-pressure radical polymerization method, JI
MFR measured according to S-K6760 is 2g/10
Ethylene/2-(dimethylamino)ethyl methacrylate copolymer. EDMA (2): A graft copolymer in which 2-(dimethylamino)ethyl methacrylate and styrene are grafted onto dry polymer polyethylene obtained by synthesis of EDMA (2) by the impregnation graft polymerization method shown below.
(dimethylamino)ethyl methacrylate content is 15
Weight%, styrene content 25% by weight, JIS-K67
There is a graft copolymer which exhibits a physical property value of MFR of 2 g/10 minutes as measured in accordance with 60. Synthesis capacity of EDMA (2) by impregnation graft polymerization method 1
1080 g of linear low density polyethylene pellets with an MFR of 100 g/10 min measured in accordance with JIS-K6760 in a 0 liter autoclave, 270 g of 2-(dimethylamino)ethyl methacrylate, and 45 styrene.
0 g of benzoyl peroxide, and 21 g of calcium phosphate [Ca3(PO4)2] as a dispersant were added and suspended in 4 liters of water. Next, the temperature of the suspension was maintained at 50° C. for 3 hours, and the polyethylene pellets were impregnated with these 2-(dimethylamino)ethyl methacrylate, styrene, and benzoyl peroxide. Thereafter, the reaction was carried out while gradually increasing the temperature to 94° C. over 8 hours. After the reaction, the obtained pellets were washed with water, the water was removed using a centrifuge, and the pellets were incubated at 80°C for 12
Drying was carried out under reduced pressure for hours. The resulting polymer had a 2-(dimethylamino)ethyl methacrylate content of 15% by weight, a styrene content of 25% by weight, and an MFR of 2g/1.
It indicated 0 minutes. Low molecular compound (1): Light stabilizer manufactured by Adeka Argus
Mark LA62", and its structure is a compound having the structure shown in the following formula.

[0029]

[Chemical formula 3] (R10, R11, R12, R13 in the formula are the following formulas

00
30]

[Image Omitted] or -C13H27, and these R1
At least one of 0, R11, R12, and R13 is
It is an N-methyl-2,2,6,6-tetramethyl-4-piperidyl group, and the remainder is a saturated hydrocarbon group having 13 carbon atoms. )

<Elastomer component: component (e)> EPM
(1): Mooney viscosity ML1+4 (100℃) is 70
, an ethylene-propylene copolymer rubber with a specific gravity of 0.86. EPDM (1): Mooney viscosity ML1+4 (100℃
) is 62, specific gravity is 0.87, oil content 66% by weight
Oil-extended ethylene/propylene/ethylidenenorbornene copolymer rubber containing EPDM (2): Mooney viscosity ML1+4 (100℃
) is 47 and the specific gravity is 0.86. SEBS: Number average molecular weight is 70,000, specific gravity is 0.9
1, a hydrogenated product of styrene/butadiene/styrene triblock copolymer rubber.

(2) Painting of resin moldings The flat plates molded by the above resin molding process were subjected to degreasing treatment (TCE treatment) with trichloroethane vapor for 30 seconds, and those that were not treated at all were treated with an air gun. The paint was applied using. After baking and drying, 4
A grid test was conducted after leaving the sample at room temperature for 8 hours. The results of the elastic modulus and paint adhesion of the resin compositions obtained are shown in Tables 1, 2, and 3.

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

[Table 3] In the composition shown in Comparative Example 3, the flexural modulus could not be measured by the measuring method according to JIS-K7203 because it was too soft. Furthermore, during painting, the flat plate of the test piece was severely deformed during baking and drying after coating, and the surface of the flat plate also became uneven, making it impossible to evaluate. Based on these results, comparing the formulations of Comparative Example 6 in Table 3 and Examples 8 and 12 in Table 1, it was found that the adhesion of the paint was greatly improved by incorporating either the organic tin compound or the amine compound. I can understand that. Furthermore, it can be seen that the combined use of the organotin compound of Example 13 and the amine compound further improves the effect on paint adhesion.

[0036]

Effects of the Invention The molded bodies and painted molded bodies of the present invention can be manufactured by using specific components in the resin composition forming the molded bodies, thereby achieving an improvement over the conventional "direct coating on olefin resin." Contrary to the common sense that "it is impossible to It is extremely useful industrially.

Claims (4)

[Claims] Claim 1: 100 parts by weight of an olefin resin is added with 0 diene polymer having a hydroxyl group at the end or its hydrogenated product.
．． 01 to 20 parts by weight, 0.01 to 5 parts by weight of an organic tin compound, and/or 0.01 to 20 parts by weight of a tertiary amine compound.
A molded article characterized in that it is formed from a resin composition in which parts by weight are blended. Claim 2: 100 parts by weight of an olefin resin contains 0 diene polymer having a hydroxyl group at the end or a hydrogenated product thereof.
．． 01 to 20 parts by weight, 0.01 to 5 parts by weight of an organic tin compound, and/or 0.01 to 20 parts by weight of a tertiary amine compound.
1. A molded article characterized in that it is formed from a resin composition containing 1 to 200 parts by weight of an elastomer component. 3. 100 parts by weight of an olefin resin is added with 0 diene polymer having a hydroxyl group at the end or a hydrogenated product thereof.
．． 01 to 20 parts by weight, 0.01 to 5 parts by weight of an organic tin compound, and/or 0.01 to 20 parts by weight of a tertiary amine compound.
1. A coated molded article, characterized in that the surface of the molded article is formed from a resin composition containing parts by weight, and the surface of the molded article is directly coated. 4. 100 parts by weight of an olefin resin is added with 0 diene polymer having a hydroxyl group at the end or its hydrogenated product.
．． 01 to 20 parts by weight, 0.01 to 5 parts by weight of an organic tin compound, and/or 0.01 to 20 parts by weight of a tertiary amine compound.
1. A coated molded article, characterized in that the surface of the molded article is formed from a resin composition containing 1 to 200 parts by weight of an elastomer component and an elastomer component, and the surface of the molded article is directly coated.