JPH05179080A - Coated flexible form - Google Patents

Abstract

PURPOSE:To provide a coated flexible form of high coating film adhesiveness, without the need for primer coating or plasma treatment, comprising a propylene-ethylene block copolymer, elastomer, specific copolymer, filler, and organotin compound, etc., each at specified amount. CONSTITUTION:The objective form can be obtained by providing a coating film on the surface of a resin composition form <=10000kg/cm<2> in the flexural modulus determined by the JIS-6703 which is produced by incorporating (A) a total of 100 pts.wt. of (1) 30-70 pts.wt. of a propylene-ethylene block copolymer containing 4-30wt.% of normal temperature xylene solubles of ethylene content at 20-70wt.%, 1-200g/10min in the MFR of the entire copolymer and 3-21wt.% in ethylene content and (2) 70-30 pts.wt. of an elastomer like ethylene-based one with (B) 0.1-25 pts.wt. of a copolymer of ethylene and OH-contg. unsaturated compound, (C) 0.01-7 pts.wt. of a filler like talc >=37000cm<2>/g in specific surface area, <=15mum in length, 0.8-3.0mum, in mean particle diameter and >=5 in mean aspect ratio and (D) 0.01-5 pts.wt. of an organotin compound and/or 0.01-20 pts.wt. of a tertiary amine compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coated flexible molded article, and more particularly to a coated flexible molded article molded from a resin composition containing propylene / ethylene-block copolymer and an elastomer as main components. It is a thing.

The coated molded article of the present invention is used for automobile members such as fenders, bumpers, side moldings, wheel caps and instrument panels.

[0003]

2. Description of the Related Art Polyolefin resins have a drawback in that the adhesion of coating materials is extremely poor because of the absence of polar groups in their structure, resulting in poor coatability. Conventionally, when coating the surface of a polyolefin resin, a method of applying a primer on the surface in advance or modifying the surface by plasma treatment to improve the coating property and then applying the coating Was taken.

However, such a coating method has the following problems.

That is, in the primer coating method,
In addition to the drawback that the coating cost is high due to the high price of the primer and the large number of coating processes, it is necessary to volatilize the solvent of the primer, so the working environment is bad and there is a risk of fire. There was also a problem with safety.

On the other hand, in the plasma processing method, a high degree of vacuum is required, an expensive apparatus must be installed, and the processing is batch type, so that an increase in cost is unavoidable. However, the surface after the plasma treatment is unstable, the adhesion of the paint is lowered by the contact with the foreign matter, and the coating film performance tends to vary, so that its handling is extremely inconvenient.

[0007]

Therefore, if such a pretreatment process can be omitted, the coating process can be simplified, the working environment can be improved, and the cost can be reduced. Although much research has been done on the improvement of this problem, it has not been solved yet, and in many cases, the polyolefin resin material is coated after the above primer application or plasma treatment.

[0008]

In order to solve the above-mentioned problems, the inventors of the present invention have conducted extensive studies to improve the resin material, and as a result, from a propylene-based soft resin composition having a specific composition containing a small amount of filler, The molded body can be directly coated with paint, has excellent mechanical strength and hot water resistance of the coating film, and does not change the specific gravity or rigidity of the molded body, impairing the characteristics as a soft resin. The present invention has been completed by finding out that there is nothing.

That is, the present invention relates to the following component (a):
Consisting of (e) component, flexural modulus according to JIS-6703 is 10,0
A coated soft molded article having a coating film formed on the surface of a resin composition molded article of 00 kg / cm ² or less.

Component (a): ethylene content of 20 to 70% by weight
It contains 4 to 30% by weight of room temperature xylene solubles, the total MFR is 1 to 200 g / 10 min and the ethylene content is 3 to 21%.
Propylene / ethylene-block copolymer in% by weight
30 to 70 parts by weight, component (b): ethylene-based elastomer,
70-30 parts by weight of at least one elastomer selected from hydrogenated styrene / butadiene-block copolymer and hydrogenated styrene / isoprene-block copolymer,

Component (c): 0.1 to 25 parts by weight of a copolymer of ethylene and a hydroxyl group-containing unsaturated compound, and component (d) to 100 parts by weight of the total of the components (a) and (b). : Specific surface area of 37,000 cm ² / g or more, length of 15 μm or less, average particle size of 0.8 to 3.0 μm, and average aspect ratio of 5
Selected from the above talc, aluminum borate whiskers having an average diameter of 2 μm or less and an average aspect ratio of 5 or more, potassium titanate whiskers, magnesium oxysulfate whiskers, titanium oxide whiskers, calcium carbonate whiskers, and calcium carbonate whiskers. 0.01 to 7 parts by weight of at least one filler, component (e): 0.01 to 5 parts by weight of organotin compound and / or 0.01 to 20 parts by weight of tertiary amine compound.

[I] Molded Resin Composition (1) Component (a) Component: Propylene / Ethylene-Block Copolymer The propylene / ethylene-block copolymer of the component (a) used in the present invention is ethylene. It contains 4 to 30% by weight, preferably 6 to 25% by weight, of substantially amorphous room temperature xylene solubles in a content of 20 to 70% by weight, and the MFR of the entire copolymer (230 ° C, load 2.16kg). ) Is 1 to 200 g / 10 minutes, preferably 2 to 100 g / 10 minutes, and has an ethylene content of 3 to 21% by weight, preferably 3 to 16% by weight. The higher the room temperature xylene-soluble content is, the better the coating strength is, which is advantageous, but if the content exceeds the above range, the surface of the molded article becomes sticky, which is not preferable.

Here, the ethylene content is a value measured by an infrared absorption spectrum analysis method or the like. Room temperature xylene solubles was calculated by immersing a 2g sample in 500g boiling xylene for 20 minutes to dissolve it, then cooling it to room temperature, filtering the precipitated solid phase with a glass filter, and drying it to calculate the solid phase weight. It is a value. MFR is measured according to JIS-K7210.

The propylene / ethylene-block copolymer may be a ternary or higher terpolymer containing other unsaturated monomer within a range that does not significantly impair the effects of the present invention. Examples of such unsaturated monomers include butene.
-1, α-olefins such as hexene-1, vinyl esters such as vinyl acetate, unsaturated silane compounds such as vinyltrimethoxysilane, (meth) acrylic acid (ester),
An unsaturated organic acid such as maleic anhydride or a derivative thereof can be mentioned. The polymerized form of these unsaturated monomers may be any of graft type, random type and block type.

Component (b): Elastomer The component (b) elastomer used in the present invention is an ethylene / propylene binary copolymer rubber (EPM), an ethylene / propylene / non-conjugated diene terpolymer rubber (EP).
DM), ethylene / butene-1 terpolymer rubber, ethylene / propylene / butene-1 terpolymer rubber, ethylene elastomer, hydrogenated styrene / butadiene-
Block copolymer and hydrogenated styrene-isoprene-
It is at least one elastomer selected from block copolymers.

In the above EPM, the propylene content is 20 to 55.
%, Preferably 25-55% by weight, with Mooney viscosity (ML
Those having a temperature of _{1 + 4} 100 ° C.) of 10 to 100, especially 15 to 90 are suitable. EPDM preferably has an iodine value of 20 or less, particularly 18 or less. The ethylene / butene-1 binary copolymer rubber is
Butene-1 content 5 to 30% by weight, preferably 10 to 25% by weight
Are preferred. Ethylene / Propylene / Butene-1
The terpolymer rubber has a propylene content of 20 to 55% by weight,
It is preferably 25 to 50% by weight and a butene-1 content of 3 to 15% by weight, preferably 5 to 12% by weight.

Here, the amount of each component of the ethylene elastomer is a value measured by a conventional method such as an infrared absorption spectrum analysis method or an NMR method. The crystallinity of these rubbers is preferably 30% or less. The manufacturing method and shape are not particularly limited.

The hydrogenated styrene / butadiene-block copolymer and the hydrogenated styrene / isoprene-block copolymer are each completely or partially hydrogenated, so-called styrene / ethylene / styrene-block copolymer ( SEBS) and styrene / ethylene / propylene / styrene-block copolymer (SEPS). Usually the hydrogenation rate is 95% or more,
It is preferably 99% or more. Also, the styrene content is 5 ~
It is preferably 50% by weight, particularly preferably 15 to 50% by weight.

The elastomers having the above-mentioned physical property ranges are excellent in coating performance and physical property balance of the composition.

Component (c): Copolymer of ethylene and a hydroxyl group-containing unsaturated compound The component (c) used in the present invention is a copolymer of ethylene and a hydroxyl group-containing unsaturated compound, and is branched or linear. It has a structure in which a hydroxyl group-containing unsaturated compound is copolymerized irregularly or at regular intervals in the carbon chain.

As the hydroxyl group-containing unsaturated compound, for example,
2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, poly (ethylene glycol) monomethacrylate and the like can be mentioned.

Specifically, the content of the hydroxyl 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 the molecular weight is 200 to 20%.
0,000, preferably 500 to 100,000, particularly preferably 8
It is a polymer that is liquid, semi-solid or solid at room temperature of 00 to 10,000. When the molecular weight is out of the above range, the coating property of the molded product is significantly reduced.

The copolymer of ethylene and a hydroxyl group-containing unsaturated compound can be produced by a known method using ethylene and a hydroxyl group-containing unsaturated compound as a raw material, for example, a high pressure radical polymerization method.

In the case of the high-pressure radical polymerization method, ethylene, a hydroxyl group-containing unsaturated compound and a radical polymerization initiator are added, for example, in a reaction region kept at a pressure of 1,000 to 3,000 atm and a temperature of 90 to 280 ° C. Insert continuously so that the ratio of unsaturated compounds is 1: 0.0001 to 0.02,
20% ethylene is converted to copolymer and the copolymer is continuously removed from the reaction zone.

The copolymer (c) can be used as a ternary or multi-component copolymer by using a third copolymer component in addition to ethylene and a hydroxyl group-containing unsaturated compound. As such a third component, unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate and methyl methacrylate, vinyl aromatic compounds such as styrene, α-methylstyrene and vinyltoluene, acrylonitrile and methacrylonitrile. Nitrile compounds such as, vinyl pyridines such as 2-vinyl pyridine and 4-vinyl pyridine, vinyl ethers such as methyl vinyl ether and 2-chloroethyl vinyl ether, vinyl halides such as vinyl chloride and vinyl bromide, vinyl esters such as vinyl acetate and To list acrylamide etc. You can

These copolymers of component (c) can be used either individually or as a mixture of a plurality of them.

Component (d): Filler The filler of component (d) used in the present invention has a specific surface area of 37,000 cm ² / g or more, preferably 40,000 cm ² / g or more and a length of substantially 15 μm or less, Talc having an average aspect ratio of 5 or more, preferably 6 or more, preferably 10 μm or less, an average particle size of 0.8 to 3.0 μm, preferably 0.8 to 2.5 μm,
The average diameter of 2μm or less, preferably having an average aspect ratio of 5 or more at 1.5μm or less, preferably 10 or more aluminum borate whiskers, the potassium titanate whisker, said magnesium oxysulfate whiskers (MgSO ₄ · 5M
g (OH) ₂ .3H ₂ O, also referred to as magnesium sulfate whiskers), titanium oxide whiskers, calcium carbonate whiskers, and calcium carbonate.

Here, the term "substantially" the length of talc means that the length of most talc particles is within this range. Talc is produced, for example, by crushing raw talc with an impact crusher or a micron mill crusher, further finely crushing it with an Icron mill or a jet crusher, and then classifying and adjusting it with a cyclone or a micron separator. As a rough stone, it is preferable that it is produced in China because it contains a small amount of metal irregularity components.

The average particle diameter is measured by a liquid phase sedimentation light transmission method, and the measuring apparatus is, for example, Shimadzu SA-CP type. The specific surface area is measured by the air permeation method. As a measuring device, for example, SS-100 manufactured by Shimadzu Corporation
There is a mold. Length and aspect ratio are measured by microscopy.

Regarding the whiskers such as aluminum borate whiskers, potassium titanate whiskers, magnesium sulfate whiskers, titanium oxide whiskers, calcium carbonate whiskers, etc., if the average diameter exceeds the above range, the appearance of the molded article and high temperature The dimensional stability of is reduced.

Of the above-mentioned fillers, talc, aluminum borate whiskers and magnesium sulfate whiskers are preferably used alone, and talc and each of the above whiskers are preferably used, and particularly talc and aluminum borate whiskers or magnesium sulfate whiskers are preferably used. preferable.

These fillers may be surface-treated with a surfactant, a coupling agent or the like.

Component (e): Organotin Compound The organotin compound used in the present invention is represented by the following chemical formula 1.

[0034]

[Chemical 1]

Here, R ¹ , R ² , R ³ and R ⁴ are each independently a saturated hydrocarbon group having 1 to 12 carbon atoms, preferably 3 to 12 carbon atoms, Y ¹ and Y ² are each independently To a fatty acid, a maleic acid derivative, a mercaptan, a mercapto acid, etc., preferably a fatty acid or a maleic acid derivative, X ¹ is an oxygen atom, a sulfur atom, a maleic acid group, etc., preferably an oxygen atom or a maleic acid group. is there. n is 0 or 1 to 30, preferably 0 or an integer of 1 to 25, particularly preferably 0 or 1 to
It is an integer of 20.

Specific examples of the organotin compound of the above general formula include monobutyl-tin-trimethylmalate, monobutyl-tin-trioctylmalate, dibutyl-tin-
Dilaurate, dibutyl-tin-laurate-methylmalate, dibutyl-tin-dioylmalate, dibutyl-tin-dimethylmalate, dibutyl-tin-malate, dibutyl-tin-methoxymethylmalate, dibutyl-tin-dioctylmalate, Dibutyl-tin-dioctyl-thioglycolate, dibutyl-tin-dilauryl-mercaptide, tribenzyl-tin-octylmalate, tribenzyl-tin-trimethylmaleate, etc. can be mentioned, and these organotin compounds each alone, It can be used as a mixture of a plurality of kinds, and usually, it can be appropriately selected and used from commercially available products.

Component (e): Tertiary amine compound The tertiary amine compound used in the present invention includes from low molecular weight compounds having a tertiary amine structure to high molecular weight compounds.

Low Molecular Weight Compound Having a Tertiary Amine Structure The low molecular weight compound having a tertiary amine structure is one having a molecular weight of 1,000 or less. Specifically, for example, triethylenediamine, dimethylaminopropylamine, diethylaminopropylamine, tetraguanidine, 1,8-diazabicyclo- (5,4,0) -7-undecene, N, N-
Bis (2-hydroxyethyl) laurylamine, tetrakis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl)
1,2,3,4-butanetetracarboxylate and the like can be mentioned. These can be appropriately selected and used from commercially available products.

Polymer Compound Having a Tertiary Amine Structure As the polymer compound having a tertiary amine structure, a polymer having a molecular weight of 1,000 or more and being liquid, semi-solid or solid at room temperature is included. An amino group-containing modified olefin polymer can be mentioned.

The modified olefin polymer containing a tertiary amino group has a structure in which a branched or linear carbon chain is irregularly or regularly copolymerized with an unsaturated compound containing a tertiary amino group, or a tertiary amino group-containing unsaturated compound. It has a structure in which a side chain having an amine structure is grafted, and the content of the tertiary amino group-containing unsaturated compound is 0.1 to 50% by weight, preferably 0.5 to 40%.
%, Particularly preferably 1 to 40% by weight, and the melt flow rate (MFR) measured according to JIS-K6760 is 0.1.
~ 1,000 g / 10 min, preferably 0.5-700 g / 10 min.

This tertiary amino group-containing olefin polymer can be produced by a known method using a tertiary amino group-containing unsaturated compound. For example, in the case of production by a high-pressure radical polymerization method, ethylene, a tertiary amino group-containing unsaturated compound and a radical polymerization initiator are added under pressure, for example.
Conversion rate is continuously supplied to the reaction zone kept at 1,000 to 3,000 atm and temperature 90 to 300 ° C so that the ratio of ethylene: unsaturated compound containing tertiary amino group is 1: 0.0001 to 0.1. It is produced by making an ethylene polymer at 3 to 20% and removing the copolymer from the reaction zone.

Further, also in the case of production by the graft polymerization method, it can be produced by a known method. That is, an olefin polymer, a tertiary amino group-containing unsaturated compound and a radical polymerization initiator are suspended in an aqueous solution,
It is produced by heating the system to the decomposition temperature of the radical polymerization initiator to cause a graft reaction on the polyolefin to modify it.

Such a tertiary amino group-containing unsaturated compound is represented by the following chemical formula 2.

[0044]

[Chemical 2]

Here, R ⁵ is hydrogen or a saturated hydrocarbon having 1 to 4 carbon atoms, preferably hydrogen or a saturated hydrocarbon group having 1 to 2 carbon atoms, and R ⁶ is 2 to 12 carbon atoms, preferably 2 to 6
A saturated hydrocarbon group, R ⁷ and R ⁸ each independently have 1 to
12, preferably 1 to 6, particularly preferably 1 to 3 saturated hydrocarbons. X is an oxygen atom, a sulfur atom or -NR ⁹ - and,
It is preferably an oxygen atom or —NR ⁹ —, where R ⁹ is a hydrogen atom or a saturated hydrocarbon group having 1 to 12 carbon atoms, preferably hydrogen or a saturated hydrocarbon group having 1 to 6 carbon atoms.

Examples of such a tertiary amino group-containing unsaturated compound include 2- (dimethylamino) ethyl acrylate, 2- (diethylamino) ethyl acrylate, and 2- (diethylamino) ethyl acrylate.
(Dimethylamino) ethyl methacrylate, 2- (diethylamino) ethyl methacrylate, 2- [di (tert.butyl) amino] ethyl acrylate, 2- [di (tert.butyl) amino] ethyl methacrylate, 3- (dimethyl Amino) propyl acrylamide and 3- (dimethylamino) propyl methacrylamide may be mentioned.

The olefinic monomer component in the case of copolymerizing with the above-mentioned unsaturated compound containing a tertiary amino group is
Examples thereof include α-olefins such as ethylene, propylene, and 1-butene, with ethylene being preferred.

The olefin polymer used as a trunk polymer in the case of grafting the above-mentioned tertiary amino group-containing unsaturated compound is an olefin resin as the component (a) and an olefin elastomer as the component (b). And the like, and polyethylene resins, propylene resins and ethylene elastomers are particularly preferable.

When a modified olefin polymer containing a tertiary amino group is produced, a monomer which can be copolymerized with the unsaturated compound containing a tertiary amino group is allowed to coexist to give a ternary system or even a multi-component system. It can also be used as a modified polyolefin.

Examples of such a monomer component include unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate and methyl imethacrylate, vinyl aromatic compounds such as styrene, α-methylstyrene and vinyltoluene, acrylonitrile and methacrylic acid. Nitrile compounds such as ronitrile, vinyl pyridines such as 2-vinyl pyridine and 4-vinyl pyridine, vinyl ethers such as methyl vinyl ether and 2-chloroethyl vinyl ether, vinyl halides such as vinyl chloride and vinyl bromide, vinyl such as vinyl acetate. Ester, acrylamide, etc. can be mentioned.

Among these tertiary amine compounds listed as the component (e), the modified olefin polymer containing a tertiary amino group is less likely to bleed out during use.

(2) Amount Ratio In the resin composition of the present invention, other components are added to 100 parts by weight of the total amount of the above components (a) and (b).

The blending amounts of the component (a) are the same as those of the component (a) and the component (b).
30 to 70 parts by weight, preferably 55 to 65 parts by weight, out of 100 parts by weight of the total amount of the components, therefore component (b) is 70 to 30 parts by weight, preferably 45 to 35 parts by weight. When the amount of the component (a) exceeds the above range, that is, when the amount of the component (b) is less than the above range, the coating strength and impact strength of the coated molded article are poor,
If the blending amount of the component (a) is less than the above range, the heat resistance rigidity and mechanical strength of the molded product will be reduced.

The blending amounts of the component (c) are the components (a) and (b).
The total amount of the components is 0.1 to 25 parts by weight, preferably 0.1 to 18 parts by weight, and particularly preferably 0.5 to 12 parts by weight, based on 100 parts by weight. If it is less than the above range, the reproducibility of the adhesion of the coating material to the molded article is poor and the coating strength is also low. A compounding amount exceeding the above range is economically disadvantageous and causes bleed-out of the component (c), which may rather lower the coating strength.

The blending amount of the component (d) is 0.01 to 7 parts by weight, preferably 0.1 to 6 parts by weight, particularly preferably 0.5 to 10 parts by weight based on 100 parts by weight of the total amount of the components (a) and (b).
5 parts by weight. If it is less than the above range, the coating property as an automobile member is not sufficient, and if it exceeds this range, whitening due to scratches occurs, which is not suitable.

The compounding amount of the organotin compound as the component (e) is
The total amount of the components (a) and (b) is 0.
01 to 5 parts by weight, preferably 0.05 to 4 parts by weight, particularly preferably 0.1 to 3 parts by weight. If it is less than the above range, the coating strength is poor, and if it exceeds the above range, bleeding out occurs and the coating strength is rather lowered.

The content of the tertiary amine compound as the component (e) is 0.01 to 20 parts by weight, preferably 0.05 to 18 parts by weight, based on 100 parts by weight of the total amount of the components (a) and (b). Particularly preferred is 0.1 to 17 parts by weight. If it is less than the above range, the coating strength will be poor, and if it exceeds the above range, the physical property balance of the molded article will be deteriorated.

The two kinds of the component (e) may be blended either alone or in combination.

(3) Additional component Since the resin composition molded product of the present invention is coated, it is not necessary to add a pigment for coloring, but the addition of the pigment is not excluded. In order to improve various performances of compositions and molded articles, for example, softening agents for hydrocarbon rubber (average molecular weight 300 to 1,000), various plasticizers, antioxidants, antistatic agents, flame retardants, dispersants, etc. Various additives can be added.

In addition to the components (a) to (e), various resins, various elastomers, compounding agents such as various fillers such as glass fibers, glass balloons, carbon fibers, etc. may be added within a range that does not significantly impair the effects of the present invention. It can be blended.

Among these additional components, the ethylene polymer (f) and the hydrocarbon type rubber softening agent (g) are particularly preferable.

Component (f): Ethylene Polymer Preferred ethylene polymers as additional components include low density polyethylene (branched polyethylene), medium density and high density polyethylene (straight chain ethylene polymer), especially heat resistance. From the viewpoint of properties, medium-density and high-density linear ethylene polymers are preferable.

The linear ethylene polymer has a density of
In ^{0.915~0.970g / cm 3, MFR (190} ℃, 2.16kg) is
0.5-200 g / 10 min, preferably 10-150 g / 10 min of ethylene homopolymer or ethylene and α-olefin directly copolymerized by the method described in JP-B-56-18132, for example. It is a chain ethylene polymer. Here, as the α-olefin, butene-1, hexene-1, 4-methylpentene
-1, octene-1 and the like, and two or more of these may be used in combination.

The addition of the component (f) has the effect of improving the coating strength of the molded product, and its amount is generally 3 to 25 parts by weight per 100 parts by weight of the total amount of the components (a) and (b). Parts, preferably 3 to 20 parts by weight, particularly preferably 3 to 15 parts
If the weight part exceeds the above range, the balance of the physical properties of the molded product deteriorates.

(G) Hydrocarbon Rubber Softener A preferred hydrocarbon rubber softener as an additional component is
It plays an important role in controlling the processability and flexibility of the molded product. The hydrocarbon-based softening agent for rubber is a mixture of three aromatic rings, naphthene rings and paraffin chains, and paraffinic chains having a paraffin chain carbon number of 50% or more of the total carbon are preferred. The blending amount thereof is preferably 200 parts by weight or less based on 100 parts by weight of the total amount of the components (a) and (b).

[II] Manufacture of Molded Body A resin composition obtained by mixing the constituent components of the present invention and, if necessary, additional components is, for example, a single-screw extruder, a twin-screw extruder, a Banbury mixer, a roll, The kneading is carried out using an ordinary kneading machine such as a lavender plastograph and a kneader. A kneading method is selected so as to make each component well dispersed, and a twin-screw extruder is generally used.

For molding, any molding method such as injection molding, compression molding, extrusion molding (sheet molding, blow molding) may be used depending on the shape of the desired molded product. Injection molding is preferable as the molding of the soft automobile member.

[III] Coating A coating material is directly applied to the surface of the molded body obtained above to form a coating film. As a coating method, the conventional coating process can be performed by removing the primer coating process. Further, the plasma treatment process performed to enhance the adhesion of the coating film can be omitted. However,
An auxiliary surface treatment such as a normal degreasing treatment for washing and removing hand dust, machine oil, and the like, which are inevitably attached to the surface of the molded product before coating, is performed as necessary.

The degreasing treatment includes a cleaning method using an organic solvent or its vapor, water, steam, an acid, an alkaline solution, an aqueous solution of a surfactant, etc. Among these, cleaning using vapor of an organic solvent, water, hot water, and an alkaline solution. Cleaning using water or warm water to which a neutral detergent is added, alcohol cleaning, etc. are preferably used.

The coating material can be applied by spraying, brush coating, roller coating or the like, and any method can be adopted.

Examples of the paint include generally widely used paints such as acrylic paints, epoxy paints, polyester paints, urethane paints, alkyd paints and melamine paints. Among these, acrylic paints, melamine paints, polyester paints and urethane paints are preferably used.

The coated flexible molded article of the present invention has a coating film of generally 10 to 100 μm, preferably 15 to 70 μm and 50
It exhibits a peel strength of 0 g / cm or more and is particularly excellent in hot water resistance. In addition, the weather resistance of unpainted parts that are directly exposed to sunlight is also high, so fenders, door panels, bumpers, spoilers, mudguards, side moldings, wheel caps, instrument panels, trims, consoles, handle pads, etc. Highly practical as a member.

[0073]

EXAMPLES The present invention will be described more specifically by showing examples and comparative examples below. The raw materials used here,
The coating method and evaluation method are as follows.

(1) Raw materials (a) Component a-1: Contains 14% by weight of room temperature xylene-soluble matter having an ethylene content of 40% by weight, the total ethylene content of the copolymer is 9% by weight, and the MFR is 40 g. / 10 minutes propylene ethylene
-Block copolymer a-2: Contains 16% by weight of room temperature xylene-soluble components having an ethylene content of 30% by weight, and the ethylene content of the entire copolymer is 7.5.
Wt% and MFR of 10 g / 10 min Propylene / ethylene-block copolymer a-3: Ethylene content of the entire copolymer containing 16 wt% of room temperature xylene solubles with an ethylene content of 30 wt% Of 12% by weight and MFR of 80 g / 10 min
-Block copolymer a-4: Polypropylene having a flexural modulus of 13,000 kg / cm ² and MFR of 25 g / 10 min a-5: Ethylene content of 13.8% by weight, flexural elasticity measured according to JIS-K7203 Rate is 13,000kg / cm ² and ASTM-D1238
Vinyltrimethoxysilane graft-propylene-ethylene-block copolymer (trade name "Linklon XPM700B" manufactured by Mitsubishi Petrochemical Co., Ltd.) having MFR of 11 g / 10 minutes and silane compound content of 2.2% by weight measured in accordance with )

(B) Component b-1: Mooney viscosity ML _{1 + 4} (100 ° C.) of 47, propylene content
26% by weight of ethylene / propylene copolymer rubber (EPM) b-2: styrene content of 33%, molecular weight of 25,000, styrene / ethylene / butylene / styrene-block copolymer

Component (c) c-1: 2-hydroxyethyl methacrylate content of 10% by weight, ethylene / 2-hydroxyethyl methacrylate copolymer having a molecular weight of 54,000, obtained by high pressure radical polymerization method c-2: high pressure radical 2-Hydroxyethyl methacrylate content 10% by weight, methyl acrylate content 10% by weight, molecular weight 32,000 ethylene-2-hydroxyethyl methacrylate / methyl acrylate copolymer obtained by polymerization method c-3: high pressure radical polymerization method Ethylene 2-hydroxymethacrylate copolymer having a 2-hydroxyethylmethacrylate content of 10% by weight and a molecular weight of 9,000 obtained in step c-4: 2-hydroxyethylmethacrylate content of 35% by weight obtained by the high-pressure radical polymerization method. , 2-hydroxyethyl methacrylate copolymer with a molecular weight of 2,300

(D) Component d-1: Specific surface area 34,000 to 39,000 cm ² / g, average particle size
1.5-2,0 μm talc d-2: average particle size 0.2-0.5 μm, fiber length 10-20 μm
Potassium titanate whiskers d-3: specific surface area 10,000 ~ 11,500 cm ² / g, average particle size
0.15-0.30 μm calcium carbonate

Component (e) e-1: dibutyl tin dilaurate e-2: light stabilizer "Mark LA62" manufactured by ADEKA ARGUS CORPORATION
And its structure is the compound shown in Chemical formula 3.

[0079]

[Chemical 3]

(In the formula, R ¹⁰ , R ¹¹ , R ¹² and R ¹³ represent the following chemical formula 4 or —C ₁₃ H ₂₇ , and these R ¹⁰ , R ¹¹ and R ₁₃
^At least one of ¹² , R ¹³ is N-methyl-2,2,6,6-
Tetramethyl-4-piperidyl group, the remaining 13 carbons
Of saturated hydrocarbon group)

[0081]

[Chemical 4]

E-3: 2- (dimethylamino) ethyl methacrylate content of 30% by weight obtained by high pressure radical polymerization method, MFR measured according to JIS-K6760 is 2 g /
Ethylene 2- (dimethylamino) ethyl methacrylate copolymer for 10 minutes e-4: 2- (dimethylamino) was added to polyethylene, which is the backbone polymer obtained by the synthesis of EDMA (2) by the graft polymerization method shown below. Graft copolymer grafted with ethylmethacrylate and styrene with a 2- (dimethylamino) ethylmethacrylate content of 15% by weight, a styrene content of 25% by weight, and an MFR of 2 g measured according to JIS-K6760. / 1
Graft copolymer showing 0 minute physical properties

(Synthesis of e-4 by graft polymerization method) Capacity
In a 10 liter autoclave, MFR measured according to JIS-K6760 is 100 g / 10 min linear low density polyethylene pellets 1,080 g, 2- (dimethylamino) ethyl methacrylate 270 g, styrene 450 g, benzoylper. 6,5 g of oxide and calcium phosphate as a dispersant (Ca ₃ (PO ₄ )
₂ ] 21 g was added and suspended in 4 liters of water. Then, the temperature of the suspension was kept at 50 ° C. for 3 hours, and the reaction was performed while further gradually increasing the temperature to 94 ° C. over 8 hours. After the reaction was completed, the obtained pellets were washed with water, removed of water with a centrifuge, and dried under reduced pressure at 80 ° C. for 12 hours. The resulting polymer has a 2- (dimethylamino) ethyl methacrylate content of 15% by weight, a styrene content of 25% by weight,
The MFR was 2 g / 10 min.

Component (f) f-1: Density 0,958 g / cm ³ , MFR (190 ° C, 2.16 kg) 20 g / 10 min ethylene polymer

(G) Component g-1: Paraffin oil having an average molecular weight of 746 and a ring analysis of 0%

(2) Coating method (pretreatment, baking treatment) The molded flat plate was subjected to the following pretreatment, that is, degreasing treatment (TCE) for 20 seconds with trichloroethane vapor.
(Treatment) After completely unwashed (non-treated), the paint was applied using an air gun. After finishing baking and drying,
It was left at room temperature for 48 hours and a paintability test was conducted. (Paint) Coating was performed using a commercially available polyester urethane-based paint. (Coating) Each coating material was prepared and spray-coated with an air spray gun so that the coating film thickness was about 30 μm and about 100 μm.

(3) Evaluation [Evaluation of mechanical strength] (Flexural modulus) The molded specimen was measured according to JIS-K7203. The measurement temperature is 23 ° C. (Scratchability) The test sheet was rubbed with a 100-yen coin, and the mark was visually observed to determine the degree of whitening due to scratches. (Peeling of cross-cut) 1 mm of 11 horizontal and vertical lines perpendicular to the surface of a test piece coated with a single-edged razor about 30 μm thick
Draw at intervals to make 100 squares. Adhere enough cellophane adhesive tape (JIS-Z1522) on it, peel it off at a stretch while keeping it at about 30 degrees with the painted surface, observe the state of the part surrounded by the grid, and check that it did not peel The number of eyes was recorded. (Peel strength) The surface of a test piece coated to a thickness of about 100 μm was cut straight with a 1 cm width with a single-edged razor, and the strip of the coating film was 180 ° at a speed of 50 mm / min with a tensile tester.
The load when pulling and peeling in an inverted form was read. (Hot water resistance test) The TCE-treated coated test pieces were immersed in warm water at 40 ° C for 240 hours, and then evaluated by a cross-cut test.

Examples 1 to 23 and Comparative Examples 1 to 11 (a) component, (b) component, (c) component, (d) component,
The components (e), (f) and (g) are mixed in the proportions shown in Tables 1 to 3, and further tris (2,4-di-tert.butylphenyl) phosphite and 3,9-bis [ 2- {3- (3-tert.Butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane The total of components (a) to (e) 1
0.1 parts by weight, 3.0 parts by weight of carbon black masterbatch and 3.0 parts by weight of oleic acid amide for each 00 parts by weight.
0.3 parts by weight of each was mixed and thoroughly mixed with a high-speed mixer. Then, using a high-speed twin-screw extruder, kneading and granulating at a temperature condition of 210 ° C., the obtained colored pellets are supplied to a screw in-line injection molding machine, and a paintability and weather resistance evaluation sheet (100 mm × 100 mm × 3 mm) and test pieces for physical property evaluation 2
Molded at 10 ° C. The evaluation results are shown in Tables 1 to 3.

[0089]

[Table 1]

[Table 2]

[Table 3]

[0090]

[Effect of the invention] The coated flexible molded article of the present invention has a weight of 500 g.
Shows a peeling strength of coating film of not less than / cm, especially excellent in hot water resistance,
In addition, the weather resistance of unpainted parts exposed directly to sunlight is also good. Therefore, it is highly practical as an automobile member such as a fender, a door panel, a bumper, a spoiler, a mudguard, a side molding, a wheel cap, an instrument panel, a trim, a console and a handle pad.

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Claims (1)

[Claims] 1. A coating film is formed on the surface of a resin composition molded article comprising the following components (a) to (e) and having a flexural modulus according to JIS-6703 of 10,000 kg / cm ² or less. A painted soft molded article characterized by the above. Component (a): MFR of the whole copolymer containing 4-30% by weight of room temperature xylene solubles with an ethylene content of 20-70% by weight.
Of 1 to 200 g / 10 min and an ethylene content of 3 to 21% by weight, 30 to 70 parts by weight of a propylene / ethylene-block copolymer, (b) component: ethylene elastomer, hydrogenated styrene / butadiene-block copolymer 70 to 30 parts by weight of at least one elastomer selected from polymers and hydrogenated styrene-isoprene-block copolymer, (c) with respect to 100 parts by weight of the total amount of the components (a) and (b). Component: 0.1 to 25 parts by weight of a copolymer of ethylene and a hydroxyl group-containing unsaturated compound, (d) component: specific surface area of 37,000 cm ² / g or more, length of substantially 15 μm or less, average particle diameter of 0.8 to Talc with an average aspect ratio of 5 or more at 3.0 μm, aluminum borate whiskers with an average diameter of 2 μm or less and an average aspect ratio of 5 or more, potassium titanate whiskers, and magnesium oxysulfate whiskers 0.01 to 7 parts by weight of at least one filler selected from titanium oxide whiskers, calcium carbonate whiskers and calcium carbonate, (e) component: organotin compound 0.01 to 5 parts by weight and / or tertiary amine compound 0.01 to 20 parts by weight Parts by weight.