JPH07310046A - Paintable resin composition - Google Patents

Abstract

(57) [Summary] [Structure] A paintable resin composition comprising the following components (a) and (b). (A) Modified olefin resin obtained by graft-reacting an α, β-unsaturated carboxylic acid ester having a hydroxyl group and an aromatic vinyl compound on an olefin resin (b) at least one selected from the following group (B-1) Aromatic vinyl compound having a hydroxyl group and α, β having a hydroxyl group
-Copolymer with unsaturated carboxylic acid ester (b-2) Copolymer of α-olefin and α-olefin having hydroxyl group (b-3) Maleimide compound-modified olefin resin having hydroxyl group (b-4) Polymer having a ring-opened chain of lactone [Effect] The coating property and printability can be improved without impairing the excellent mechanical strength and moldability of the olefin resin, and without subjecting it to solvent treatment, primer treatment or plasma treatment. It is a remarkably excellent composition.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an olefin resin composition having excellent coating adhesion and high mechanical strength without the need for applying a primer and / or cleaning with an organic solvent such as trichloroethane during coating. Regarding things.

[0002]

2. Description of the Related Art Olefin resins do not have polar groups in their molecular structure, and because of their high crystallinity, the adhesion of paints is extremely poor and their coatability is poor. The coating was applied after applying a primer in advance, modifying the surface by plasma treatment or the like, or cleaning the surface with an organic solvent such as trichloroethane to improve the adhesion. However, such a method has conventionally had the following problems. In the primer coating method, there is a disadvantage that an expensive primer must be used and the cost is high due to the large number of steps, and the solvent for the primer needs to be volatilized. Becomes worse,
There was a safety issue with the danger of fire.

On the other hand, in the plasma processing method, since a high vacuum condition is required, it is necessary to install an expensive device, and further, the cost increase cannot be avoided because of the batch type. Furthermore, the surface after the plasma treatment is unstable, and when it comes into contact with a foreign substance, the adhesion of the paint, adhesive or printing ink is reduced, which may cause variations in the adhesion performance, which makes handling very inconvenient. In addition, the cleaning method using an organic solvent such as trichloroethane has an increase in the number of steps, a deterioration of the work environment due to the evaporation of the solvent, and a risk of fire.

Therefore, such primer application,
If the plasma treatment process and the cleaning process with an organic solvent can be omitted, the process can be simplified, the working environment can be improved, and the cost can be reduced. Much research has been done.

In order to improve this drawback, for example, JP-A-59-196344 and JP-A-62-207344 disclose methods for modifying an olefin resin with a compound having a hydroxyl group. However, in these methods, molecular breakage of the olefinic resin due to organic peroxide occurs, resulting in deterioration of physical properties of the base material and modification amount cannot be increased. There has been a demand for a method of improving.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides, in an olefin resin composition, a composition in which the above-mentioned problems are solved and the paintability is drastically improved without impairing the physical properties of the olefin resin. The purpose is to do.

[0007]

[Means for Solving the Problems] As a result of intensive studies, the present inventors have found that an olefin resin modified with an α, β-unsaturated carboxylic acid ester having a hydroxyl group and an aromatic vinyl compound is The present inventors have found that a resin composition containing a polymer having a specific hydroxyl group can solve the above problems, and have completed the present invention.

That is, the present invention is a paintable resin composition containing the following components (a) and (b). (A) Modified olefin resin modified by graft-reacting an α, β-unsaturated carboxylic acid ester having a hydroxyl group and an aromatic vinyl compound to an olefin resin (b) At least one selected from the following group Polymer having a hydroxyl group of (b-1) α, β having an aromatic vinyl compound and a hydroxyl group
-Copolymer with unsaturated carboxylic acid ester (b-2) Copolymer of α-olefin and α-olefin having hydroxyl group (b-3) Maleimide compound-modified olefin resin having hydroxyl group (b-4) Polymers having ring-opened lactone chains

The present invention will be described in detail below.

<Modified Olefin Resin (a)> (1) Olefin Resin The olefin resin used in the component (a) of the present invention is an α-olefin having 2 to 12, preferably 2 to 8 carbon atoms. It is a polymer or a copolymer containing them as a main component. Specific examples of these α-olefins include ethylene, propylene, 1-butene, 1-hexene and 3-methyl-1-.
Butene, 3-methyl-1-pentene, 4-methyl-1-
Pentene, 3,3-dimethyl-1-butene, 4,4-dimethyl-1-pentene, 3-methyl-1-hexene, 4
-Methyl-1-hexene, 4,4-dimethyl-1-hexene, 5-methyl-1-hexene, allylcyclopentane, allylcyclohexane, allylbenzene, 3-cyclohexyl-1-butene, vinylcyclopropane, vinylcyclohexane, 2-Vinylbicyclo [2.2.1]
Heptane etc. can be mentioned.

Of these, ethylene, propylene, 1-butene, 1-hexene and 3-methyl-1- are preferred.
Butene, 4-methyl-1-pentene and the like can be mentioned, and propylene is particularly preferable. These α-olefins may be used alone or in combination of two or more. When two or more α-olefins are used,
Each α-olefin may be randomly or block-distributed in the copolymer. In addition, up to about 15 mol% of other monomers such as 1,9-decadiene, 7-methyl-1,6-octadiene, styrene, divinylbenzene, butadiene, isoprene, and 2-hydroxyethyl (meth) acrylate. It may be a copolymer or a graft polymer.

These olefin-based resins are JIS K
The flexural modulus measured according to 7203 is preferably 1,000 to 50,000 kg / cm ² , more preferably 3,
000 to 30,000 kg / cm ² . The melt flow rate (hereinafter referred to as "MFR") is not particularly limited, but the value measured according to ASTM D 1238 is usually 0.01 to 200 g / 10 minutes, preferably 0.1 to 100 g / 10. Those within the range of minutes are optimal.

(2) α, β-Unsaturated Carboxylic Acid Ester Having a Hydroxyl Group α, β having a hydroxyl group used in the component (a) of the present invention
Examples of the unsaturated carboxylic acid ester include the following compounds. Here, the name (meth) acrylate means acrylate and methacrylate. That is, 2-hydroxyethyl (meth) acrylate,
2-hydroxypropyl (meth) acrylate, 2,3
-Dihydroxypropyl (meth) acrylate, 2-hydroxymethyl-3-hydroxypropyl (meth) acrylate, 2,2-bishydroxymethyl-3-hydroxypropyl (meth) acrylate, oligoethylene glycol or oligo having 4 to 40 carbon atoms Examples thereof include (meth) acrylic acid ester of propylene glycol.

Further, bis (2-hydroxyethyl) malate, bis (2-hydroxypropyl) malate, bis (2,3-dihydroxypropyl) malate, bis (2
-Hydroxymethyl-3-hydroxypropyl) malate, bis (2,2-dihydroxymethyl-3-hydroxypropyl) malate, etc. and their isomers such as fumarate, oligoethylene glycol or oligopropylene glycol having 4 to 40 carbon atoms Examples thereof include maleic acid or fumaric acid ester. Note that maleic acid or fumaric acid ester can be exemplified as a similar compound when both carboxylic acids are not esters of hydroxyalkyl groups as described above and only one is present.

The above α, β-unsaturated carboxylic acid ester having a hydroxyl group can be used alone or in combination of two or more kinds. Among them, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, oligoethylene glycol having 4 to 40 carbon atoms, or (meth) acrylic acid ester of propylene glycol is preferable.

(3) Aromatic vinyl compound Examples of the aromatic vinyl compound include styrene and α-
Methylstyrene, α-methoxystyrene, methylstyrene, dimethylstyrene, 2,4,6-trimethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, nitrostyrene, chloromethylstyrene, cyanostyrene, t-butylstyrene, vinylnaphthalene, etc. Among them, styrene, α-methylstyrene and methylstyrene are preferable. These can be used alone or in combination of two or more.

(4) Modification of olefin resin The amount of the α, β-unsaturated carboxylic acid ester having a hydroxyl group added is 0.5 with respect to 100 parts by weight of the olefin resin.
-50 parts by weight, preferably 1-40 parts by weight. The addition amount of the aromatic vinyl compound used in combination with these compounds is in the range of 0.5 to 100 parts by weight, preferably 1 to 80 parts by weight, based on 100 parts by weight of the olefin resin.

The weight ratio of the α, β-unsaturated carboxylic acid ester having a hydroxyl group to the aromatic vinyl compound may be in the range of 1:99 to 99: 1, but is preferably. It is in the range of 5:95 to 95: 5. If the aromatic vinyl compound is not added or if the ratio is too low, molecular cutting of the olefin resin occurs, and α having a hydroxyl group graft-polymerized to the olefin resin,
The residual rate of hydroxyl groups in the β-unsaturated carboxylic acid ester decreases, and it is not possible to introduce a sufficient amount of hydroxyl groups for modifying the olefin resin. The residual ratio of hydroxyl groups calculated by the following method is preferably 50% or more, more preferably 6%.
It is 0% or more.

Method for Quantifying α, β-Unsaturated Carboxylic Acid Esters Having Hydroxyl Group and Calculating Hydroxyl Residual Rate Infrared spectroscopy (IR method): Purified modified olefin resin is pressed into a film to measure IR spectrum. To do. The quantification is performed using a calibration curve prepared from the absorption at 1724 cm ⁻¹ derived from carbonyl. Proton nuclear magnetic resonance spectroscopy ⁽¹ H-NMR method): Purified modified olefin resin 50mg dissolved by heating in o- dichlorobenzene about 2 ml 130 ° C., the sample was prepared using a heavy benzene as a standard, ¹ 1 H-NMR spectrum is measured. The residual ratio of hydroxyl groups is calculated from the formula (A) using the ratio of the contents obtained by these two kinds of measuring methods.

[0020]

[Equation 1]

The modification of the olefin resin can be carried out by a method such as a solution reaction and a melt reaction which are generally known in the graft copolymerization reaction. For example, the reaction temperature in the case of the melting reaction is arbitrary as long as it is a temperature at which the olefin resin melts, but is 100 to 300 ° C. from the viewpoint of preventing deterioration of the resin and the like.
Is preferred. The reaction time is 0.01 to 10 minutes, preferably 0.05 to 5 minutes. The reaction atmosphere may be air, but is preferably in an inert gas or in a state where the oxygen concentration is reduced by reducing the pressure. Further, for the purpose of improving the reaction efficiency, for example, an unreacted component or the like can be removed by adding an organic solvent such as xylene or by kneading under reduced pressure.

<Polymer Having Hydroxyl Group (b)> The polymer having a hydroxyl group used in the present invention is a polymer having at least one hydroxyl group in its molecule and is a component other than the component (a). Yes, but is not particularly limited, for example, unsaturated compounds having a hydroxyl group, or homopolymers such as unsaturated compounds having a polar group capable of introducing or generating a hydroxyl group by some chemical modification after polymerization, other polymerization A copolymer with a polymerizable monomer or a graft or block copolymer with another polymer, structurally having a branched or linear molecular chain with hydroxyl groups regularly or irregularly pendant, or a hydroxyl group. Refers to all of the oligomers to high molecular weight compounds in which the side chains having is attached in a graft or block manner. A suitable molecular weight has an optimum range depending on the polymer having each hydroxyl group.

Some specific examples will be shown below. (B-1) α, β having an aromatic vinyl compound and a hydroxyl group
-Copolymer with Unsaturated Carboxylic Acid Ester Aromatic Vinyl Compound As the aromatic vinyl compound, the matters described in the section (3) Aromatic vinyl compound of the modified olefin resin (a) are directly applied.

Α, β-Unsaturated Carboxylic Acid Ester Having Hydroxyl Group As the α, β-unsaturated carboxylic acid ester having a hydroxyl group, α, β-having a hydroxyl group of (2) of the modified olefin resin (a) is used. The matters described in the section of unsaturated carboxylic acid ester are applied as they are.

The method for synthesizing the copolymer (b-1) is not particularly limited, and may be a known anion polymerization, cationic polymerization or radical polymerization method, and bulk polymerization method, solution polymerization method, melt polymerization method or suspension method. It can be synthesized by a polymerization method or the like. These copolymers may contain other copolymerizable monomers in an amount not exceeding 30 mol%.

The molecular weight of this copolymer is not particularly limited, but the number average molecular weight is preferably 100 to 100,000.
0, more preferably 200 to 50,000, and particularly preferably 200 to 10,000.

(B-2) Copolymer of α-olefin and α-olefin having a hydroxyl group From the structural point of view, this copolymer has a regular or irregular structure in a branched or linear carbon chain. Α- having regular hydroxyl groups
An olefin generally refers to one having a structure in which it is copolymerized with an α-olefin. Specifically, α having a hydroxyl group
The olefin content is preferably 0.1 to 50% by weight, more preferably 0.5 to 45% by weight, particularly preferably 1 to 40% by weight.

Such a copolymer of an α-olefin and an α-olefin having a hydroxyl group can be prepared by a known method using an α-olefin having an α-olefin and a hydroxyl group as a raw material.
For example, it can be produced by a high pressure radical polymerization method, a polymerization method using a Ziegler-Natta catalyst, or the like. In the case of production by the high-pressure radical polymerization method, an α-olefin, an α-olefin having a hydroxyl group, and a radical polymerization initiator,
For example, pressure of 1,000 to 3,000 atm and temperature of 90 to 3
In the reaction zone kept at 00 ° C., the ratio of α-olefin: α-olefin having a hydroxyl group is 1: 0.0001 to
It is continuously fed so that it becomes 1: 0.1, and the conversion rate is 3 ~.
It is produced by making α-olefin copolymer at 20% and continuously taking out the copolymer from the reaction zone.

In the case of production by a polymerization method using a Ziegler-Natta catalyst, propylene or the like obtained by complexing an α-olefin having a hydroxyl group with an organoaluminum compound or the like is used in a known Ziegler catalyst or the like, for example, a heptane solvent. In the presence or absence of, the polymerization is carried out at a pressure of normal pressure to 20 atm and a temperature of 30 to 150 ° C.

Examples of the α-olefin having a hydroxyl group used here include allyl alcohol and 4-pentene-1-.
All, 5-hexene-1-ol, 9-decene-1-
Unsaturated alcohols such as ol, 10-undecen-1-ol; vinyl ethers such as 2-hydroxyethyl vinyl ether and diethylene glycol monovinyl ether; allyl ethers such as hydroxyethyl allyl ether; 2,6-dimethyl-4-allylphenol And allylphenols. As the α-olefin which is the other copolymerization component, the α-olefin described in (1) Olefin resin of the modified olefin resin (a) is used.
Olefin is applied.

In addition to the above-mentioned α-olefin and α-olefin component having a hydroxyl group, a third copolymerization monomer component may be used, and examples thereof include methyl acrylate, ethyl acrylate, butyl acrylate and methyl meta. Unsaturated carboxylic acid esters such as acrylates; aromatic vinyl compounds such as α-methylstyrene and vinyltoluene; nitrile compounds such as acrylonitrile and methacrylonitrile; vinylpyridines such as 2-vinylpyridine and 4-vinylpyridine; methyl vinyl ether, 2 -Vinyl ether such as chloroethyl vinyl ether; vinyl halide such as vinyl chloride and vinyl bromide; vinyl ester such as vinyl acetate; acrylic aluminide;
Conjugated dienes such as 3-butadiene, 1,3-pentadiene and isoprene; α, ω-dienes such as 1,9-decadiene and 1,13-tetradecadiene; 7-methyl-1,
Non-conjugated dienes such as 6-octadiene; divinylbenzene and the like can be mentioned, and they can also be used as a ternary or multi-component copolymer.

These copolymers may be used either individually or as a mixture of plural kinds. The molecular weight of this copolymer is not particularly limited, but the number average molecular weight is preferably 500 to 500,000, more preferably 1,000 to 100,000.

(B-3) Maleimide Compound-Modified Olefin Resin Having Hydroxyl Group The maleimide compound-modified olefin resin having a hydroxyl group is a maleimide compound residue having a hydroxyl group represented by the general formula (I) in an olefin resin. It is the introduced polymer.

[0034]

[Chemical 1]

(In the formula, R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and n is an integer of 1 to 3.) The olefin resin used here is the modified olefin resin (a). The olefin resin described in (1) Olefin resin is applied.

The method for introducing a maleimide compound residue having a hydroxyl group into an olefin resin is usually obtained by introducing maleic anhydride into the olefin resin, and then reacting a compound having both an amino group and a hydroxyl group to imidize it. You can Known techniques are used for these reaction conditions, and there is no particular limitation.

Examples of the compound having both an amino group and a hydroxyl group include 2-amino-1-ethanol and 3-amino-
1-propanol, 4-amino-1-butanol, 2-
Amino-1-butanol, 5-amino-1-pentanol, 2-amino-1-pentanol, 6-amino-1-
Hexanol, 3-amino-1,2-propanediol, p-amino-2-hydroxyethylbenzene and the like can be mentioned.

Although the molecular weight of the maleimide compound-modified olefin resin having a hydroxyl group is not particularly limited, the number average molecular weight is preferably 100 to 500,000, more preferably 1,000 to 100,000, and particularly preferably 1.0.
It is from 00 to 50,000.

(B-4) Polymer Having Ring-Opening Chain of Lactone Examples of polymers having ring-opening chain of lactone include polymers represented by the following general formulas (II) and (III).

[0040]

[Chemical 2]

(In the formula, R ² represents a hydrocarbon group having 1 to 20 carbon atoms, h and m each represent an integer of 2 to 10, and o and p each represent an integer of 1 to 20)

[0042]

[Chemical 3]

(In the formula, R ³ represents a hydrocarbon group having 1 to 20 carbon atoms, q, r and s are integers of 2 to 10 respectively, T and U
And V each represent an integer of 1 to 20). Also, a structure derived from an unsaturated bond and a ring-opening chain of a lactone, for example, a compound exemplified by the general formula (IV) is copolymerized or graft-polymerized with an olefin resin. It may be a polymer.

[0044]

[Chemical 4]

(In the formula, R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents a hydrocarbon group having 2 to 10 carbon atoms, and W represents 2
An integer of 10 to 10, X is an integer of 1 to 20 and Y is an integer of 1 to 3) Here, as the olefin-based resin, (1) olefin-based resin of the modified olefin-based resin (a) is described. Matters are applied as they are.

As a copolymerization method or a graft copolymerization method for obtaining a polymer having a ring-opened chain of a lactone, known techniques can be used.

The molecular weight of the above polymer is not particularly limited,
In the case of the compounds represented by the general formulas (II) and (III), the number average molecular weight is preferably 50 to 100,000, more preferably 100 to 50,000, particularly preferably 100.
When the compound represented by the general formula (IV) is introduced into the olefin resin, the number average molecular weight is preferably 100 to 500,000, more preferably 1,000 to 100,000. Particularly preferably 1,0
It is from 00 to 50,000.

The above-mentioned polymer having a hydroxyl group can be obtained by the method described in the above item (b-
The polymers are not limited to the polymers described in 1) to (b-4), and may be used alone or in combination of two or more, preferably (b-1) to (b-4). ), More preferably (b-2) to (b-) above.
It is a polymer of 4).

<Additional Component> The coatable resin composition of the present invention may contain a component other than the above components (a) and (b). For example, up to 50% by weight of the component (a) may be replaced with other olefin resin or thermoplastic resin such as polyphenyl ether, and various elastomers may be contained in the resin composition at 50% by weight or less. .
Further, an antioxidant, a weather resistance improver, a nucleating agent, a flame retardant, a plasticizer, a fluidity improver and the like may be contained in the resin composition in an amount of 20% by weight or less. In addition, organic or inorganic fillers, for example, glass fiber, mica, talc, wollastonite, potassium titanate, calcium carbonate, silica and the like are contained in an amount of 50% by weight or less, and a dispersant of these fillers is included in an amount of 5% by weight or less. You can also

<Composition Ratio of Constituent Components> In the present invention, the mixing ratio of the modified olefin resin as the component (a) and the polymer having a hydroxyl group as the component (b) is 100 parts by weight of the component (a). (B) is 0.5 to 50 parts by weight, preferably 0.5 to 40 parts by weight, more preferably 1 to 30 parts by weight,
It is particularly preferably 1 to 25 parts by weight. When the amount of the component (b) is less than 0.5 part by weight, the effect of improving the coatability is small,
If it exceeds 100 parts by weight, it has better chemical resistance than propylene resin.
There is a problem that it is inferior in terms of rigidity and the like.

<Production of Resin Composition> As a melt-kneading method for obtaining the paintable resin composition of the present invention, a kneading method generally used for thermoplastic resins can be applied. For example, powdery or granular components, if necessary,
After being uniformly mixed with the additives and the like described in the section of additional components by a Henschel mixer, a ribbon blender, a V-type blender, etc., they can be kneaded by a uniaxial or multiaxial kneading extruder, a roll, a Banbury mixer and the like. A solvent or the like may be used during kneading.

Molding processability of the paintable resin composition of the present invention is not particularly limited, and a molding method generally used for thermoplastic resins, that is, injection molding,
Blow molding, extrusion molding, sheet molding, thermoforming, rotational molding,
Various molding methods such as lamination molding and press molding can be applied.

<Coating> The paintable resin composition of the present invention does not undergo primer coating or surface modification such as plasma treatment,
In addition, good paint adhesion can be obtained without washing with an organic solvent such as trichloroethane, and it is surprising that it is impossible to directly coat conventional olefin resin directly. is there. This is a result based on the use of the above resin composition, and it is extremely difficult to predict it from the conventionally known fact.

As a method for coating the resin composition of the present invention, the conventional coating process can be omitted from the processes such as primer coating, plasma treatment and organic solvent cleaning. That is, in the molded body obtained by molding the resin composition,
The paint can be applied directly by a usual method.

As a method for applying the coating material, there are spray application by spraying, brush application, application by a roller and the like, and any method can be adopted. As the paint that can be used, generally widely used paints such as acrylic paints, epoxy paints, polyester paints, urethane paints and alkyd paints can be used.

[0056]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Reference Example 1: Production of modified polypropylene (a) Propylene homopolymer powder (JIS K 7210)
MFR measured in accordance with 1 g / 10 min, melting point about 164
C.) 2,000 g, 2-hydroxyethyl methacrylate 100 g, styrene 100 g and 1,3-bis (t-
After mixing 10 g of butylperoxyisopropyl) benzene with a super mixer, using a twin-screw extruder (manufactured by Japan Steel Works, trade name: TEX-30 type), a cylinder temperature of 180 ° C., a screw rotation speed of 250 rpm, and a discharge rate. 5 kg
A modified olefin resin (hereinafter referred to as "resin A") was obtained by kneading under reduced pressure under the conditions of / hr and vent pressure of 50 mmHg.
The contents of 2-hydroxyethyl methacrylate and styrene in Resin A were quantified by infrared spectroscopy. as a result,
The 2-hydroxyethyl methacrylate content was 4.0% by weight and the styrene content was 3.4% by weight.

Reference Example 2: Production of Modified Polypropylene (a) 100 parts by weight of homopolymer powder of propylene (the same as used in Reference Example 1) was used with a twin-screw extruder, the cylinder temperature was 180 ° C. and the screw was used. Rotation speed 250 rpm,
When carrying out reduced pressure kneading under the conditions of a discharge rate of 4.5 kg / hr and a vent pressure of 50 mmHg, 5 parts by weight of styrene and 5 parts of 2-hydroxyethyl methacrylate were added from the middle of the extruder cylinder.
A mixture of 1 part by weight and 0.5 part by weight of 1,3-bis (t-butylperoxyisopropyl) benzene was added under pressure to obtain a modified olefin resin (hereinafter referred to as “resin B”).
The content of 2-hydroxyethyl methacrylate in Resin B was 3.8% by weight and the content of styrene was 3.6% by weight.

Reference Example 3: Production of styrene-2-hydroxyethyl methacrylate copolymer (b-1) 2.5 L of dimethylformamide, 1.5 kg of styrene, and 2-hydroxyethyl were placed in a 10 L separable flask which had been sufficiently replaced with nitrogen. 1.5 kg of methacrylate was added and the temperature was raised to 100 ° C with stirring, then benzoyl peroxide 1
A solution of 8 g and 150 ml of dodecyl mercaptan dissolved in 500 ml of dimethylformamide was added dropwise over 4 hours. After polymerizing for an additional 1 hour, the polymerization solution is added to water 20
It was poured into L and the precipitated copolymer was separated by filtration and dried. The recovered copolymer (hereinafter referred to as “resin C”) was 1,010
g, and the result of analysis by infrared spectroscopy was 2
Hydroxyethyl methacrylate content is 47.7% by weight
And the number average molecular weight by gel permeation chromatography (hereinafter referred to as “GPC”) is 2,41.
0, the weight average molecular weight was 13,700.

Reference Example 4 Production of Styrene-2-hydroxyethylmethacrylate Copolymer (b-1) 3 L of dimethylformamide, 750 g of styrene and 2,250 g of 2-hydroxyethyl methacrylate were placed in a 10 L separable flask which had been sufficiently replaced with nitrogen. And 18 g of benzoyl peroxide were added, the temperature was raised to 100 ° C. with stirring, 50 ml of dodecyl mercaptan was added, polymerization was performed for 2 hours and 30 minutes, 50 ml of dodecyl mercaptan was further added, and polymerization was further performed for 2 hours and 30 minutes. Polymerize the solution with water 20
It was poured into L and the precipitated copolymer was separated by filtration and dried. 1,636 g of the recovered copolymer (hereinafter referred to as "resin D")
As a result of analysis by infrared spectroscopy, the content of 2-hydroxyethyl methacrylate was 76.9% by weight, the number average molecular weight by GPC was 940, and the weight average molecular weight was 3,600.

Reference Example 5: Preparation of propylene-10-undecen-1-ol copolymer (b-2) 230 ml of a heptane solution of diethylaluminum chloride (20% by weight) was added to a 500 ml glass flask thoroughly purged with nitrogen. Then, 46 g of 10-undecen-1-ol was added dropwise thereto with stirring over 1 hour, and then 7
It heated up at 0 degreeC and stirred for 1 hour. In a 1 L stainless steel autoclave equipped with a stirrer and temperature controller, the previously prepared diethylaluminum chloride and 10
Undecen-1-ol in heptane solution, diethylaluminum chloride in heptane solution (20% by weight)
30.5 ml and TiCl ₃ catalyst (made by Marubeni Solvay)
After introducing 1.0 g and adding 60 ml of hydrogen, propylene was fed so that the pressure was 0.5 kg / cm ² G, and polymerization was carried out at 65 ° C. for 2 hours. After completion of the polymerization, the polymerization solution was treated in the same manner as in Reference Example 1 to prepare a copolymer (hereinafter referred to as "resin E") 85.
0 g was obtained. Infrared spectroscopic analysis showed absorption at 3,340 cm ^-1 due to the hydroxyl group. The MFR of this resin was 4.1 g / 10 minutes, and the polypropylene-equivalent number average molecular weight measured by GPC was 61,000. Again 10
The content of undecen-1-ol was 17.4% by weight by ¹ H-NMR.

Reference Example 6: Production of Modified Polypropylene (b-4) Having Ring-Opening Chain of Lactone Homopolymer powder of propylene (same as in Reference Example 1)
2,000g, lactone modified hydroxyethyl (meth)
Acrylate monomer (manufactured by Daicel Chemical Industries, Ltd., trade name: PLACCEL F, FM-1) 200 g and 1,
After mixing 20 g of 3-bis (t-butylperoxyisopropyl) benzene with a super mixer, using a twin-screw extruder (the same as that used in Reference Example 1), a cylinder temperature of 180 ° C. and a screw rotation speed of 250 rpm A modified olefin resin (hereinafter referred to as "resin F") was obtained by kneading under reduced pressure under the conditions of a discharge rate of 5 kg / hr and a vent pressure of 50 mmHg. The content of PLACCEL F in Resin F is 7.24.
% By weight. Number average molecular weight by GPC is 32.0
00, the weight average molecular weight was 85,000.

Reference Example (Comparative) 7: Production of Modified Polypropylene The procedure of Reference Example 1 was repeated except that styrene was not added. The resin thus obtained is hereinafter referred to as "resin G". The content of 2-hydroxyethyl methacrylate in Resin G was 4.3% by weight.

Examples 1 to 12 and Comparative Examples 1 to 12 Resins A to G obtained in Reference Examples 1 to 7, polypropylene homopolymer (manufactured by Mitsubishi Yuka Co., Ltd., trade name: MA8), maleimide compound modified with a hydroxyl group Polypropylene (manufactured by Sanyo Kasei Co., trade name: Yumex 1201 and Yumex 1210) (b-3), polycaprolactone diol (manufactured by Daicel Chemical Industries, Ltd., trade name: PLACCEL
205, 220 and 240 of the 200 series) (b
-4) was kneaded with the composition shown in Tables 1 to 4 using a 30 mm diameter twin-screw extruder (the same as that used in Reference Example 1) to obtain a resin composition. From this, an injection molding machine (M40 manufactured by Meiki Seisakusho)
A-SJ) was used for injection molding under the conditions of a cylinder temperature of 230 ° C. and a mold cooling temperature of 40 ° C. to prepare a test piece. The evaluation test is carried out by the following method, and the results are shown in Table 1
Shown in FIG.

The coating test was carried out as follows using a one-pack type acrylic melamine-based paint and a two-pack type urethane-based paint. Coating method: Mix paint and use an air spray gun
Spray coating was applied so that the coating film thickness was about 40 μm in the cross-cut test and about 100 μm in the peel strength test. Then, it was baked at 120 ° C. for 60 minutes and dried. Paint adhesion evaluation (cross-cut test): Using a single-edged razor, 2 m of vertical and horizontal 11 parallel lines running perpendicular to the surface of the test piece
Draw at intervals of m to make 100 squares. Cellophane adhesive tape (JIS Z1522) was adequately pressure-bonded on top of it, and it was peeled off at once with the coating surface kept at about 30 degrees, and the state of the part surrounded by the grid was observed The number was recorded.

Flexural Modulus According to JIS K 7203, it was measured using an Instron tester.

Izod impact strength ISO R 180-1969 (JIS K 711
According to 0), the notched Izod impact strength was measured using an Izod impact tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.).

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

[Table 3]

[0071]

[Table 4]

[0072]

As described above, the paintable resin composition of the present invention does not impair the mechanical strength and moldability of the olefin resin, and does not undergo solvent treatment, primer treatment, plasma treatment or the like, Excellent paintability and printability.

Claims (1)

[Claims] 1. A paintable resin composition comprising the following components (a) and (b): (A) Modified olefin resin modified by graft-reacting an α, β-unsaturated carboxylic acid ester having a hydroxyl group and an aromatic vinyl compound to an olefin resin (b) At least one selected from the following group Polymer having a hydroxyl group of (b-1) α, β having an aromatic vinyl compound and a hydroxyl group
-Copolymer with unsaturated carboxylic acid ester (b-2) Copolymer of α-olefin and α-olefin having hydroxyl group (b-3) Maleimide compound-modified olefin resin having hydroxyl group (b-4) Polymers having ring-opened lactone chains