JPH0873694A - Paintable resin composition molding - Google Patents

Abstract

(57) [Summary] (Correction) [Structure] A molded article of a resin composition containing the following components (a) and (b) in the following compounding ratio, wherein the surface of the molded article is attenuated by infrared spectroscopy. Relative content of polyphenylene ether (X) near the surface of the molded article measured by the total reflection method (ATR method)
Is 3 or more, and the relative occupancy rate (Y) of the aromatic compound on the surface of the molded article measured by ESCA spectroscopy is 1 × 1.
A paintable resin composition molded article characterized by being 0 ^-3 or less. (A) Modified propylene-based polymer obtained by subjecting a propylene-based resin to a graft copolymerization step of an α, β-unsaturated carboxylic acid ester having a hydroxyl group and an aromatic vinyl compound 90 to 40% by weight (b) Polyphenylene ether 10 to 60% by weight [Effect] A molded product having excellent heat resistance and mechanical strength, with outstanding paintability and printability, without using a surface modifier such as a primer or an organic solvent such as trichloroethane. Is.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to heat resistance, mechanical strength and dimensional accuracy, which are excellent characteristics of polyphenylene ether (hereinafter referred to as "PPE"), and moldability and resistance, which are excellent characteristics of propylene resin. The present invention relates to a paintable resin composition molded article having an organic solvent property and having a hydroxyl group introduced into a propylene-based resin to improve paint adhesion, adhesiveness, printability, and the like. The paintable resin composition and the molded article thereof are engineering plastics useful as industrial materials such as automobile parts such as wheel caps, spoilers, gears and switch sealants, electric parts, machine parts and the like.

[0002]

2. Description of the Related Art PPE has excellent heat resistance, dimensional stability,
It is known as an engineering plastic that has non-hygroscopicity and electrical properties, but its melt flowability is poor,
Molding processing such as injection molding or extrusion molding is difficult, and the molded product has the drawbacks of poor solvent resistance and impact resistance.

On the other hand, propylene-based resins are
It is widely used for the production of molded products such as bottles, sheets and plates because of its excellent resistance to organic solvents, low specific gravity and low cost. However, the heat resistance is not as good as that of engineering plastics, which is an obstacle to the use of engineering plastics in the field of application. If a resin composition that combines the heat resistance and toughness of PPE with the organic solvent resistance of an olefin resin and complements the drawbacks of both is obtained, the field of application as an engineering plastic will expand, so many studies have been conducted. Has been done.

However, in this resin composition,
When the propylene resin is the sea and the PPE is the island,
Since the olefin resin has a non-polar molecular structure, it has a poor affinity with other substances and is extremely inferior in coating properties such as paint adhesion, adhesiveness, printability and antistatic property.

In order to improve this drawback, for example, JP-A-60-58410 and JP-A-62-207344 disclose methods for modifying an olefin resin with a compound having a hydroxyl group. However, these methods cause the molecular breakage of the olefin resin due to the organic peroxide, resulting in deterioration of physical properties. When a (meth) acrylic acid ester-based monomer (for example, 2-hydroxyethyl methacrylate) is used as a compound having a hydroxyl group, the modified product is analyzed, and as a result, a large number of ester moieties to which a hydroxyl group is bonded disappear due to hydrolysis or the like. Therefore, it was found that the effect of improving paintability was not sufficiently exhibited.

[0006]

DISCLOSURE OF THE INVENTION The present invention relates to a resin composition of PPE and a propylene-based resin, which solves the above-mentioned problems and further improves paintability and the like, and is a paintable resin having high mechanical strength. It is intended to provide a composition and a molded article thereof.

[0007]

The inventors of the present invention have made extensive studies for this reason, and as a result, modified propylene-based polymers modified with an α, β-unsaturated carboxylic acid ester having a hydroxyl group and an aromatic vinyl compound. And a PPE resin composition, or a surface of a molded article of a resin composition containing a partially hydrogenated aromatic vinyl compound-conjugated diene block copolymer is a propylene-based resin excellent in organic solvent resistance, The present invention has been completed by finding that the above-described problems can be achieved by providing a structure in which PPE having paint adhesion is present at a certain amount or more immediately inside thereof.

That is, the present invention is a molded product of a resin composition containing the following components (a) and (b) in the following compounding ratio, and the surface of the molded product is measured by an attenuated total reflection method by infrared spectroscopy ( APE relative content (X) in the vicinity of the surface of the molded product measured by ATR method) is 3 or more, and relative occupancy ratio (Y) of the aromatic compound on the surface of the molded product measured by ESCA spectroscopy
Is 1 × 10 ⁻³ or less, which is a paintable resin composition molded article, wherein (a) a propylene-based resin has an α, β-unsaturated carboxylic acid ester having a hydroxyl group and an aromatic vinyl compound. Modified polypropylene polymer obtained by subjecting and to a graft copolymerization step 90 to 40% by weight (b) PPE 10 to 60% by weight

The resin composition has the following component (a):
The above paintable resin composition molded article is a resin composition containing (b) and (c) in the following compounding ratio. (A) Modified propylene-based polymer obtained by subjecting a propylene-based resin to a graft copolymerization step of an α, β-unsaturated carboxylic acid ester having a hydroxyl group and an aromatic vinyl compound 90 to 40% by weight ( b) PPE 10 to 60% by weight (c) Partially hydrogenated aromatic vinyl compound-conjugated diene block copolymer 1 to 40 parts by weight based on 100 parts by weight of the total of components (a) and (b). The invention will be described in detail.

<Modified Propylene Polymer (a)> (1) Propylene Resin The propylene resin used in the present invention is a homopolymer of propylene and other copolymers with propylene within a range not exceeding 50 mol%. It can include possible α-olefins. Specific examples of the α-olefin include ethylene,
1-butene, 1-hexene, 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,
Examples include 5-methyl-1-hexene, allylcyclopentane, allylcyclohexane, allylbenzene, 3-cyclohexyl-1-butene, vinylcyclopropane, vinylcyclohexane, and 2-vinylbicyclo [2.2.1] heptane. it can.

Of these, ethylene, 1-
Butene, 1-hexene, 3-methyl-1-butene, 3-
Methyl-1-pentene, 4-methyl-1-pentene, 3
-Methyl-1-hexene and the like can be mentioned, with ethylene, 1-butene, 3-methyl-1-butene and 4-methyl-1-pentene being more 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.

Further, as the monomer copolymerizable with propylene, conjugated dienes such as butadiene and divinylbenzene, 4-methyl-1,4-hexadiene and 7-methyl-
1,6-octadiene, 1,9-decadiene, 1,13
And non-conjugated dienes such as tetradecadiene. However, the propylene-based resin used in the present invention is crystalline, and the crystallinity by X-ray analysis is preferably 10%.
Above, more preferably 20% or more. Furthermore,
The flexural modulus measured according to JIS K 7203 is 1,000 to 50,000 kg / cm ² , preferably 3,000.
0 to 30,000 kg / cm ² , more preferably 3,000 to
It is preferably 20,000 kg / cm ² and the melting point due to the propylene component is 140 ° C. or higher. Also, JI
It is preferable that the melt flow rate (hereinafter referred to as "MFR") according to SK7210 is 0.1 to 100 g / 10 minutes.

(2) α, β-Unsaturated Carboxylic Acid Ester Having Hydroxyl Group Examples of the α, β-unsaturated carboxylic acid ester having a hydroxyl group used in the present invention 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,
Examples thereof include 2,2-bishydroxymethyl-3-hydroxypropyl (meth) acrylate, (meth) acrylic acid ester of oligoethylene glycol or oligopropylene glycol having 4 to 40 carbon atoms.

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 esters 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 The aromatic vinyl compound is represented by the following general formula (I).

[0017]

Embedded image

(In the formula, R ¹ and R ² are selected from a hydrogen atom and a lower alkyl group having 1 to 6 carbon atoms, and R ³ and R 2 are
⁴ is selected from a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms, a chlorine atom and a bromine atom, and R ⁵ , R ⁶ and R ⁷ are hydrogen atoms, a lower alkyl group having 1 to 6 carbon atoms and an alkenyl group. Rs selected from or adjacent to each other together form a benzene ring with the carbon atom to which they are bonded).

Specific examples of the aromatic vinyl compound include styrene, paramethylstyrene, α-methylstyrene, vinylxylene, vinyltoluene, vinylnaphthalene, divinylbenzene, bromostyrene and chlorostyrene. Among these, styrene, α-methylstyrene, paramethylstyrene, vinyltoluene and vinylxylene are preferable, and styrene is more preferable. These can be used alone or in combination of two or more.

(4) Modification of Propylene 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 propylene resin.
-50 parts by weight, preferably 1-40 parts by weight, more preferably 1-20 parts by weight. The addition amount of the aromatic vinyl compound used in combination with these compounds is 0.5 to 100 parts by weight based on 100 parts by weight of the olefin resin.
It is preferably in the range of 1 to 80 parts by weight, more preferably 1 to 40 parts by weight.

The ratio of the addition amount 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 by weight, but is preferably. 5:95 to 95: 5, more preferably 5:95 to 67:33, still more preferably 20:80 to 6
It is in the range of 0 to 40, particularly preferably 20:80 to 55:45, most preferably 20:80 to 50:50. If the aromatic vinyl compound is not added or the ratio is too low, α, β- graft-polymerized on the propylene resin
The residual rate of hydroxyl groups in the unsaturated carboxylic acid ester (described later in the analytical method) decreases, and it is not possible to introduce a sufficient amount of hydroxyl groups for modifying the propylene resin. Hydroxyl group residual rate is 5
It is preferably 0% or more, more preferably 60% or more, and most preferably 70% or more.

Infrared spectroscopy in component (a) (hereinafter "IR
Method)) α, β- calculated from the carbonyl group
The content of unsaturated carboxylic acid is preferably 2 to 30% by weight,
More preferably 3 to 20% by weight, particularly preferably 5 to 2
0% by weight. When the content is low, the coating properties are not good, while when it is too high, the physical properties of the composition, particularly the impact resistance, are not good.

The modified propylene-based polymer (a) used in the present invention has a high graft efficiency of the α, β-unsaturated carboxylic acid ester having a hydroxyl group and the aromatic vinyl compound, and the gel (xylene at 130 ° C.). A small amount of insoluble matter is preferable. That is, in the total amount of the α, β-unsaturated carboxylic acid ester having a hydroxyl group and the aromatic vinyl compound in the modified propylene-based polymer, the following mathematical formula (a) is used.
The amount (α) of graft-bonding to the propylene resin calculated by is preferably 5% by weight or more, more preferably 1
It is 0% by weight or more, particularly preferably 15% by weight or more.
The contents of the α, β-unsaturated carboxylic acid ester having a hydroxyl group and the aromatic vinyl compound are I unless otherwise stated.
It is a value obtained by the R method and is the same in the following description.

The graft ratio (β) of the total of the α, β-unsaturated carboxylic acid ester having a hydroxyl group and the aromatic vinyl compound to the propylene resin is represented by the following mathematical formula (B), preferably 90% by weight. Or more, more preferably 100
% Or more, particularly preferably 120% or more. If this value is low, the paintability will be poor.

[0025]

[Equation 1]

[0026]

[Equation 2]

[In the above formulas, Mn represents the number average molecular weight, and A, B and C are as follows. That is, 1 g of the modified propylene-based polymer was dissolved in 50 ml of boiling xylene, followed by high-temperature centrifugation at 130 ° C. and 10,000 rpm for 1 hour, and the obtained 130 ° C. xylene-soluble component was poured into 200 ml of methyl ethyl ketone. The weight of the deposited precipitate (P) is Bg, and the total content of the α, β-unsaturated carboxylic acid ester having a hydroxyl group and the aromatic vinyl compound in the precipitate (P) is A% by weight. The total content of the α, β-unsaturated carboxylic acid ester having a hydroxyl group and the aromatic vinyl compound in the modified propylene-based polymer is C% by weight.
And]

Here, Mn of the modified propylene resin is
After dissolving 1 g of modified propylene-based polymer in 50 ml of boiling xylene, high-temperature centrifugation was performed at 130 ° C. and 10,000 rpm for 1 hour, the xylene-soluble component at 130 ° C. was poured into 200 ml of methyl ethyl ketone, and the deposited precipitate was subjected to gel permeation chromatography. The Mn of the copolymer portion of the α, β-unsaturated carboxylic acid ester having a hydroxyl group in the precipitate and the aromatic vinyl compound is a value calculated by polypropylene (hereinafter referred to as “GPC”) in terms of polypropylene. The value obtained by removing the methyl ethyl ketone soluble matter after the separation operation of (1) was removed by an evaporator and dried to dryness, and was calculated in terms of polystyrene by GPC. The same applies to the following.

The insoluble matter (% by weight) at 130 ° C. is 1
g of the modified propylene polymer was dissolved in 50 ml of boiling xylene and subjected to high-temperature centrifugation at 130 ° C. and 10,000 rpm for 1 hour. The 130 ° C. xylene solubles were removed by decantation, and the remaining xylene insolubles were removed with methanol. It is a value obtained by the following formula (C), where Dg is the weight when the precipitate is filtered and dried. 130 ° C xylene insoluble matter (% by weight) = D x 100 (C)

This value is preferably 30% by weight or less, more preferably 20% by weight or less, particularly preferably 15% by weight.
It is the following. When it is 30% by weight or more, the paintability is remarkably deteriorated.

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 from the viewpoint of preventing deterioration of the resin, it is 140 to 300 ° C
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.

As the radical initiator, organic peroxides,
An azo compound, radiation irradiation or the like can be used, but an organic peroxide having a crosslinking efficiency of 15 to 70, more preferably 20 to 60, particularly preferably 24 to 55 is used.

Specific examples of the organic peroxide having a crosslinking efficiency of 15 to 70 include t-butylperoxyoctate, dibenzoylperoxide, t-octylperoxybenzoate and 1,1-di-t-butylperoxide. Oxy-3,3,3
5-trimethylcyclohexane, 1,1-di-t-butylperoxycyclohexane, t-butylperoxy-
3,3,5-trimethylhexanoate, 2,2-di-
t-butyl peroxybutane, t-butyl peroxyisopropyl carbonate, t-amyl peroxybenzoate, t-butyl peroxybenzoate, dicumyl peroxide, t-butyl cumyl peroxide, 2,5
-Dimethyl-2,5-di-t-butylperoxyhexane, bis (t-butylperoxyisopropyl) benzene, di-t-butylperoxide, 2,5-dimethyl-
2,5-di-t-butylperoxyhexyne-3 and the like can be mentioned.

Dilauroyl peroxide, azobisisobutyronitrile, dioctanoyl peroxide,
t-butyl peroxypivalate, t-amyl pivalate, t-butyl peroxy neodecanoate, t-butyl hydroperoxide, cumene hydroperoxide, t-octyl hydroperoxide, diisopropylbenzene monohydroperoxide, bis- 3, 5,
Crosslinking efficiency of 5-trimethylhexanoyl peroxide, dimyricityl peroxydicarbonate and the like is less than 15, which is not preferable.

Here, the crosslinking efficiency is measured by the following procedure. i) Inject into the ampoule n-pentadecane and the sample organic peroxide. The organic peroxide concentration is adjusted to 0.07 to 0.11 mol with respect to 100 L of n-pentadecane. ii) Replace the air in the ampoule with He gas and seal it. iii) 1 at the temperature where the half-life of organic peroxide is 900 seconds
Heat for 50 minutes (10 times half-life) to completely decompose the organic peroxide. iv) Cool to room temperature and n by gas chromatography
-Quantify pentadecane dimer. Crosslinking efficiency (ε): The amount of the dimer relative to 1 mol of the organic peroxide is calculated from the amount of the obtained dimer to obtain the crosslinking efficiency (ε) of the organized oxide.

When the cross-linking efficiency is low, α, β- having a hydroxyl group
Graft copolymerization of an unsaturated carboxylic acid ester and an aromatic vinyl compound onto a propylene resin is unlikely to occur, resulting in poor coatability. Further, for the purpose of improving reaction efficiency, for example, addition of an organic solvent such as xylene, particularly addition of a halogenated aromatic compound such as o-dichlorobenzene, or kneading under reduced pressure to remove unreacted components can be performed. .

<PPE (b)> PPE used in the present invention
(B) is represented by the general formula (II)

[0038]

Embedded image

(In the formula, Q ¹ represents a halogen atom, a primary or secondary alkyl group, an aryl group, an aminoalkyl group, a hydrocarbon oxy group or a halohydrocarbon oxy group, and Q ² represents a hydrogen atom. , A halogen atom, a primary or secondary alkyl group, an aryl group, a haloalkyl group, a hydrocarbon oxy group or a halohydrocarbon oxy group, and m represents a number of 10 or more). It is a polymer or a copolymer.

Preferable examples of the primary alkyl group for Q ¹ and Q ² include methyl, ethyl, n-propyl, n-butyl and n.
-Amyl, isoamyl, 2-methylbutyl, n-hexyl, 2,3-dimethylbutyl, 2-, 3- or 4-
It is a methylpentyl or heptyl group. Suitable examples of secondary alkyl groups include isopropyl, sec-butyl or 1-
It is ethylpropyl. In many cases, each Q ¹ is an alkyl group or a phenyl group, especially an alkyl group having 1 to 4 carbon atoms, and Q ² is a hydrogen atom.

Suitable homopolymers of PPE are those composed of, for example, 2,6-dimethyl-1,4-phenylene ether units. A preferred copolymer is a random copolymer composed of a combination of the above units and 2,3,6-trimethyl-1,4-phenylene ether units.
Many suitable homopolymers or random copolymers are described in the patents and literature. Also suitable are PPEs that include a molecular moiety that improves properties such as molecular weight, melt viscosity and / or impact strength. For example, it is a resin in which a vinyl monomer such as an acrylonitrile or an aromatic vinyl compound such as styrene or a polymer such as polystyrene or an elastomer is graft-copolymerized on PPE. P
The molecular weight of PE is usually 30 ° C measured in chloroform.
Has an intrinsic viscosity of about 0.2 to 0.8 dl / g.

PPE is usually produced by oxidative coupling of the above-mentioned monomers. Numerous catalyst systems are known for the oxidative coupling polymerization of PPE. There is no particular limitation on the selection of the catalyst, and any known catalyst can be used. For example, those containing at least one heavy metal compound such as copper, manganese, or cobalt, usually in combination with various other substances, and the like.

<Partially Hydrogenated Aromatic Vinyl Compound-Conjugated Diene Block Copolymer (c)> The partially hydrogenated block copolymer (c) used in the present invention is conjugated with a chain block A derived from an aromatic vinyl compound. It is a block copolymer in which the aliphatic unsaturated group of block B of the aromatic vinyl compound-conjugated diene block copolymer having a structure having at least one chain block B derived from a diene is reduced by hydrogenation. The arrangement of blocks A and B is
It has a linear structure or a branched structure, and the branched structure includes a radial teleblock structure. Further, a part of these structures may contain a random chain formed by random copolymerization of an aromatic vinyl compound and a conjugated diene. Among these, those having a chain structure are preferable, and those having an ABA triblock structure are more preferable. As the aromatic vinyl compound forming the block A, the aromatic vinyl compound described in the section (3) Aromatic vinyl compound of the modified olefin resin (a) can be applied.

Specific examples of the conjugated diene include 1,3-butadiene, 2-methyl-1,3-butadiene and 2,3-
Examples thereof include dimethyl-1,3-butadiene and 1,3-pentadiene. Of these, 1,3-butadiene and 2-methyl-1,3-butadiene are preferable, and 2-methyl-1,3 is most preferable. -Butadiene. In addition to these conjugated dienes, small amounts of ethylene, propylene, 1
-Lower olefins such as butene and cyclopentadiene,
Non-conjugated dienes may be included.

The proportion of the repeating units derived from the aromatic vinyl compound in the partially hydrogenated aromatic vinyl compound-conjugated diene block copolymer (c) is preferably 10 to 80% by weight, and 30 to 80% by weight. Is more preferable, and still more preferably 50 to 80% by weight. The proportion of hydrogenation in these partially hydrogenated block copolymers (c) is arbitrary, but the proportion of unsaturated bonds remaining in the block B without being hydrogenated is preferably 20% or less, preferably 10%.
The following is more preferable. Further, 25% or less of the aromatic unsaturated bond in the block A may be hydrogenated.

These partially hydrogenated block copolymers (c) have a toluene solution viscosity of 30% at a concentration of 15% by weight at 25 ° C. as a measure of their molecular weight.
1000 at 0 to 30 cP or 20% by weight
Those in the range of 0 to 50 cP are preferable. If it exceeds the range, molding processability of the composition will be difficult, and if it is smaller, the mechanical strength level of the composition will be low, which is not preferable.

Many methods have been proposed as a method for producing an aromatic vinyl compound-conjugated diene block copolymer. As a typical method, for example, Japanese Patent Publication No. 40-2
3798, U.S. Pat. No. 3,595,942 or 4,09
There is a method described in each specification of No. 0,990, and block copolymerization is carried out in an inert catalyst using a lithium catalyst or a Ziegler type catalyst.

The hydrogenation treatment of these block copolymers is carried out, for example, in Japanese Examined Patent Publication Nos. 42-8704 and 43-6636.
No. 45-20814, etc., in the presence of a hydrogenation catalyst in an inert solvent. In this hydrogenation, at least 50%, preferably 80% or more of the olefinic double bonds in the polymer block B are hydrogenated, and 25% or less of the aromatic unsaturated bonds in the polymer block A are hydrogenated. To be done.

These hydrogenated products are, for example, CX-1 under the trade name of "Kraton-G" from Shell Chemical Company.
It is sold under grade names such as 701 and C-1652.

<Molded Product> The paintable resin composition molded product of the present invention is required to have PPE near the surface,
The relative PPE content (X) in the vicinity of the surface represented by the following mathematical formula (D) is 3 or more, preferably 6 or more, more preferably 1
It is 0 or more.

[0051]

(Equation 3)

(In the formula, A ₁₁₈₉ and A ₂₈₃₉ are as follows. That is, the surface of the molded body is subjected to IRE (Internal Reflectance Ele) by the attenuated total reflection method (ATR method) of IR method.
ment) as Ge, incidence angle of 45 degrees, the resolution is measured under the conditions of 2 cm ^-1, represents the absorbance of the peak of 1189cm ^-1 in A _1189, the absorbance peak of 2839cm ^-1 in A ₂₈₃₉₎
If the PPE relative content (X) near the surface is less than 3, sufficient coatability cannot be obtained.

The surface of the paintable resin composition molding of the present invention is a modified propylene-based polymer,
The relative occupancy ratio (Y) of the aromatic compound on the surface measured by A spectroscopy is 1 × 10 ⁻³ or less, preferably 5 × 10 ⁻⁴ or less. Surface relative aromatic compound occupancy (Y) is 1 ×
If it exceeds 10 ^-3 , the amount of components other than the modified propylene-based polymer increases on the surface of the molded product, and the physical properties such as resistance to organic solvents deteriorate. Here, the relative occupancy ratio (Y) of the surface aromatic compound is calculated by the following mathematical expression (e).

[0054]

[Equation 4]

(In the formula, Shake up peak is a peak appearing at a binding energy of 6 to 7 ev higher than the main peak, and shows a peak attributed to aromatic carbon.)

That is, the paintable resin composition molding of the present invention has a structure in which the surface is a modified propylene polymer and a component having a high affinity for the paint such as PPE is present immediately inside. is there. The presence of PPE near the surface not only improves the paintability of PPE itself because it has a high affinity with the coating material, but it also has α, β having a hydroxyl group in component (a).
A high affinity with the polymer (G) of the unsaturated carboxylic acid ester and the aromatic vinyl compound, the (G) is exposed to the surface of the molded body, and is delaminated to form a physical property,
It is considered that the deterioration of the coating property is prevented and the component (G), which adversely affects the coating property due to the presence of (G) in the vicinity of the surface, is changed to a component effective for coating.

<Additional Components> The paintable resin composition molded product of the present invention may contain components other than the above components (a) to (c). For example, up to 80% by weight of component (a) can be used for other olefinic resins, such as unmodified olefinic resin, and up to 50% by weight of component (b) for other thermoplastic resins, such as PPE and PPE having hydroxyl groups. It may be replaced with a styrene resin soluble in water, a styrene resin soluble in PPE and having a hydroxyl group, or the like. 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. Further, organic and inorganic fillers such as glass fiber, mica, talc, wollastonite, potassium titanate, calcium carbonate and silica may be contained in an amount of 50% by weight or less, and a colorant dispersant may be included in an amount of 5% by weight or less. it can.

In order to further improve the coatability, a polymer having a hydroxyl group other than the component (a), such as Umex 1210 manufactured by Sanyo Kasei Co., a copolymer of propylene and undecenol, or Praxel 20 manufactured by Daicel Chemical Co., Ltd.
5% or the like may be contained in an amount of 30% by weight or less.

Furthermore, in order to further improve the mechanical properties, an impact strength improver is added, for example, a styrene-conjugated diene copolymer rubber, an ethylene-propylene- (diene) copolymer rubber, and Those α, β-unsaturated carboxylic acid anhydride modified products or modified products with unsaturated glycidyl esters or unsaturated glycidyl ethers, copolymers composed of unsaturated epoxy compounds and ethylene, or unsaturated epoxy compounds, ethylene and You may contain 5-30 weight% of copolymers etc. which consist of ethylenically unsaturated compounds. These additional components may be used alone or in combination of two or more. Also, such as polystyrene or PPE and polypropylene block or graft copolymers such as P
A compatibilizing agent for controlling the dispersed state of PE may be contained in an amount of 30% by weight or less.

<Composition Ratio of Constituents> In the present invention, the modified olefin resin as the component (a) and the PPE as the component (b) are used.
The mixing ratio of the components (a) and (b) is 100% by weight in total.
On the other hand, the modified olefin resin as the component (a) is 40 to
90% by weight, preferably 40 to 70% by weight. If the amount of the modified olefin resin is less than 40% by weight, the moldability and organic solvent resistance are inferior to those of the olefin resin, and if the amount of the modified olefin resin is more than 90% by weight, the heat resistance and the effect of improving rigidity are small and the coating property is low. There is a problem that it also decreases.

The mixing ratio of the partially hydrogenated aromatic vinyl compound-conjugated diene block copolymer of the component (c) is 1 to 4 relative to 100 parts by weight of the total of the components (a) and (b).
It is 0 part by weight, preferably 5 to 20 parts by weight. If the amount of the component (c) is less than 1 part by weight, the effect of improving the compatibility between the modified olefin resin of the component (a) and the PPE of the component (b) cannot be sufficiently obtained, resulting in delamination and delamination. Of the component (c) is reduced to 40%.
If it exceeds the weight part, the heat resistance, rigidity and organic solvent resistance of the composition may be deteriorated.

<Production of Paintable Resin Composition> As a melt-kneading method for obtaining the paintable resin composition used in the present invention, a kneading method which is generally used for thermoplastic resins can be applied. For example, powdery or granular components,
If necessary, after uniformly mixing together with the additives and the like described in the section of additional components by a Henschel mixer, ribbon blender, V-type blender, etc., kneading with a single-screw or multi-screw kneading extruder, roll, Banbury mixer, etc. can do. A solvent or the like may be used during kneading.

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

<Coating> The resin composition molded body of the present invention can obtain good paint adhesion without the need for primer coating or surface modification such as plasma treatment. It overturns the common knowledge that it is impossible to directly coat olefin resins. 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 of coating the resin composition molded body of the present invention, the conventional coating process can be omitted from the surface modification process such as primer coating and plasma treatment. 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.

[0067]

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: Preparation of 2-hydroxyethyl methacrylate / styrene modified polypropylene Homopolymer powder of propylene (JIS K 7210)
MFR: 1g / 10min, melting point: approx. 164
° C, hereinafter referred to as "PP-1") 2000 g, 2-hydroxyethyl methacrylate (hereinafter referred to as "HEMA")
100 g, styrene 100 g, and 1,3-bis (t-butylperoxyisopropyl) benzene (hereinafter referred to as “BPI
After mixing 10 g (referred to as "B") with a super mixer,
Twin screw extruder (manufactured by Japan Steel Works, trade name: TEX-30)
Type), cylinder temperature 180 ° C, screw speed 250 rpm, discharge rate 20 kg / hr, vent pressure 50 mm
Modified polypropylene (hereinafter referred to as "resin A") was obtained by kneading under reduced pressure under Hg conditions.

The resin A was press-molded and the contents of HEMA and styrene contained in the resin A were measured by the following method. Further, 1 g of Resin A was dissolved in 50 ml of boiling xylene, and then subjected to high-temperature centrifugation at 130 ° C. and 10,000 rpm for 1 hour, and the obtained xylene solution at 130 ° C. was poured into 200 ml of methyl ethyl ketone. Methyl ethyl ketone was removed and dried to obtain an ungrafted HEMA / styrene polymer. The deposited precipitate was recovered and the contents of HEMA and styrene were measured in the same manner. The molecular weight of each separated product was measured by GPC. Table 1 shows the above measured values and the values calculated based on the measured values.

1) Quantification of HEMA Infrared spectroscopy (IR method): A sample was press molded into a film, and the IR spectrum was measured. The quantification was 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): Sample 5
0 mg was dissolved in about 2 ml of o-dichlorobenzene by heating at 130 ° C., a sample was prepared using deuterated benzene as a standard substance, and ¹ H-NMR spectrum was measured. These two
The residual ratio of hydroxyl groups was calculated from the mathematical formula (f) using the ratio of the contents obtained by various measuring methods.

[0071]

(Equation 5)

2) Styrene (or α-methylstyrene)
Quantification was carried out based on the above IR spectrum.

3) MFR of the modified olefin resin is JI
It was measured at 230 ° C. according to SK 7210.

Reference Example 2: Production of HEMA / styrene-modified polypropylene HEMA 200 g, styrene 400 g, t-butyl peroxybenzoate (hereinafter referred to as "BPB") instead of BPIB.
Is used, and the discharge rate is set to 5 kg / hr,
A modified polypropylene (hereinafter referred to as "resin B") was obtained in the same manner as in Reference Example 1. The analysis results are shown in Table 1.

Reference Example 3: Production of HEMA / styrene-modified polypropylene 100 parts by weight of PP-1 was heated using a twin-screw extruder at a cylinder temperature of 180 ° C., a screw rotation speed of 250 rpm, a discharge rate of 3.3 kg / hr, and a vent pressure. When performing kneading under reduced pressure under the condition of 50 mmHg, a mixture of 40 parts by weight of styrene, 10 parts by weight of HEMA, and 1 part by weight of BPIB was added under pressure from the middle of the extruder cylinder to obtain a modified polypropylene (hereinafter referred to as "resin C"). Obtained. The resin C was treated and analyzed in the same manner as in Reference Example 1. The results are shown in Table 1.

Reference Example 4: Production of HEMA-modified polypropylene (for comparison) Modification was carried out in the same manner as Reference Example 3 except that styrene was not used and the discharge rate was 4.5 kg / hr. Polypropylene (hereinafter referred to as "resin D") was obtained. The results are shown in Table 1 after being analyzed in the same manner as in Reference Example 1.

[0077]

[Table 1]

Reference Example 5 (1) Production of Ethylene-Propylene-Divinylbenzene Copolymer A stainless steel autoclave having an internal volume of 100 liter and equipped with a stirring and temperature control device was sufficiently replaced with propylene, and then sufficiently dehydrated and deoxygenated. Then, 30 liters of n-heptane, 450 ml of divinylbenzene and 46 g of diethylaluminum chloride were added, and the temperature was raised to 55 ° C with stirring. Titanium trichloride (TT Toufer Co., TT
After adding 15 g of A-12) and raising the temperature to 60 ° C., the hydrogen concentration was maintained at 5% by volume, ethylene was supplied at 114 g / hr and propylene was supplied at 4.2 kg / hr, and copolymerization was carried out at 60 ° C. for 5 hours. . After completion of the copolymerization, the residual monomer was purged and the polymer slurry was filtered to obtain 16.1 kg of a copolymer (JIS K
MFR measured according to 7210: 4.93 g / 10 min, ethylene content: 2.59% by weight, divinylbenzene content:
0.27% by weight). This polymer has 4-methyl-2,6
-Di-t-butylphenol (0.05% by weight) was mixed and then granulated at 230 ° C with a single-screw extruder to obtain pellets.

(2) Production of styrene-modified copolymer In a stainless steel autoclave having an internal volume of 1150 ml equipped with a stirrer and a temperature controller, 495 ml of pure water, 9.9 g of tricalcium phosphate as a suspending agent and sodium dodecylbenzene sulfonate were added. 16 mg was added to make an aqueous suspension, to which ethylene having a particle size of 4 to 5 mm obtained in (1) above was added.
50 g of propylene-divinylbenzene copolymer particles were suspended by stirring. Separately, as a polymerization initiator, BPB
(Decomposition temperature to obtain a half-life of 10 hours: 104 ° C)
0.33 g, 0.25 g of α-methylstyrene dimer (manufactured by NOF CORPORATION) as a chain transfer agent was dissolved in 50 g of styrene, and this was added to the suspension, and the temperature inside the autoclave was raised to 90 ° C. , Hold at that temperature for 3 hours,
Propylene-containing styrene containing a polymerization initiator and a chain transfer agent
It was impregnated in a divinylbenzene copolymer. The temperature of this aqueous suspension was raised to 105 ° C., the temperature was maintained for 3 hours for polymerization, and the temperature was further raised to 135 ° C. for 3 hours to complete the polymerization. After cooling, the content was taken out, washed with water and dried to obtain 98.7 g of a particulate resin having a particle size of 5 to 6 mm (hereinafter referred to as "resin E").

The resin E was Soxhlet extracted with methyl ethyl ketone for 8 hours, and the polymer after extraction was subjected to 3
It was found to contain 8.7% by weight of styrene component. Moreover, when the molecular weight of polystyrene extracted with methyl ethyl ketone was measured by GPC, Mn in terms of polystyrene was calculated.
Was 26,000 and Mw was 85,000.

Examples 1 to 7 and Comparative Examples 1 to 4 Resins A to E obtained in Reference Examples 1 to 5 and polypropylene homopolymer (manufactured by Mitsubishi Petrochemical Co., Ltd., trade name: MA8, referred to as "PP"), And poly (2,6-dimethyl-1,4-
Phenylene ether) (manufactured by Nippon Polyether) having an intrinsic viscosity of 0.30 dl / g (expressed as "PPE H30") measured in chloroform at 30 ° C,
0.41 dl / g (expressed as "PPE H41") and 0.53 dl / g (expressed as "PPE H53"), and styrene-butadiene rubber (manufactured by Japan Synthetic Rubber Co., Ltd., trade name: TR2900, "SBR") and hydrogenated styrene-isoprene rubber (manufactured by Kuraray Co., Ltd., trade name: Septon 2104, referred to as "SIPR") having the composition shown in Table 2 and a 30 mm diameter twin-screw extruder (Japan Steel Works) The resin composition was obtained by kneading with TEX). An injection molding machine (IS55 manufactured by Toshiba Machine Co., Ltd.) was used to perform injection molding under the conditions of a cylinder temperature of 280 ° C. and a mold cooling temperature of 60 ° C. to prepare a test piece, and the test piece was evaluated by the following methods. Table 2 shows the results. The PPE relative content (X) near the surface and the relative aromatic compound occupancy ratio (Y) in the molded body were measured by the following methods, and the results are shown in the same table.

(1) Flexural modulus According to JIS K 7203, it was measured using an Instron tester. (2) Izod impact strength The notched Izod impact strength was measured using an Izod impact tester (manufactured by Toyo Seiki Seisakusho, Ltd.) according to ISO R 180-1969 (JIS K 7110).

(3) Coating test A coating test was conducted using a one-pack acrylic melamine-based paint and a two-pack 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.

Evaluation of paint adhesion: (i) Cross-cut test Vertically and horizontally 11 perpendicular to the surface of the test piece using a single-edged razor.
Draw 100 parallel lines at 2mm intervals to make 100 squares. Cellophane adhesive tape (JIS Z 1522) was sufficiently pressure-bonded on top of it, kept at about 30 degrees from the coating surface, and peeled off at once in front, observing the state of the part surrounded by the grid, and not peeled Recorded the number of. (Ii) Peel strength After a treatment to prevent the paint from adhering to the upper half of the test piece, each paint was applied to a coating film thickness of 100 μm and baked and dried. Cellophane adhesive tape (eg Nichiban width 24mm) is adhered to the entire surface of the test piece, and the width is 1cm.
Then, make a cut in the vertical direction to reach the substrate. Remove the side without the coating film by hand and attach it to the tensile tester 180
The load when peeled off at a speed of 50 mm / min in the direction of degree was recorded. In addition, when the coating film was ruptured, it was described as rupture.

(4) Measurement of relative content (X) of PPE near the surface An injection-molded sheet having a size of 75 mm × 75 mm and a thickness of 2 mm was used, and the measurement was carried out with an infrared spectroscope (Perkin Elmer, FT-IR) having a resolution of 2 cm ^−1. Spectrometer 1725X),
G as IRE (Internal Reflectance Element)
e, the sample surface was measured by the ATR method at an incident angle of 45 degrees, and X was calculated according to the mathematical expression (d).

(5) Measurement of relative occupancy ratio (Y) of aromatic compound on surface The surface of an injection-molded sheet having a size of 75 mm × 75 mm and a thickness of 2 mm was measured by ESCA-1000 manufactured by Shimadzu Corporation, and a mathematical expression (e) was used. Y was calculated according to

[0087]

[Table 2]

[0088]

As described above, the paintable resin composition molding of the present invention has the composition having the moldability and organic solvent resistance of an olefin resin, and the heat resistance and mechanical strength of PPE. Since the molded product has remarkably excellent coatability and printability without using a surface modifier such as a primer or an organic solvent such as trichloroethane, it has a wide range of uses and can be an industrially useful material. is there.

Claims (2)

[Claims] 1. A molded article of a resin composition containing the following components (a) and (b) in the following compounding ratio, the surface of the molded article being measured by an attenuated total reflection method (ATR method) of infrared spectroscopy. The relative content (X) of polyphenylene ether in the vicinity of the surface of the molded product measured is 3 or more, and the relative occupancy ratio (Y) of the aromatic compound on the surface of the molded product measured by ESCA spectroscopy is 1 × 10 ^-3 or less. A paintable resin composition molded article characterized by the above. (A) Modified propylene-based polymer obtained by subjecting a propylene-based resin to a graft copolymerization step of an α, β-unsaturated carboxylic acid ester having a hydroxyl group and an aromatic vinyl compound 90 to 40% by weight ( b) Polyphenylene ether 10 to 60% by weight 2. The resin composition comprises the following component (a):
The coatable resin composition molded article according to claim 1, which is a resin composition containing (b) and (c) in the following mixing ratio. (A) Modified propylene-based polymer obtained by subjecting a propylene-based resin to a graft copolymerization step of an α, β-unsaturated carboxylic acid ester having a hydroxyl group and an aromatic vinyl compound 90 to 40% by weight ( b) Polyphenylene ether 10 to 60% by weight (c) Partially hydrogenated aromatic vinyl compound-conjugated diene block copolymer 1 to 40 parts by weight based on 100 parts by weight of the total of components (a) and (b).