JPH04224846A - Propylene polymer composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. which adheres well to a polyurethane coating material or a polyurethane foam. CONSTITUTION:The title compsn. comprises a propylene homopolymer or an ethylene-propylene random copolymer contg. 10wt.% or lower ethylene units and an ethylene-unsatd. carboxylic ester copolymer grafted with a hydroxylated org. compd.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a propylene polymer composition that exhibits excellent adhesion to polyurethane resins even without the use of a primer.

0002

[Prior Art] As is well known, polyolefin resins (polypropylene resins, polyethylene resins) not only have excellent moldability, but also have excellent mechanical properties, heat resistance, solvent resistance, oil resistance, and chemical resistance. Because of their excellent properties, they are widely manufactured industrially and used in a wide variety of applications, including parts and packaging materials for automobiles, electrical appliances, and electronic devices, various containers, and other daily necessities. but,
Since it does not have a polar group in its molecule (it is so-called inert), it has poor adhesion to various substances. Of these,
Adhesion with polyurethane resin will be explained.

Currently, exterior parts such as bumpers and bumper corners of automobiles are made of propylene-based polymers containing propylene as the main component, ethylene-propylene copolymer rubber, and inorganic in order to reduce the weight and cost of automobiles. Molding a composition containing a filler (mainly talc),
The molded product is subjected to surface treatments such as electrical treatment (e.g. corona discharge treatment, plasma treatment), mechanical roughening, flame treatment, oxygen or ozone treatment, and is then undercoated with a primer that has good adhesion to propylene polymers. and coated with polyurethane paint. However, in the step of applying this primer, generally after applying the primer, the primer is completely adhered (baked). This process requires a long time (usually about 40 to 80 minutes). Moreover, a large amount of organic solvent (for example, toluene) must be used to perform the two-coating process, which poses problems in terms of working environment and air pollution.

[0004] Polyurethane foam is also used as a cushioning material for interior parts of automobiles such as instrument panels, armrests, and seat backs by taking advantage of its heat insulating and cushioning properties, and is also used in home appliances such as electric refrigerators and air conditioners. It is used as an insulator for products and refrigerated trucks. When polyurethane foam is used in such fields, it is often necessary that the polyurethane foam be firmly adhered to the base material or surface material of the product. By the way, if the base material or surface material has high surface activity such as metal, wood, or ABS resin (acrylonitrile-butadiene-styrene ternary copolymer resin), it has excellent adhesion with polyurethane foam. If the urethane polymer formation reaction and foaming are performed simultaneously on a base material using a method similar to injection foaming used in the production of polyurethane foam, a product with strong adhesion (laminate) can be obtained. . However, as mentioned above, it is impossible to manufacture a laminate with polyurethane foam using an inert polyolefin resin as a base material or surface material because the adhesiveness is extremely low. For this reason, when a polyolefin resin and a polyurethane foam are brought into close contact with each other, a primer must be applied in advance to the surface of the polyolefin resin molded product as described above.

For these reasons, polyolefin resins contain at least one double bond in the molecule and an organic compound containing a hydroxyl group (hereinafter referred to as "hydroxyl compound") and at least an organic peroxide. Modified polyolefin resin obtained by treatment [
Hereinafter referred to as "modified product (A)"] has been proposed for improving the adhesion with polyurethane paints and polyurethane foam (for example, JP-A-58-154732;
No. 58-191706, No. 58-185344, No. 61-272417). In addition, among polyolefin resins, propylene polymers (polypropylene resins)
A composition of a modified product obtained by treating in the same manner as above, a crystalline ethylene-propylene block copolymer, an amorphous ethylene-propylene copolymer, an inorganic filler, etc. can be used to form polyurethane without applying a primer. Not only does it have excellent adhesion with other parts, but it also has good bending modulus and impact resistance at low temperatures, and it also has excellent processability and formability, so it can be molded into bumpers and other automotive exterior parts. It has previously been proposed that the product be compatible with
No. 19243, No. 62-209150, No. 62-20
No. 7344, No. 62-257945).

Furthermore, the composition of the modified product (A) and a crystalline ethylene-propylene block copolymer, ethylene-vinyl acetate copolymer, etc. can be used as a chloroprene-based two-component mixed type solvent without applying a primer. It not only has good adhesion with adhesives at room temperature, but also has excellent adhesion at temperatures of 80°C, and also has good flexural modulus and impact resistance, making it suitable for automobile interior parts (e.g. , door liner) has previously been proposed (Japanese Patent Application Laid-open Nos. 664-29446 and 64-3).
No. 6636, No. 64-45446, No. 64-4884
No. 2, No. 64-72946). Furthermore, some of the present inventors have proposed that ``ethylene-vinyl acetate copolymers, hydroxyl compounds, and organic peroxides, or those obtained by treating them with organotin compounds and/or tertiary amine compounds, The adhesion of the "modified ethylene polymer" [hereinafter referred to as "modified product (B)"] to polyurethane paints and polyurethane foams is higher than that of nonpolar polyolefin resins such as polypropylene resins when similarly treated. We found that it is superior and proposed it previously (Japanese Patent Application Laid-open Nos. 1-298941 and 1-3)
No. 15460).

[0007]

[Problem to be Solved by the Invention] The modified product (A) obtained by treating a polyolefin resin such as the polypropylene resin with at least a hydroxyl compound and an organic peroxide has a high adhesion property with a polyurethane paint or polyurethane foam. It is possible to improve the characteristics. However, in practical terms, the adhesion is not necessarily sufficient. In particular, compositions of the modified product (A) with the aforementioned polypropylene resins (e.g., propylene homopolymer, crystalline ethylene-propylene block copolymer), etc., can be used as exterior and interior components of automobiles, as described above. Form into
If a polyurethane paint or a polychloroprene adhesive is applied without applying a primer, the adhesion with these paints is not always sufficient, which poses a practical problem. Furthermore, the modified product (B) previously proposed by some of the present inventors has improved adhesion to polyurethane paints and polyurethane foams as described above, compared to the modified product (A) and its composition. can be done. However, the modified product (B)
It cannot be said that the rigidity (flexural modulus) is necessarily sufficient for use.

Based on these facts, the present invention has extremely good adhesion to polyurethane paints and polyurethane foam without using a primer, and has excellent mechanical properties such as flexural modulus (rigidity) and impact resistance. is good,
Furthermore, the purpose is to produce a composition that has excellent moldability and processability and is suitable for the exterior and interior parts of automobiles.

[0009]

[Means for Solving the Problems] The present invention has been made to solve these problems, and its gist is that (A) the copolymerization ratio of propylene homopolymer and/or ethylene is at most 10% by weight. Propylene-ethylene random copolymer (hereinafter referred to as "propylene polymer"), (
B) A composition consisting of an ethylene-unsaturated carboxylic acid ester copolymer (hereinafter referred to as "modified ethylene-unsaturated carboxylic ester polymer") grafted with a hydroxyl compound; The ratio of the hydroxyl-based compound to 100 parts by weight of the copolymer is 0.01 to 20 parts by weight, and the composition ratio of the propylene-based polymer in the composition is 50 to 95% by weight as a total amount of propylene. based polymer composition. The present invention will be explained in detail below.

(A) Propylene polymer The propylene polymer used in the present invention is a propylene homopolymer and a propylene-ethylene random copolymer copolymerized with a small amount of ethylene. MF of the propylene polymer
R(l) is 2.0 to 100 g/10 minutes, and 3.0 to
80 g/10 min is preferable, especially 5.0 to 50 g/10
minutes is preferred. If a propylene polymer having an MFR of less than 2.0 g/10 minutes is used, the resulting composition will have poor moldability. On the other hand, if it exceeds 100 g/10 minutes, the resulting composition will have poor mechanical properties (for example, impact resistance). Further, the copolymerization ratio of ethylene in the propylene-ethylene random copolymer is at most 10% by weight, and 8.
The content is preferably 0% by weight or less, particularly preferably 6.0% by weight or less. If a propylene-ethylene random copolymer with an ethylene copolymerization ratio of more than 10% by weight is used, the resulting composition will have a low flexural modulus.

(B) Modified ethylene-unsaturated carboxylic ester copolymer The ethylene-unsaturated carboxylic ester copolymer used to produce this copolymer is a copolymer of at least ethylene and an unsaturated carboxylic ester described below. It is a polymer (including a multicomponent copolymer with a third comonomer). The copolymerization ratio of the unsaturated carboxylic ester in the ethylene-unsaturated carboxylic ester copolymer is 3.0 to 50% by weight, and 4.0% by weight.
~45% by weight is preferred, and 5.0~40% by weight is particularly preferred. The copolymerization ratio of unsaturated carboxylic acid ester is 3
．． If less than 0% by weight of ethylene-unsaturated carboxylic acid ester copolymer is used, the adhesion with polyurethane paints or polyurethane foam will be low; When coalescence is used, the physical properties of the modified product and the composition of the present invention are deteriorated. The melt flow index (measured according to JIS K7210 under conditions 4 in Table 1, hereinafter referred to as "MFR") of the ethylene-unsaturated carboxylic acid ester copolymer is generally 0.5 to 300 g/10 minutes. and 0
．． 5-200g/10 minutes is desirable, especially 0.5-200g/10 minutes
150 g/10 minutes is suitable. MFR is 0.5g/1
If the ethylene-unsaturated carboxylic acid ester copolymer is used for less than 0 minutes, not only will the kneading properties be poor, but also the kneading properties and molding of the composition will be poor when producing the composition of the present invention from the resulting modified product. I don't have good sex. On the other hand, 300g/10
If an ethylene-unsaturated carboxylic acid ester copolymer exceeding 100% is used, the mechanical strength will be poor.

The unsaturated carboxylic acid ester usually has 4 to 40 carbon atoms, and preferably 4 to 20 carbon atoms. Representative examples of unsaturated carboxylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, and alkoxyalkyl (meth)acrylate. The alkoxy group of the alkoxyalkyl (meth)acrylate has 1 to 8 carbon atoms (preferably 1 to 8 carbon atoms)
4) and the alkyl group has 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms). Representative examples of suitable alkoxyalkyl (meth)acrylates include methoxyethyl (meth)acrylate, ethoxyethyl (
Mention may be made of meth)acrylate and butoxyethyl (meth)acrylate. The third comonomer preferably has at most 20 carbon atoms (preferably 4 to 16 carbon atoms). Typical examples thereof include vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl piperate. The copolymerization proportion of the third comonomer is usually at most 10% by weight, preferably 5.0% by weight or less.

(C) Hydroxyl Compound The hydroxyl compound used in the present invention is an organic compound having one double bond and a hydroxyl group. The general formula of the hydroxyl compound is usually the following formula [(
I) Formula]

[Formula 1] In formula (I), R1 is a hydrogen atom or has 1 carbon atom
~6 alkyl groups. Also, R2 has 1 carbon number
~20 alkylene groups. In formula (I), R
1 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, particularly preferably a hydrogen atom, a methyl group, or an ethyl group. Further, R2 is preferably an alkylene group having 1 to 6 carbon atoms, and particularly preferably an alkylene group having 1 to 4 carbon atoms. Suitable hydroxyl compounds include 2-
Hydroxy-ethyl-methacrylate, 2-hydroxy-ethyl-acrylate, 2-hydroxy-propyl-
Mention may be made of methacrylate and 2-hydroxy-methyl-methacrylate.

(D) Organic peroxide Furthermore, the organic peroxide used in the present invention is generally used as an initiator in radical polymerization and a crosslinking agent for polymers, and has a half-life of 1 minute. 100
A temperature of 110°C or higher is preferred, and a temperature of 110°C or higher is particularly preferred. If the above temperature is less than 100℃,
Not only is it difficult to handle, but the effects of using it are not very noticeable, so it is not desirable. Representative examples of preferred organic peroxides include ketone peroxides such as 1,1-bis-tertiary-butylperoxy-3,3,5-trimethylcyclohexane, dialkyl peroxides such as dicumyl peroxide, , 5-dimethylhexane-2,5-hydroperoxide, diacyl peroxides such as benzoyl peroxide, and peroxyesters such as 2,5-dimethyl-2,5-dibenzoyl peroxyhexane. It will be done.

The modified ethylene-unsaturated carboxylic acid ester copolymer of the present invention can be prepared by treating the above-mentioned ethylene-unsaturated carboxylic ester copolymer with a hydroxyl compound and an organic peroxide, The reactivity can be improved by adding an organic tin compound and/or a tertiary amine compound to be described later.

(E) Organic tin compound Examples of the organic tin compound include those represented by the following formula [Formula (II)].

[Image Omitted] In formula (II), R3, R4, R5 and R6
may be the same or different and are hydrocarbon groups having at most 12 carbon atoms; Y1 and Y2 may be the same or different and are monovalent or divalent carboxylic acids having at most 18 carbon atoms; These are acid derivatives (alkyl esters), alcohols, mercaptans, and mercapto acids. X1 has an oxygen atom, a sulfur atom and a carbon number of at most 4
is a carboxylic acid group having double bonds, and l is 0 or an integer of 1 to 20. Typical examples of this organic tin compound include monobutyl tin trimethyl malate, dibutyl tin dilaurate, a mixture of dibutyl tin dimalate and dibutyl tin dimethyl maleate, dibutyl tin dioctyl maleate, and tribenzyl・Tin and trimethyl malate are listed.

(F) Tertiary amine compounds Furthermore, tertiary amine compounds are used as catalysts in the curing reaction of so-called urethane polyols and isocyanates. Typical examples include dimethylaminopropylamine, diethylaminopropylamine, tris(dimethylaminomethyl)phenol, tetraguanidine, N,N,-dibutylethanolamine, N-methyl-N,N,-diethanolamine, 1,4 -diazabicyclo(2,2,2)octane and 1,8-diazabicyclo(5,4,0)-7undecene.

(G) Usage ratio In producing the modified ethylene polymer of the present invention, the hydroxyl compound, organic peroxide, and organic tin compound are added to 100 parts by weight of the ethylene-unsaturated carboxylic acid ester copolymer. The ratio of the tertiary amine compound used is as follows. The proportion of the hydroxyl compound to be used is 0.1 to 20 parts by weight, preferably 0.1 to 15 parts by weight, particularly 0.2 to 1 part by weight, based on 100 parts by weight of the ethylene-unsaturated carboxylic acid ester copolymer.
5 parts by weight is preferred. If the proportion of the hydroxyl compound used is less than 0.1 part by weight, the effect of improving adhesion is insufficient. On the other hand, if it exceeds 20 parts by weight, no improvement in adhesion is observed depending on the amount used.

The proportion of the organic peroxide to be used is 0.01 to 10 parts by weight, preferably 0.02 to 10 parts by weight, particularly 0. 0.05 to 7.0 parts by weight are preferred. If the proportion of organic peroxide used is less than 0.01 parts by weight, the effect of improving adhesion is low. On the other hand, even if it is used in an amount exceeding 10 parts by weight, not only the adhesion cannot be further improved, but also the ethylene-vinyl acetate copolymer itself may be crosslinked, which is not preferable. moreover,
When using an organic tin compound and a tertiary amine compound, the mixing ratio thereof, either alone or in total, is at most 10 parts by weight per 100 parts by weight of the ethylene-unsaturated carboxylic acid ester copolymer. Yes, 5.
The amount is preferably 0 parts by weight or less, particularly preferably 0.05 to 3 parts by weight. Even if the total mixing ratio of the organic tin compound and the tertiary amine compound exceeds 10 parts by weight, the effect will not be improved and, on the contrary, adverse effects such as bleeding may occur.

(H) Treatment method To produce the modified ethylene-unsaturated carboxylic ester copolymer of the present invention, the above-mentioned ethylene-unsaturated carboxylic ester copolymer, hydroxyl compound, organic peroxide, or When producing a normal modified olefin polymer using these and an organic tin compound and/or a tertiary amine compound in the above-mentioned proportions, commonly used methods (e.g., solution method, suspension method, This can be achieved by processing using any method (melting method). Among these processing methods, the melt method is industrially desirable because of its short processing time and the need for no post-treatment (eg, removal of organic solvents and water).

When producing a modified ethylene-unsaturated carboxylic acid ester copolymer by the melt method, kneading machines such as Banbury mixers, kneaders, roll mills, and screw extruders, which are commonly used in the field of general synthetic resins, are used. In particular, it can be produced by melt-kneading using a screw extruder (preferably because it is simple). At this time, a more uniform modified ethylene-unsaturated carboxylic acid ester copolymer can be obtained by dry blending in advance using a mixer such as a Henschel mixer and then melt-kneading the resulting mixture, or by performing melt-kneading two or more times. A combination can be produced. Melt kneading must be carried out at a temperature at which the organic peroxide used is decomposed. However, it goes without saying that the ethylene-unsaturated carboxylic acid ester copolymer used must not deteriorate and the treatment must be carried out at a temperature that can be controlled. For these reasons, the treatment temperature is generally 100 to 250°C, particularly preferably 120 to 230°C.

[0022] Unreacted (ungrafted) hydroxyl compounds may remain in the modified ethylene-unsaturated carboxylic acid ester copolymer thus obtained. At this time, the hydroxyl compound is used in the production of the composition described later without being removed. Additionally, ungrafted ethylene-unsaturated carboxylic ester copolymers may be present. At this time, the ungrafted ethylene-unsaturated carboxylic acid ester copolymer is similarly used in the production of the composition described later without being removed.

(J) Composition ratio The composition ratio of the propylene polymer in the composition of the present invention is 50 to 95% by weight, preferably 50 to 90% by weight, particularly preferably 55 to 90% by weight. be. When the proportion of the propylene polymer in the composition is less than 50% by weight, the flexural modulus of the resulting composition is significantly reduced. On the other hand, if it exceeds 95% by weight, there is a problem in terms of adhesion to the polyurethane resin. Further, the ratio of the hydroxyl compound to 100 parts by weight of the modified ethylene-unsaturated carboxylic acid ester copolymer is 0.01 to 20 parts by weight, preferably 0.02 to 15 parts by weight, particularly 0.1 to 15 parts by weight.
10 parts by weight is preferred. If the ratio of the hydroxyl compound to 100 parts by weight of the modified ethylene-unsaturated carboxylic acid ester copolymer is less than 0.01 parts by weight, the adhesion to the polyurethane resin is poor. On the other hand, even if the amount exceeds 20 parts by weight, no effect of improving adhesion is observed depending on the proportion.

The proportion of the modified ethylene-unsaturated carboxylic acid ester copolymer in the composition is 5 to 50% by weight, preferably 10 to 45% by weight, and preferably 15 to 40% by weight. If the amount of the modified ethylene-unsaturated carboxylic acid ester copolymer in the composition is less than 5% by weight, there will be problems in adhesion to polyurethane. On the other hand, when the amount exceeds 50% by weight, the flexural modulus of the resulting composition decreases significantly.

(K) Manufacture of Composition The propylene polymer composition of the present invention is obtained by uniformly mixing the propylene polymer and the modified ethylene-unsaturated carboxylic acid ester copolymer in the composition ratio range described above. It can be manufactured by When producing the composition of the present invention, stabilizers against oxygen, heat and ultraviolet rays, metal deterioration inhibitors, flame retardants, colorants, electricity, etc., which are commonly used in the field of polyolefin resins, are used depending on the purpose of use. Additives such as physical property improvers, fillers, antistatic agents, lubricants, processability improvers, and tack improvers may be mixed as long as they do not impair the properties of the modified ethylene polymer of the present invention. It's okay.

The compositions of the present invention may be prepared by dry blending using mixers such as Henschel mixers, or by using mixers such as Banbury mixers, kneaders, roll mills and screw extruders. It may be melt-kneaded. At this time, a more uniform composition can be obtained by performing dry blending in advance and further melt-kneading the resulting mixture, or by performing melt-kneading two or more times.

(L) Molding method The propylene polymer composition obtained as described above can be produced into a desired molded article by a molding method commonly used in the field of polyolefin resins. Examples of the molding method include injection molding, extrusion molding, blow molding, stamping molding, compression molding, and vacuum molding. A molded product whose surface is coated with polyurethane can be obtained by applying a polyurethane paint to the molded product thus obtained using a commonly used method. Further, in order to adhere closely to the polyurethane foam, the urethane polymer formation reaction and foaming may be simultaneously performed on the surface of the molded product obtained as described above.

[0028] In order to achieve close contact, no special equipment or special method is required. That is,
Foaming methods commonly used in the field of polyurethane foam manufacturing such as injection foaming, mold foaming, and spray foaming may be used. Furthermore, the polyols, isocyanate compounds, blowing agents, etc. used as raw materials for polyurethane foam do not need to be special materials, and any commonly used materials may be used without any limitation.

[0029]

[Function] Although the mechanism of the development of adhesion between the propylene polymer composition obtained by the method of the present invention and polyurethane is not clear, it is presumed to be due to the following mechanism of action. The modified ethylene-unsaturated carboxylic acid ester copolymer in the propylene-based polymer composition obtained by the method of the present invention has a hydroxyl-based compound bonded to the ethylene-unsaturated carboxylic ester copolymer by the above-mentioned treatment. The hydroxyl group (−
By bonding the isocyanate group of polyurethane with OH), strong adhesion is developed between, for example, a polyurethane paint and a molded article of a modified ethylene-unsaturated carboxylic acid ester copolymer.

[0030] Ethylene-unsaturated carboxylic acid ester copolymers also have superior wettability compared to polyolefin resins that do not have polar groups, such as polyethylene resins and polypropylene resins, so they can be used in polyurethane paints, for example. The compound having an isocyanate group therein easily approaches the surface of the copolymer, and the rate of reaction between the isocyanate group and the hydroxyl group increases, resulting in stronger adhesion. Additionally, organotin compounds and/or
Alternatively, when tertiary amines are used in the production of modified ethylene-unsaturated carboxylic acid ester copolymers, they act as catalysts in the curing reaction between the polyol and isocyanate compound of the so-called polyurethane resin, and the resulting It is thought that stronger adhesion is developed because the reaction between the hydroxyl groups of the modified ethylene polymer and the isocyanate groups in the polyurethane paint or polyurethane foam is promoted.

[0031]

[Examples] The present invention will be explained in more detail with reference to Examples below. In the Examples and Comparative Examples, the adhesion strength of the coating film was determined by making a 1 cm wide stripe on a molded flat plate and measuring the 180°C peel strength of the coating film at a tensile rate of 50 mm/min. In addition, the Izod pincer strength is determined according to ASTM D256 with a notch.
Measurements were made at a temperature of 20°C. Additionally, flexural modulus was measured according to ASTM D790. In addition, the propylene polymer used in Examples and Comparative Examples, the ethylene-unsaturated carboxylic ester copolymer, hydroxyl-based compound, and organic peroxide used in the production of the modified ethylene-unsaturated carboxylic ester copolymer , the physical properties of the organic tin compound and the tertiary amine are shown below.

[(A) Propylene polymer] As a propylene polymer, a propylene homopolymer having an MFR (l) of 8.5 g/10 minutes [hereinafter referred to as "PP(a)"]
and propylene with an ethylene copolymerization ratio of 4.0% by weight and an MFR (l) of 8.0g/10min.
An ethylene random copolymer (hereinafter referred to as "PP(b)") was used.

[(B) Modified ethylene-unsaturated carboxylic acid ester copolymer] To produce this copolymer, as the ethylene-unsaturated carboxylic acid ester copolymer, the copolymerization ratio of ethyl acrylate was 11% by weight. Yes and M
An ethylene-ethyl acrylate copolymer (hereinafter referred to as "EEA(l)") having an FR of 20 g/10 minutes, a copolymerization ratio of ethyl acrylate of 23% by weight, and M
An ethylene-ethyl acrylate copolymer (hereinafter referred to as "EEA (2)") having an FR of 24 g/10 minutes, a copolymerization ratio of methyl methacrylate of 9.0% by weight, and an MFR of 18 g/10 minutes. A certain ethylene-methyl methacrylate copolymer [hereinafter referred to as "EMMA(a)"]
and methyl methacrylate copolymerization ratio is 20% by weight
and has an MFR of 21 g/10 min.
A methyl methacrylate copolymer [referred to as EMMA(b)] was used.

[(C) Hydroxyl compound] Furthermore,
2-hydroxyl-ethyl-methacrylate (hereinafter referred to as "HEMA") was used as the hydroxyl compound. [(D) Organic peroxide] Dicumyl peroxide (hereinafter referred to as "DCP") was also used as the organic peroxide. [(E) Organic tin compound] Further, as an organic tin compound, dibutyl tin malate [hereinafter referred to as "compound (l)"] and dibutyl tin laurate [
Hereinafter referred to as "compound (2)"] was used.

[(F) Tertiary amine compound] Also, as a tertiary amine compound, 1,4-diazabicyclo[
2,2,2]Octane [hereinafter referred to as "compound (3)"]
was used. [Production of modified ethylene-unsaturated carboxylic acid ester copolymer] To 100 parts by weight of EEA and EMMA whose types are shown as resin components in Table 1, HEMA, DCP and organic tin whose blending amounts are shown in Table 1 are added. The compounds or tertiary amine compounds were each dry blended for 10 minutes using a super mixer. Each of the obtained mixtures was passed through a vented twin-screw extruder (diameter 40 mm).
) was used to produce pellets [modified ethylene-unsaturated carboxylic acid ester copolymer] while kneading at 180°C. Table 1 shows the abbreviations of the obtained modified EEA and modified EMMA.

The propylene polymers and modified EEA, modified EMMA, or unmodified EEA and EMMA whose types and amounts are shown in Table 2 were heated using a vented twin-screw extruder (diameter 30 mm) to maintain the resin temperature. Pellets (composition) were produced while kneading at 210°C. Each of the obtained pellets was injection molded at a resin temperature of 210°C, and a flat specimen (2 mm thick, 120×
120 mm), and to measure Izod impact strength and flexural modulus. A two-component polyurethane paint (manufactured by Nippon P Chemical Co., Ltd., trade name: R271, Pure White) was uniformly sprayed onto each test piece thus obtained using a spray gun. Then, it was heated and dried at a temperature of 60° C. for 90 minutes. The coating film adhesion strength of each specimen thus obtained was measured. In addition, the Izod impact strength and flexural modulus of each of the test pieces were measured. Table 2 shows the results.
Shown below.

[0037]

[0038]

[Table 2]

[0039]

Effect of the invention: The propylene polymer composition obtained by the method of the present invention has excellent adhesion to polyurethane paints even without the use of a primer, and also has excellent adhesion to polyurethane adhesives and polyurethane foam. The quality is also good. As a result, it is possible to improve productivity by omitting steps such as applying a primer and drying the resulting molded product, and to significantly improve adhesion with these polyurethane-based paints, adhesives, and foams. The propylene polymer composition obtained by the method of the present invention can be used in a wide variety of ways to exhibit the above-mentioned effects. Typical applications include exterior parts such as automobile bumpers and bumper corners, interior parts such as instrument panels and door liners, and motorcycle parts such as fenders.

Claims (1)

[Claims] Claim 1: (A) propylene homopolymer and/or
or a propylene-ethylene random copolymer in which the copolymerization ratio of ethylene is at most 10% by weight; (B) an ethylene-unsaturated carboxyl group containing one double bond and grafted with an organic compound containing a hydroxyl group; The composition is composed of an acid ester copolymer, and the ratio of the organic compound to 100 parts by weight of the ethylene-unsaturated carboxylic acid ester copolymer grafted with the organic compound is 0.
01 to 20 parts by weight, and the composition ratio of propylene homopolymer and propylene-ethylene random copolymer in the composition is 50 to 95% by weight as their total amount.
A propylene polymer composition.