JPH04202449A - Propylene polymer composition - Google Patents

Abstract

PURPOSE:To improve the adhesion to a polyurethane resin by compounding a polypropylene and/or a specific propylene-ethylene random copolymer, an ethylene-propylene random copolymer, an ethylene-vinyl acetate copolymer, and a grafted ethylene-vinyl acetate copolymer. CONSTITUTION:95.0-60wt.% PP having a xylene solubles content at 30 deg.C of 5% or lower and/or propylene-ethylene random copolymer having an ethylene content of 10wt.% or lower (A) is compounded with 5.0-40wt.% ethylene- propylene random copolymer (B) having a xylene insolubles content at 30 deg.C of 5% or lower, a ratio of the wt.-average mol.wt. to the number-average mol.wt. (by gel permeation chromatography) of 10-100, and a propylene content of 30-75wt.% to give a polymer compsn. having a melt flow rate of 2.0-100g/10min. 100wt.% the compsn. is compounded with 5-50wt.% modified ethylene-vinyl acetate copolymer (C) which comprises an ethylene-vinyl acetate copolymer having a vinyl acetate content of 3.0-40wt.%, a grafted ethylene-vinyl acetate copolymer (D) obtd. by grafting an org. compd. having a double bond and a hydroxyl group onto C, and the org. compd. in an amt. of 0.01-20 pts.wt. based on 100 pts.wt. the sum of C and D.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a propylene polymer composition that has excellent adhesion to a polyurethane resin even without the use of a brimer.

[Prior art 1] 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, and
Because it has good properties such as tura property and straw resistance,
It is widely manufactured industrially and used in a wide range of applications, including parts and packaging materials for automobiles, electrical appliances, and electronic devices, various containers, and other daily necessities. However, because it does not have a polar group in its molecule (it is so-called inert), it does not have good adhesion to various substances. Among these, the adhesiveness with polyurethane resin will be explained.

Currently, exterior parts such as automobile bumpers and bumper corners have been made using propylene-based polymers with propylene as the bottom component, ethylene-propylene rubber, and inorganic A composition containing a filler (for example, Kuruk) is molded, and the molded product is subjected to electrical treatment (e.g., corona discharge treatment, plasma treatment),
The surface is subjected to surface treatments such as mechanical roughening, flame treatment, oxygen or ozone treatment, undercoated with a propylene-based polymer and a brimer with good adhesion, and then coated with a polyurethane-based paint. However, in the process of applying this brimer, generally after applying the brimer, the brimer 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.

In addition, polyurethane foam has insulation properties,
Due to its cushioning properties, it is used as a cushioning material for automobile interior parts such as instrument panels, armrests, and seat backs, and as a heat insulating material for home appliances such as electric refrigerators and air conditioners, and refrigerated trucks. When polyurethane foam is used in such fields, it is often necessary that the base material or surface material of the product and the polyurethane foam are in strong contact with each other. By the way, if the base material or surface material is a material with 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 substrate 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 brimer must be applied in advance to the surface of the polyolefin resin molded product as described above.

For these reasons, polyolefin resins are treated with an organic compound (hereinafter referred to as "hydroxyl compound") having at least one unsaturated bond in its molecule and containing a hydroxyl group, and at least an organic peroxide. A modified polyolefin resin [hereinafter referred to as "modified product (A)]" obtained by , 58-
No. 191706, No. 58-185344, No. 61-2
No. 72417).

Among polyolefin resins, modified products obtained by treating propylene polymers (polypropylene resins) in the same manner as above, crystalline ethylene-propylene block copolymers, amorphous ethylene-propylene copolymers, Compositions containing inorganic fillers and the like not only have excellent adhesion to polyurethane without the need for applying a brimer, but also have good flexural modulus and low-temperature impact resistance. Because it has excellent moldability, it has previously been proposed that it can be molded to be used as exterior parts of automobiles such as bumpers (for example, Japanese Patent Application Laid-open No. 119243/1983,
-209150, 62-207344, 62-
No. 257945).

Furthermore, compositions of the modified product fA) and crystalline ethylene-propylene block copolymers, ethylene-vinyl acetate copolymers, etc. can be used with chloroprene-based two-WIR type solvent adhesives without applying a primer. It not only has good adhesion 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 liners). It has been previously proposed to be compatible with JP-A Nos. 64-29446, 64-36636, 64-45446, 64-48842, 6
No. 4-72946).

Modified products (A) (low-density polyethylene resin, copolymer with a-olefin mainly composed of ethylene, high-density polyethylene resin, propylene homopolymer, small amount of ethylene and/or mainly composed of propylene) other α
- Polyurethane foams and modified products obtained by simultaneously carrying out a urethane polymer production reaction and foaming on the surface of a molded product (mixture consisting of a block or random copolymer with an olefin, a hydroxyl compound, and an organic peroxide) It has previously been proposed that a laminate consisting of the molded product (A) and the molded product have improved mutual adhesion (for example, JP-A-58-185244, JP-A-58-185244;
-194834, 58-194835).

Furthermore, some of the present inventors have proposed that ``ethylene-vinyl acetate copolymer can be obtained by treating ethylene-vinyl acetate copolymer with a hydroxyl compound and an organic peroxide, or with an organic tin compound and/or a tertiary amine compound. A modified ethylene polymer [hereinafter referred to as "modified product (B)"] has a higher adhesion to polyurethane paints and polyurethane foam than when non-polar polyolefin resins such as polypropylene resins are treated in the same way. I discovered that it was excellent and proposed it earlier (Japanese Patent Application Laid-Open No. 1-298).
No. 9410 and No. 1-315460).

[Problems to be Solved by the Invention] Polyolefin resins such as polypropylene resins contain a small amount of iAl, a modified product obtained by treating both hydroxyl compounds and organic peroxides. The adhesion can be improved. However, in practice, the adhesion is not always sufficient. In particular, the modified product fA) and the above-mentioned polypropylene resins (e.g., propylene homopolymer, crystalline ethylene- As mentioned above, when a composition with a propylene block copolymer (propylene block copolymer) etc. is molded into the exterior or interior parts of an automobile, and a polyurethane paint or polychloroprene adhesive is applied without applying a primer,
The adhesion with these materials is not always sufficient and there are problems in use.

Furthermore, the modified fB previously proposed by some of the inventors
) can improve the adhesion to polyurethane paints and polyurethane foams as described above compared to Al and its compositions. However, the modified product iBl has a lower rigidity (flexural modulus) However, it cannot be said that this is necessarily sufficient for practical purposes.

Based on these facts, the present invention has extremely good adhesion with polyurethane paints and polyurethane foam even without the use of a brimer, and also has a high flexural modulus (rigidity).
and 1ii- The purpose is to produce a composition that has good mechanical properties such as impact resistance, and has excellent moldability and processability, and is suitable for the exterior and interior parts of the above-mentioned automobiles. It is.

[Means for Solving the Problems] The present invention has been made to solve these problems, and the gist thereof is (A1) A propylene homopolymer having a xylene soluble content of at most 5% at a temperature of 30°C; /or a propylene-ethylene random copolymer with a copolymerization proportion of ethylene of at most 10% by weight, fil having a xylene insoluble content of at most 5% at a temperature of 30°C, determined by gel permeation chromatography Weight average molecular weight, which is an indicator of molecular weight distribution
Ethylene-propylene random copolymer having a number average molecular weight of more than 10 and less than 100, and a copolymerization ratio of propylene of 30 to 75%, and a copolymerization ratio of fcl vinyl acetate of 3.0 to 40%. The ethylene-vinyl acetate copolymer is grafted with a small amount of ethylene-vinyl acetate copolymer and a compound containing one (0)r double bond and a hydroxyl group [referred to as a "hydroxyl-based compound"]. Polymer [“
Modified ethylene-vinyl acetate copolymer] is a composition consisting of ethylene-propylene random copolymer in the total amount of propylene homopolymer, propylene-ethylene copolymer and ethylene-propylene random copolymer. The composition ratio of the polymer is 5.0 to 40% by weight, and the total MFR (melt flow rate) of these polymers is 2.0 to 100 g/10 min.
The ratio of the hydroxyl compound to 100 parts by weight of the total amount of the vinyl acetate copolymer and the modified ethylene-vinyl acetate copolymer is 0.01 to 20 parts by weight, and the proportion of the hydroxyl compound in the composition is 0.01 to 20 parts by weight. A propylene polymer composition, wherein the composition ratio of the ethylene-vinyl acetate copolymer as a graph of the polymer and the organic compound is 5 to 50% by weight as a total amount thereof.

It is. The present invention will be explained in detail below.

1A) - Propylene homopolymer and propylene-ethylene random copolymer The propylene homopolymer used in the present invention is obtained by homopolymerizing propylene.

In addition, the propylene-ethylene random copolymer is at most 10% by weight (preferably 9.0% by weight) of propylene.
Hereinafter, it is preferably obtained by copolymerizing ethylene (7.0% by weight or less).

Each of these propylene homopolymers and propylene-ethylene random copolymers contains at most 5% (preferably 3%) of components that are soluble in xylene at a temperature of 30°C. Furthermore, the MFR of these polymers is generally between 20 and 100 g/10 min;
A rate of 30 to 100 g/10 minutes is desirable, and a rate of 130 to 80 g/10 minutes is particularly preferred. If the MFR of the propylene homopolymer and propylene-ethylene random copolymer is less than the lower limit, there will be poor wire crosstalk and the moldability of the composition will be poor.On the other hand, if it exceeds the upper limit, the impact resistance of the composition I don't have good sex.

tBi ethylene-propylene random copolymer,
The copolymerization ratio of propylene in the ethylene-propylene random copolymer used in the present invention is 30 to 75% by weight, preferably 30 to 70% by weight, particularly 35% by weight.
~70% by weight is preferred. If an ethylene-propylene random copolymer with a propylene copolymerization ratio of less than 30% is used, the impact resistance of the composition will be poor. on the other hand,
Ethylene with an ethylene copolymerization ratio exceeding 75% by weight
Propylene random copolymers are not only difficult to manufacture, but also have low rigidity and problems in terms of shape retention and the like.

The ethylene-propylene random copolymer contains at most 5% by weight of components insoluble in xylene at a temperature of 30°C;
The content is preferably 4.5% by weight or less.

Furthermore, M of the ethylene-propylene random copolymer
FR is the above-mentioned propylene homopolymer and propylene-
For the same reason as in the case of ethylene random copolymers, 0. Old~5. Og/10 minutes, 002~3.0g
/10 minutes is preferable, especially 002~Lo g/lo
Minutes are suitable.

Further, the weight average molecular weight (Mw)/number average molecular weight (Mn), which is an index of molecular weight distribution measured by gel permeation chromatography of the ethylene-propylene random copolymer, is usually more than IO and less than 100, More than IO and less than 70 is suitable.

When M w /M n is less than IO or more than 100, manufacturing constraints occur.

These propylene homopolymer, propylene-ethylene random copolymer and ethylene-propylene random copolymer are each produced by homopolymerization or copolymerization, and when producing the composition of the present invention, or in advance, propylene homopolymer and /Or a brobylene-ethylene random copolymer and an ethylene-propylene random copolymer may be mixed, and this mixture and other composition components may be mixed in the composition ratios described below, or the propylene homopolymer and / or so-called blocks in which propylene-ethylene random copolymers are produced and ethylene and propylene are copolymerized in the same polymerization vessel or in separate polymerization vessels in the presence of these polymers and the catalyst system used for the production of the polymers. It may also be produced by copolymerization.

In any of the above cases, M of the total amount of propylene homopolymer and/or propylene-ethylene random copolymer and ethylene-propylene random copolymer
FR is 5.0-100 g/10 min, 10-7
0 g/lo min is preferred, particularly 10-50 g/710 min. Propylene homopolymer and/or propylene-ethylene random copolymer and ethylene-
MFR of the total amount of propylene random copolymer is 5.0
g/10 minutes, the crosstalk and the moldability of the composition are poor. On the other hand, if it exceeds 100 g/10 minutes, the mechanical properties of the composition, especially the impact resistance, will be poor.

In addition, the content of ethylene in the total amount of these polymers is generally 1.0 to 25% by weight, preferably 2.0 to 20% by weight, particularly 3.0 to 25% by weight, as a monomer unit.
20% by weight is preferred. The content of ethylene in the total amount of these polymers is 1.0% by weight as a monomer unit.
If it is less than 1, there is a problem in terms of impact resistance of the composition. on the other hand,
If it exceeds 25% by weight, there will be problems in terms of the rigidity of the composition.

fcl ethylene-vinyl acetate copolymer Modified ethylene-vinyl acetate copolymer may also be used as a component of the composition of the present invention.
The copolymerization ratio of vinyl acetate in the ethylene-vinyl acetate copolymer used to produce vinyl acetate copolymer is 30 to 40.
% by weight, preferably 3.5 to 35% by weight, especially 5% by weight.
．． 0 to 35% overlap is suitable. If the copolymerization ratio of vinyl acetate in the ethylene-vinyl acetate copolymer is less than 30% by weight, the adhesion to polyurethane paints and polyurethane foam will be low. On the other hand, when an ethylene-vinyl acetate copolymer with a molecular weight exceeding 40 is used, physical properties such as rigidity and impact resistance of the composition deteriorate.

The melt flow index of the ethylene-vinyl acetate i East combination [, J [According to S K7210, the conditions in Table 1 are 4 and 111 constant. J, hereinafter referred to as rMFR121J, is:
Generally it is 0.1 to 200g/10 minutes, and 0.1 to 1
50 g/10 minutes is desirable, especially 0°5-100
g/10 minutes is preferred. M F R (21 is 0.1
g/10 minutes or less when using an ethylene-vinyl acetate copolymer, when producing the following treatment by melt kneading,
Not only is the wire cross-mixing property poor, but also the kneading properties and moldability of the composition are poor when producing a single composition. Meanwhile, 200 g
/ If it exceeds 10 minutes, mechanical strength is low.

(0) Hydroxyl Compound Furthermore, the hydroxyl compound used to produce the modified ethylene-vinyl acetate copolymer of the present invention is an organic compound having one double bond and a hydroxyl group. The general formula of the hydroxyl compound is usually represented by the following formula [(I) Formula 1].

CI4□=C−R.

1 (I)0 =
C-0-R2-OH (In formula 11, R1 is a hydrogen atom or has 1 to 1 carbon atoms
There are 6 alkyl groups. Furthermore, R2 has 1 to 2 carbon atoms.
0 alkylene groups. In formula (1), R1 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and 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-methacrylate, and 2-hydroxy-ethyl-methacrylate.
Mention may be made of acrylate, 2-hydroxy-propyl-methacrylate and 2-hydroxy-methyl-methacrylate.

fEl organic peroxide Furthermore, the organic peroxide used in the production of the modified ethylene-vinyl acetate copolymer of the present invention is generally used as an initiator in radical polymerization and a crosslinking agent for polymers, and 1 Those with a half-life of 100° C. or more are preferred, and those with a half-life of 110° C. or more are particularly preferred. If the temperature is less than 100° C., it is not only difficult to handle, but also the effect of using it is not very noticeable, so it is not desirable. Representative examples of preferred organic peroxides include 1.1-bis-tert-butylperoxy-3,3,
Ketone peroxides such as 5-1-limethylcyclohexane, dialkyl peroxides such as dicumyl peroxide, hydroperoxides such as 2,5-dimethylhexane-2,5-hydroperoxide, diacylperoxides such as benzoyl peroxide. Mention may be made of oxides and peroxy esters such as 2,5-dimethyl-2,5-dibenzoyl peroxyhexane.

Although the modified ethylene-vinyl acetate copolymer of the present invention can be prepared by treating the ethylene-vinyl acetate copolymer with a hydroxyl compound and an organic peroxide, the modified ethylene-vinyl acetate copolymer may be further treated with an organic tin compound and/or a third compound as described below. The reactivity can be improved by adding a grade amine compound to the treatment.

fFl Organotin compound Examples of the organotin compound include those represented by the following formula [(H) Formula 1].

R, R5 + 1 ([1)YISn+X+
Sn←, Y2 R, R.

In formula (II), R3, R4, R5 and R6 may be the same or different and are hydrocarbon groups having at most 12 carbon atoms, ¥1 and Y2 may be the same or different,
These include monovalent or divalent carboxylic acids having at most 18 carbon atoms, derivatives (alkyl esters) of the carboxylic acids, alcohols, mercaptans, and mercapto acids. X is an oxygen atom, a 6M yellow frozen atom, and a carboxylic acid group having at most 4 carbon atoms and a double bond; 1 is O or an integer from 1 to 20;

Typical examples of these organic tin compounds include monobutyl tin trimethyl malate, dibutyl tin dilaurate, mixtures of dibutyl tin cimarate and dibutyl tin dimethyl maleate, dibutyl tin dioctyl maleate, and tribenzyl・Tin and trimethyl malate are listed.

fGl Tertiary Amine Compound Further, the tertiary amine compound is used as a catalyst in the curing reaction of so-called urethane polyol and incyanate.

Typical examples include dimethylaminopropylamine,
Diethylaminoprobylamine, tris(dimethylaminomethyl)phenol, tetraquanidine, N,N-dibutylethanolamine, N-methyl-N,N-jetanolamine, 1,4-diazabicyclo(2,2,2
+ octane and 1.8-diazabicyclo + 5.4.0
1-7 undecene is mentioned.

(Convenient proportions When producing the modified ethylene-vinyl acetate copolymer of the present invention by TA, the hydroxyl compound described in Aii, the organic peroxide, the organotin compound, and the The proportion of the tertiary amine compound used is as follows.

The proportion of the hydroxyl compound used is 0.1 to 20 parts by weight based on the total amount of the ethylene-vinyl acetate copolymer and the modified ethylene-vinyl acetate copolymer in order to contain a predetermined amount of the hydroxyl compound described below. .1-
15 parts by weight is preferred, and 0.2 to 15 parts by weight is particularly preferred.

The proportion of organic peroxide used is 0 to 10 parts by weight, preferably 0.02 to 10 parts by weight, particularly 0.0 to 10 parts by weight.
5 to 7.0 overlapping parts are suitable. The usage ratio of organic peroxide is 0. If it is less than part by weight, the effect of improving adhesion is low.

On the other hand, even if it is used beyond the 1-mouth overlapping part, not only the adhesion cannot be further improved, but also the ethylene-vinyl acetate copolymer itself may be crosslinked, which is not preferable.

Furthermore, when using an organic tin compound and a tertiary amine compound, the mixing ratio thereof is at most 10 parts by weight as a total amount, preferably 5.0 parts by weight or less, particularly 0.05 to 10 parts by weight. It is preferably 3 parts by weight or less. 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, it may cause adverse effects such as bleeding.

II) Processing method To produce the modified ethylene-vinyl acetate copolymer of the present invention, the above-mentioned ethylene-vinyl acetate copolymer, a hydroxyl compound, an organic peroxide, or these together with an organic tin compound and/or a third When producing a normal modified olefin polymer using a grade amine compound in the above-mentioned usage ratio, any of the commonly practiced methods (for example, solution method, suspension method, (melting method)) This can be achieved by employing and processing

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-vinyl acetate copolymer by the melt method, kneading machines such as Banbury mixers, kneaders, roll mills, and screw extruders (especially screw It can be produced by melt-kneading using an extruder (preferable because it is simple). At this time, a more uniform modified ethylene-vinyl acetate copolymer is produced by tri-blending in advance using a mixer such as a Henschel mixer, and further melt-kneading the resulting mixture, and by performing melt-mixing two or more times. can do. Melting crosstalk must be carried out at a temperature at which the organic peroxide used decomposes. However, it goes without saying that the ethylene-vinyl acetate 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, especially
120-230°C is preferred.

Unreacted (ungrafted) hydroxyl compounds may remain in the modified ethylene-vinyl acetate 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-vinyl acetate copolymers are usually present. At this time, the ungrafted ethylene-vinyl acetate copolymer is used for producing the composition described later without being removed.

The ratio of the hydroxyl compound to 100 parts by weight of the total amount of the ethylene-vinyl acetate copolymer and the modified ethylene-vinyl acetate copolymer is 0 to 20 parts by weight, and 0.
0.02 to 15 parts by weight are preferred, particularly 0.1 to 10 parts by weight. If the ratio of the hydroxyl compound to 1'00 parts by weight of the total amount of the ethylene-vinyl acetate copolymer and modified ethylene-vinyl acetate copolymer is less than 0.4 parts by weight, the adhesion to the polyurethane resin will be poor. , even if it exceeds 20 parts by weight, no effect of improving adhesion depending on the proportion is observed.

The composition ratio of the ethylene-vinyl acetate copolymer and the modified ethylene-vinyl acetate copolymer in the composition is:
Their total amount is 5 to 50%, and 1O to 4
5% by weight is desirable, particularly 15 to 40% by weight.

If the total amount of the ethylene-vinyl acetate copolymer and the ethylene-vinyl acetate copolymer grafted with the organic compound in the composition is less than 5% by weight, there will be problems in adhesion to polyurethane. On the other hand, when the content exceeds 50%, the flexural modulus of the resulting composition decreases significantly.

Production of fJ1 Composition The propylene polymer composition of the present invention is a modified ethylene polymer composition containing the propylene homopolymer and/or propylene-ethylene random copolymer, ethylene-propylene random polymer, and ethylene-vinyl acetate copolymer. It can be produced by uniformly mixing vinyl acetate copolymers within the above composition ratio range.

When producing the composition of the present invention, depending on the purpose of use, stabilizers against oxygen, heat and ultraviolet rays, metal deterioration inhibitors, W retardants, colorants, electricity, etc. commonly used in the field of polyolefin resins are used. property improvers, fillers,
Additives such as antistatic agents, lubricants, processability improvers, and tackiness improvers may be mixed as long as they do not impair the properties of the modified ethylene polymer of the present invention.

The compositions of the present invention may be prepared by tri-blending using mixers such as Henschel mixers, or by melt-melting using mixers such as Banbury mixers, kneaders, roll mills, and screw extruders. It is possible to mix wires. At this time, a more uniform composition can be obtained by tri-blending in advance and further melt-kneading the resulting mixture, or by performing melt-blending more than once.

(2) 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. Molding methods include injection molding, extrusion molding, blow molding, stamping molding, compression molding, and vacuum molding.

By applying a polyurethane paint to the thus obtained molded body using a commonly used method, a molded body whose surface is coated with polyurethane can be obtained. 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.

In order to achieve close contact, no special equipment or special method is required. That is, foaming methods such as injection foaming, mold foaming, and spray foaming that are commonly used in the field of polyurethane foam production may be applied. 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.

[Effect 1] Although the mechanism of the development of adhesiveness between the propylene polymer composition obtained by the method of the present invention and polyurethane is not clear, it is presumed that the mechanism of action is as follows.

In the modified ethylene-vinyl acetate copolymer in the propylene-based polymer composition obtained by the method of the present invention, a hydroxyl-based compound is bonded to the ethylene-vinyl acetate copolymer by the above-mentioned treatment, and the hydroxyl group that the compound has (
-OH) and the isocyanate group of polyurethane, a strong adhesive force is developed between, for example, a polyurethane paint and a molded article of a modified ethylene-vinyl acetate copolymer.

In addition, ethylene-vinyl acetate copolymers have superior wettability compared to, for example, polyethylene resins and polypropylene resins (polyolefin resins that do not have polar groups), so they can be used for example in cyanate groups in polyurethane paints. The compound possessing the copolymer is easily accessible to the surface of the copolymer, and the rate of reaction between isocyanate groups and hydroxyl groups increases, resulting in stronger adhesion.

Furthermore, when organotin compounds and/or tertiary amines are used in the production of modified ethylene-vinyl acetate copolymers, they act as catalysts in the curing reaction between polyols and isocyanate compounds in so-called polyurethane resins. Furthermore, it promotes the reaction between the hydroxyl groups of the resulting modified ethylene polymer and the incyanate groups in polyurethane paints and polyurethane foams.

-It is thought that strong layer adhesion is developed.

[Examples and Comparative Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples.

In the Examples and Comparative Examples, the coating 1Ifi adhesion strength was determined by making a 1 cm wide stripe on a molded flat plate and measuring the 180 degree peel strength of the coating film at a tensile rate of 50 mm/min. Further, Izot impact strength was measured at a temperature of 23° C. with a notch according to ASTM D256. Additionally, the flexural modulus is ASTM
Measured according to 0790.

In addition, the propylene polymer used in Examples and Comparative Examples and the ethylene-vinyl acetate copolymer, hydroxyl compound, organic peroxide, organic tin compound, and tin compound used in the production of the modified ethylene-vinyl acetate copolymer were The physical properties of the tertiary amine are shown below.

[(A) Propylene polymer] The following polymer was used as the propylene polymer.

Only propylene was polymerized in a polymerization vessel using a Ziegler-Natsuta catalyst without using a solvent. Then, ethylene was supplied to this polymerization vessel to produce a random copolymer of ethylene and propylene. The obtained propylene-based polymer [hereinafter referred to as rPP(A)J] contains 75% by weight of a propylene homopolymer (totally insoluble in xylene at a temperature of 30 minutes at a MFR of 60 g/10 minutes) and a copolymer of ethylene. Ethyl-brobylene random copolymer with a polymerization ratio of 50% by weight (MFRfl, Ig/l).

Minutes, fully soluble in xylene at a temperature of 30°C, weight average fraction device/number average molecular weight, which is an indicator of molecular weight distribution measured by gel permeation chromatography, is 33
). The MFR of this PPfA) is 1
It was 3g/10 minutes. For comparison, propylene single hand coalescence [M F R20g/
1, hereinafter referred to as "rPPf old" was used for 10 minutes.

[(Former ethylene-vinyl acetate copolymer 1) Furthermore, as an ethylene-vinyl acetate copolymer, the copolymerization ratio of vinyl acetate is 6.2% by weight, and M F Rf2+ is 19
g/10 min of ethylene-vinyl acetate copolymer [
Hereinafter, rEVA (referred to as IIJ), the copolymerization ratio of vinyl acetate is 11%, and MFR (21 is 21g
/10 minutes of ethylene-vinyl acetate copolymer [r
The copolymerization ratio of 1 called EVAf21J and vinyl acetate is 24% by weight, and M F R (2) is 20g/
Ethylene-vinyl acetate copolymer with In content [hereinafter referred to as rE
An ethylene-vinyl acetate copolymer with a copolymerization ratio of VA (1 called 31J) and vinyl acetate of 35% by weight, and an MFR of 30 g/Il1 min [rEVA (under toss)
1 called 41J was used.

[(C) Hydroxyl-based compound 1 Furthermore, as a hydroxyl-based compound, 1, referred to as 2-hydroxyl-ethyl-methacrylate [hereinafter r)lEMAJ, was used.

[(D) Organic peroxide l Also, as an organic peroxide, dicumyl peroxide [
Hereinafter referred to as rDcPJ] was used.

[(E) Organotin compound 1 Furthermore, as an organic tin compound, dibutyl tin, malate [hereinafter referred to as "compound (1) 1" and dibutyl tin]
Tin laurate [hereinafter referred to as "compound (2)" 1] was used.

[(F) Tertiary amine compound 1 In addition, as a tertiary amine compound, 1,4-diazabicyclo[2,2,21 octane [hereinafter referred to as "compound (3)]
” was used.

[Manufacture of modified ethylene-vinyl acetate copolymer 1 Table 1 shows l-l1 types as the resin content. HEMA (2-hydroxyl-ethyl-methacrylate, as a hydroxyl compound), DcP (dicumyl peroxide, as an organic peroxide) and [organotin compound or tertiary amine compound] ] were each tri-blended for 10 minutes using a super mixer.

Each of the obtained mixtures was subjected to vented twin screw extrusion a! (Diameter 40m
m) at 180℃ while kneading pellets [
Modified ethylene-vinyl acetate coelectrolyte, hereinafter referred to as [modified EVA]
1 called J was manufactured. Table 1 shows the abbreviations of each modified EVA obtained.

Example 1-13. Comparative Examples 1 to 3 Propylene polymers and modified EVA or unmodified EVA whose types and amounts are shown in Table 2 were heated to a resin temperature of 210°C using a vented twin-screw extruder (diameter 30 mm). Beret (composition) while kneading in
was manufactured. Each of the obtained pellets was injection molded at a resin temperature of 210°C to form a flat specimen (thickness 2
mm, +20×120 mm1, specimens were prepared to measure Izot impact strength and flexural modulus.

A two-component polyurethane paint (manufactured by Nippon P Chemical Co., Ltd., trade name: R271,
Pure White) was sprayed evenly using a spray gun. Then, it was heated and dried at a temperature of 80° C. for 45 minutes. The coating film adhesion strength of each specimen thus obtained was measured. In addition, the Izot impact strength and flexural modulus of each of the test pieces were measured. The results are shown in Table 2.

(Bottom margin of toss) Table 1 "Effects of the Invention 1 The propylene polymer composition obtained by the method of the present invention has excellent adhesion to polyurethane paints even without the use of a brimer, and also has excellent adhesion to polyurethane paints. It also has good adhesion to the molding agent and polyurethane foam.
It improves productivity by omitting processes such as drying, and significantly improves adhesion to these polyurethane 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 two-wheeled parts such as fenders.

Claims (1)

Scope of Claims: (A) A propylene homopolymer having a xylene soluble content of at most 5% at a temperature of 30°C and/or a propylene-ethylene random copolymer having an ethylene copolymerization ratio of at most 10% by weight. (B) The xylene insoluble content is at most 5% at a temperature of 30°C, and the weight average molecular weight/number average molecular weight, which is an index of molecular weight distribution measured by gel permeation chromatography, is more than 10 and less than 100. ethylene with a propylene copolymerization ratio of 30 to 75% by weight.
Propylene random copolymer, (C) ethylene-vinyl acetate copolymer with a vinyl acetate copolymerization ratio of 3.0 to 40% by weight, and (D) containing one double bond and containing a hydroxyl group. A composition comprising the ethylene-vinyl acetate copolymer grafted with an organic compound that accounts for ethylene-propylene random in the total amount of propylene homopolymer, propylene-ethylene copolymer, and ethylene-propylene random copolymer. The composition ratio of the copolymer is 5.0 to 40% by weight, and the melt flow rate of these polymer compositions is 2.
．． 0 to 100 g/10 minutes, and the ratio of the organic compound to 100 parts by weight of the total amount of the ethylene-vinyl acetate copolymer and the ethylene-vinyl acetate copolymer grafted with the organic compound is 0.01 to 20 parts by weight. A propylene polymer composition in which the composition ratio of the ethylene-vinyl acetate copolymer and the ethylene-vinyl acetate copolymer grafted with the organic compound is 5 to 50% by weight in total. thing.