JPH03177404A - Preparation of modified ethylenic polymer - Google Patents

Abstract

PURPOSE:To prepare the subject polymer excellent in adhesivity to polyurethane coatings, also as excellent adhesives and foams by treating a specified ethylene- vinyl acetate copolymer, an organic compound, an organic peroxide, an organic tin compound, etc., at a specific temperature. CONSTITUTION:100 pts.wt. of ethylene-vinyl acetate copolymer having a copolymerized vinyl acetate content of 3.0-40wt.%, preferably 5.0-35wt.%, (preferably the copolymer having a melt flow index of 0.5-100g/10min), (B) 0.1-20 pts.wt., preferably 0.2-15 pts.wt. of an organic compound having a double bond and a hydroxyl group (e.g. 2-hydroxy-ethyl methacrylate), (C) 0.01-10 pts.wt. preferably 0.05-7 pts.wt. of an organic peroxide (e.g. ketone peroxide) and (D) 0.005-10 pts.wt., preferably 0.05-3 pts.wt. of an organic tin compound (e.g. monobutyl tin trimethyl maleate) and/or a tertiary amine compound are treated at 60-250 deg.C to provide the objective polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a modified ethylene polymer that has excellent adhesion to polyurethane. More specifically, the present invention relates to a method for producing a modified ethylene polymer that has good adhesion to polyurethane.

[Conventional Technique 11] 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. However, since it does not have a polar group in its molecule (it is so-called inert), it has poor adhesion to various substances. In particular, we will explain the adhesion with polyurethane resin.

Currently, exterior parts such as bumpers and bumper corners of automobiles are made of propylene-based polymers containing propylene as the main component, as well as ethylene-propylene copolymer rubber and inorganic fillers, in order to reduce the weight and cost of automobiles. Mainly, a composition containing talc) 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, in order to perform the two-layer coating process, it is necessary to use a large amount of an organic solvent (for example, toluene) as a solvent for the brimer, which poses problems in terms of working environment and air pollution.

In addition, by taking advantage of the insulation and cushioning properties of polyurethane foam, it is used as a cushioning material for interior parts of automobiles such as instrument panels, armrests, and seat backs, as well as for home appliances such as electric refrigerators and air conditioners, and refrigerated trucks. Used as a heat insulator. 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, the base material and surface material are metal, wood, and ABS.
In the case of resins with high surface activity such as acrylonitrile-butadiene-styrene ternary copolymer resin, they have excellent adhesion to polyurethane foam, so they cannot be used for injection as is done in the production of polyurethane foam. If the urethane polymer formation reaction and foaming are performed simultaneously on a base material using a method such as foaming, a product (laminate) with strong adhesion 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 have at least one unsaturated bond in their molecules and organic compounds containing hydroxyl groups (hereinafter referred to as "hydroxyl compounds").
A modified polyolefin resin (hereinafter referred to as "modified product (A)") obtained by treating at least an organic peroxide (hereinafter referred to as "modified product (A)") has been proposed for improving the adhesion with polyurethane paints and polyurethane foams. (For example, Japanese Patent Publication No. 58-154732, Japanese Patent Application Publication No. 58-1
No. 91706, No. 58-185344, No. 61-27
No. 2417).

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 with inorganic fillers, etc. not only have excellent adhesion to polyurethane even without applying a brimer, but also have good 1 flexural modulus and impact resistance at low temperatures, as well as processability and moldability. It has also been proposed in the past to be molded to be suitable for automobile exterior parts such as bumpers.
No. 2-209150, No. 62-207344, No. 62
-'257945).

Furthermore, compositions of the above-mentioned modified products and crystalline ethylene-propylene block copolymers, ethylene-vinyl acetate copolymers, etc., can be used at room temperature with chloroprene-based two-component solvent adhesives without applying a brimer. Not only does it have good adhesion, it also has excellent adhesion even at temperatures of 80°C, and it also has good flexural modulus and impact resistance, making it suitable for automobile interior parts (e.g. door liners). As previously proposed (Unexamined Japanese Patent Publication No. 6
No. 4-29446, No. 64-36636, No. 64-4
No. 5446, No. 64-48842, No. 64-7294
No. 6).

In addition, olefin polymers (low density polyethylene resin,
Copolymer with α-olefin mainly composed of ethylene,
Molded product of a mixture consisting of a high-density polyethylene resin, a propylene homopolymer, a block or random copolymer mainly composed of propylene with a small amount of ethylene and/or other α-olefins, a human mixyl compound, and an organic peroxide. A laminate consisting of a polyurethane foam and a molded product of an olefin polymer (polyolefin resin) mixture obtained by simultaneously carrying out a urethane polymer production reaction and foaming on the surface of the laminate has been improved in mutual adhesion. As previously proposed (
For example, JP-A-58-185244, JP-A-58-194
No. 834, No. 58-194835).

Furthermore, the present inventors have proposed a "modified ethylene polymer obtained by treating an ethylene-vinyl acetate copolymer, a hydroxyl compound, and an organic peroxide" [hereinafter referred to as "modified product (B)"] was previously submitted because it has superior adhesion to polyurethane paints and polyurethane foams compared to when non-polar polyolefin resins such as polypropylene resins are treated at the same time.

[Problem to be solved by the invention]

A modified product obtained by treating a polyolefin resin such as the polypropylene resin with at least a hydroxyl compound and an organic peroxide can improve adhesion to a polyurethane paint or polyurethane foam. However, in practical terms, the adhesion is not necessarily sufficient. In particular, the modified product may be added to the above-mentioned polypropylene resins (e.g. propylene homopolymer,
As mentioned above, when a composition with a crystalline ethylene-propylene block copolymer (crystalline ethylene-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 product (B) previously proposed by the present inventors is
Compared to the modified product (A) and its composition, the adhesion to polyurethane paints and polyurethane foams can be improved as described above. However, this modified product (B
), the adhesion cannot necessarily be said to be sufficient for practical use.

From these facts, the present invention has extremely good adhesion to polyurethane paints and polyurethane foams even without the use of a brimer, and can be applied to polypropylene resins such as ethylene-propylene block copolymers or polypropylene resins. When mixed with amorphous ethylene-propylene copolymer rubber, etc., not only does it have excellent adhesion to polyurethane paints and polyurethane foam without the use of a brimer, but it also improves flexural modulus (rigidity) and impact resistance. It has good mechanical properties such as
Moreover, it is an object of the present invention to produce a modified ethylene polymer that has excellent moldability and processability and can be used as a composition suitable for the exterior and interior parts of automobiles.

[Means and effects for solving the problems] According to the present invention, these problems are solved by (100% by weight of an ethylene-vinyl acetate copolymer in which the copolymerization ratio of Al-vinyl acetate is 3.0 to 40% by weight) (B) Organic compound having one double bond and one hydroxyl group (i.e. "hydroxyl compound J") 0.1 to 20 parts by weight, fcl organic peroxide o, ot-io weight Department as well.

(DJ organic tin compound and/or (E) tertiary amine compound 0.005 to 10 parts by weight at 60 to 250°C
The problem can be solved by a method for producing a modified ethylene polymer, which is characterized in that it is treated in the following manner. The present invention will be specifically explained below.

(Al ethylene-vinyl acetate copolymer The copolymerization ratio of vinyl acetate in the ethylene-vinyl acetate copolymer used in the present invention is 3.0 to 40% by weight, preferably 3.5 to 35% by weight, particularly 5.0 to 35% by weight is preferred. If the copolymerization ratio of vinyl acetate in the ethylene-vinyl acetate copolymer is less than 3.0% 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, the physical properties of the modified product and the composition when the composition is produced are deteriorated.

The melt flow index (measured according to JIS K7210 under conditions 4 in Table 1, hereinafter referred to as rMFRJ) of the ethylene-vinyl acetate copolymer is generally 0.
1 to 200 g/10 minutes, and 0.1 to 150 g/
10 minutes is preferred, especially 0.5 to io.

g/10 minutes is preferred. If an ethylene-vinyl acetate copolymer with an MFR of less than 0.1 g 710 min is used, not only will kneadability be poor when producing the following treatment by melt mixing, but the resulting modified product will not be mixed with polypropylene resin, etc. When producing the composition, crosstalk and moldability of the composition are poor.

On the other hand, if the time exceeds 200 g and 710 minutes, the mechanical strength is low.

(B) 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 represented by the following formula [(I) Formula 1].

( ]) In the formula, R9 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 (I), nl 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.

IcI Organic Peroxide Furthermore, the organic peroxide used in the present invention is generally used as an initiator in radical polymerization and as a crosslinking agent for polymers.

Preferably, the half-life of 1 minute is 0°C or higher, particularly preferably 110°C or higher. The above temperature is 10
If the temperature is lower than 0°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 l, l-
Ketone peroxides such as bis-tertiary-butylperoxy-3,3,5-1-limethylcyclohexane, dialkyl peroxides such as dicumyl peroxide, 2
．． Examples include hydroperoxides such as 5-dimethylhexane-2,5-hydroperoxide, diacyl peroxides such as benzoyl peroxide, and peroxy esters such as 2,5-dimethyl-2,5-dibenzoylperoxyhexane. .

(DiOrganotin compound) Also, examples of the organic tin compound used in the present invention include those represented by the following formula [(■) Formula J].

In the RJ Rs formula (II), R1, R4, R5 and R6 may be the same or different and are hydrocarbon groups having at most 12 carbon atoms, Y 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. xl is an oxygen atom, a sulfur atom, and a carboxylic acid group having at most 4 carbon atoms and a double bond; l is O or 1 to 2;
It is an integer of 0.

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

fEl Tertiary Amine Compound Furthermore, the tertiary amine compound used in the present invention is one that is used as a catalyst in the curing reaction of so-called urethane polyol and isocyanate. Typical examples include dimethylaminopropylamine, diethylaminopropylamine, tris(dimethylaminomethyl)phenol, tetraguanidine, N,N
- dibdel, ethanolamine, N-methyl-N, N-
jetanolamine, 1,4-diazabicyclo(2,2
,2) octane and 1,8-diazabicyclo(5,4
, O) -7 undecene.

fFl usage ratio In producing the modified ethylene polymer of the present invention, 1
The ratios of the hydroxyl compound, organic peroxide, organic tin compound, and tertiary amine compound to 00 parts by weight of the ethylene-vinyl acetate copolymer are as follows.

The proportion of the hydroxyl compound used is 0.11 to 20 parts by weight, preferably 0.1 to 15 parts by weight, particularly 2 to 2 parts by weight.
15 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 the amount exceeds 20 parts by weight, no improvement in adhesion will be observed depending on the amount used, and rather ethylene-
This is undesirable because it impairs the original properties of the vinyl acetate copolymer and unreacted hydroxyl compounds remain in the resulting modified ethylene polymer.

In addition, the usage ratio of organic peroxide is 0. 10 parts by weight, preferably 0.02 to 10 parts by weight, especially 0.02 to 10 parts by weight.
05 to 7.0 parts by weight is suitable. 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.

Furthermore, the mixing ratio of the organotin compound and the tertiary amine compound is 0,005 to 10 parts by weight as their total amount, and 0,02 to 5 parts by weight (IT preferable, especially 0,05 parts by weight). ~3 parts by weight is suitable.The mixing ratio of the organotin compound and the tertiary amine compound is 0 as the total amount.
, less than oos parts by weight, the effect is poor. On the other hand, even if it is added in an amount exceeding 10 parts by weight, the effect will not be improved and, on the contrary, it may cause adverse effects such as bleeding.

(G) Processing method To produce the modified ethylene polymer of the present invention, the above-mentioned ethylene-vinyl acetate copolymer, hydroxyl compound,
When producing a conventional modified olefin polymer using an organic peroxide, an organic tin compound, and/or a tertiary amine compound in the above-mentioned proportions, commonly used methods (e.g., solution method, suspension method) are used. This can be achieved by processing using any of the methods (turbidity method, melting method).

When producing modified ethylene polymers by solution method,
It can be produced by adding an ethylene-vinyl acetate copolymer and a hydroxyl compound and/or a tertiary amine compound to an inert organic solvent and thoroughly stirring the mixture at the temperature range shown below. . Examples of the inert organic solvent include hexane, heptane, toluene, xylene, and chlorobenzene. In this solution method, the treatment temperature varies depending on the type of organic peroxide and the type of ethylene-vinyl acetate copolymer, but is generally 60 to 120°C, particularly preferably 70 to 110°C.

In addition, when producing modified ethylene polymers by the suspension method,
Produced by adding the ethylene-vinyl acetate copolymer and hydroxyl compound to an aqueous suspension, then adding an organic peroxide, an organic tin compound, and a tertiary amine compound, and stirring thoroughly. be able to. In this case as well, the treatment temperature usually varies depending on the type of organic peroxide and ethylene-vinyl acetate copolymer, but the treatment temperature is usually 60°C.
~100°C. In both the solution method and the suspension method, if the treatment temperature is below the lower limit, if the treatment exceeds the lower limit, the treatment time M will be shortened, but a rapid reaction will occur, making the treatment difficult and resulting in poor denaturation. It is difficult to obtain things.

In any of the above cases, not only is the treatment time long, but post-treatment such as drying is required to completely remove the organic solvent and water used after treatment. be. This poses a cost problem. In contrast to these methods, the melting method, which requires a shorter treatment time and does not require post-treatment, is industrially desirable.

When producing modified ethylene polymers by the melt method, kneading machines such as Banbury mixers, kneaders, roll mills, and screw extruders (especially screw extruders) commonly used in the field of general synthetic resins are used. (preferable because of its simplicity) can be produced by melt-kneading. At this time, a more uniform modified ethylene polymer can be produced by tri-blending in advance using a mixer such as a Henschel mixer, and then melt-kneading the resulting mixture, or by performing melt-mixing two or more times. can. 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 processing temperature is generally 10
The temperature is 0 to 250°C, particularly preferably 120 to 230°C.

(H) Molding method The modified ethylene polymer obtained in this way is generally used in the field of polyolefin resins depending on the purpose of use, when producing the desired molded product by the molding method described below. Oxygen, heat and UV stabilizers, metal deterioration inhibitors, flame retardants, colorants, electrical property modifiers, fillers, antistatic agents, lubricants, processability modifiers and tack modifiers. Additives such as the like may be mixed as long as they do not impair the properties of the modified ethylene polymer of the present invention.

Furthermore, the mechanical strength of modified ethylene polymers, molding methods,
Synthetic resins or rubbers that can improve processability and are compatible with the modified ethylene polymer may be blended. This synthetic resin, which may be blended within a range that does not practically impair adhesion, includes low-density polyethylene resin, medium to high-density polyethylene resin, linear low-density polyethylene resin, propylene homopolymer, and propylene as a main component. A random copolymer with ethylene and/or an α-olefin having 4 to 12 carbon atoms,
A polymer obtained by block copolymerizing propylene as the main component with a small amount of ethylene, and a polymer obtained by block copolymerizing propylene with a small amount of ethylene. , its derivatives, vinyl esters, unsaturated carboxylic acid esters)
Examples include copolymers with Examples of the rubber include amorphous ethylene-propylene copolymer rubber, low-crystalline ethylene-propylene copolymer, and rubber containing butadiene as a main component.

Furthermore, the rigidity can be improved by adding a filler that is generally blended into synthetic resins and rubbers.

The modified ethylene polymer of the present invention or the above synthetic resin,
A desired molded article can be produced from a composition containing rubber, additives, etc. by a molding method commonly used in the field of olefin 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.

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, incyanate compounds, blowing agents, etc. used as raw materials for polyurethane foam do not need to be special materials, and may be any commonly used materials, and are not limited in any way. .

[Effect] Although the mechanism of the development of adhesiveness between the modified ethylene-based polymer 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 polymer obtained by the method of the present invention, a hydroxyl compound is bonded to the ethylene-vinyl acetate copolymer by the above treatment, and the hydroxyl group (-OH) of the compound is bonded to the isocyanate group of the polyurethane. As a result, strong adhesion is developed between, for example, polyurethane paints and molded articles of modified ethylene polymers.

In addition, engineered tyrene-vinyl acetate copolymers have superior wettability compared to polyolefin resins that do not have polar groups, such as polyethylene resins and polypropylene resins, so they can absorb isocyanate groups in polyurethane paints, for example. The compound having the hydroxyl group 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.

Furthermore, the organotin compound and/or tertiary amine act as a catalyst in the curing reaction between the polyol of the polyurethane resin and the incyanate compound, and furthermore, the hydroxyl group of the resulting modified ethylene polymer and the polyurethane paint It is thought that this promotes the reaction with the incyanate groups in the polyurethane foam, resulting in the development of strong adhesion between the layers.

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

In addition, 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 strokes/min. .

In addition, the ethylene-
The physical properties of the vinyl acetate copolymer, hydroxyl compound, organic peroxide, organic tin compound, tertiary amine, and low density polyethylene resin used for comparison are shown below.

[(A) Ethylene-vinyl acetate copolymer J As an ethylene-vinyl acetate copolymer, the copolymerization ratio of vinyl acetate is 6
．． Ethylene-vinyl acetate copolymer having a concentration of 2% by weight and an MFR of 19 g/l [hereinafter r E V A
(referred to as 11), the copolymerization ratio of vinyl acetate is 11% by weight
and has an MFR of 21 g/10 min.
Vinyl acetate copolymer [hereinafter rEVA (referred to as 21J), an ethylene-vinyl acetate copolymer in which the copolymerization ratio of 1 and vinyl acetate is 24% by weight, and an MFR of 20g/10 minutes [hereinafter referred to as 21J] % and MFR
Ethylene-vinyl acetate copolymer [EVAT41J] was used at a rate of 30 g/10 minutes.

[(B) Hydroxyl compound]

In addition, as a hydroxyl compound, 2-hydroxyl-ethyl-methacrylate (hereinafter referred to as rHEMAJ)
It was used.

[(C) Organic Peroxide 1 Furthermore, dicumyl peroxide (hereinafter referred to as rDCPJ) was used as an organic peroxide.

[(D) Low-density polyethylene resin 1 For comparison, a low-density polyethylene resin manufactured by a so-called high-pressure method has a density of 0.917 g/cm' and an MFR of 7.2 g/1 portion. A certain low density ethylene homopolymer (hereinafter referred to as rLDPEJ) was used.

[(E) Polypropylene Resin 1 For comparison, as a polypropylene resin, melt flow index (JIS K7210g/1
A propylene homopolymer (hereinafter referred to as rPPJ) with a temperature of 0.0 min was used.

[(F) Organic tin compound] Furthermore, dibutyl tin malate [hereinafter referred to as "compound + 1" J] and dibutyl tin laurate E hereinafter referred to as "compound (2)"] were used as organic tin compounds. .

[(G) Tertiary amine compound]

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

Examples 1 to 9, Comparative Examples 1 to 4 Ethylene-vinyl acetate copolymer, low density polyethylene resin (LDPE), or propylene homopolymer (PP) whose resin content is fm ff1l shown in Table 1
100 parts by weight of HEMA, the amount of which is shown in Table 1.
(2-hydroxyl-ethyl-methacrylate, as a hydroxyl compound), DCP (dicumyl peroxide, as an organic peroxide) and "organotin compound or tertiary amine compound" (hereinafter referred to as "compound"). 1 each using a souvenir mixer
Triblend was performed for 0 minutes. Each of the obtained mixtures was heated to 180 mm using a vented twin-screw extruder (diameter 40+am).
Pellets were produced while kneading at . Each of the obtained pellets was injection molded at a resin temperature of 160 to 170°C (210°C in the case of PP),
Flat specimen (thickness 2 mm, 120X 12
Onon) was created.

Each test piece thus obtained was coated with Miura type polyurethane paint (manufactured by Nippon B 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 60'C for 90 minutes. The coating film adhesion strength of each specimen thus obtained was measured. The results are shown in Table 1.

(The following is a blank space) [Effects of the invention] The modified ethylene polymer obtained by the method of the present invention has excellent adhesion with polyurethane paints even without the use of a brimer, and also has excellent adhesion with polyurethane adhesives and polyurethane foam. The adhesion is also good. Furthermore, by molding the composition obtained by blending these with various polyolefin polymers that have poor adhesion, and omitting steps such as coating and drying the resulting molded product, productivity can be improved. It is thought that the adhesion of the system to paints, adhesives and foams can be significantly improved.

The modified ethylene polymer obtained by the method of the present invention and the composition containing the modified ethylene polymer can be used in a wide variety of fields to exhibit the above-mentioned effects. Typical applications include car bumpers,
Examples include exterior parts such as bumper corners, interior parts such as instrument panels and door liners, and motorcycle parts such as fenders.

hand Continued Supplementary Positive 1( (spontaneous) 1. Display of incident 1999 Patent Application No. 315460 2. Name of the invention Method for producing modified ethylene polymer 3. Person who makes corrections Relationship to the case Patent applicant Address: Shiba Daimon-13, Minato-ku, Tokyo Name (200) Showa Denko Co., Ltd. Representative Murata 4. Agent (zip code 5) Residence: Shiba Daimon-13, Minato-ku, Tokyo Within Showa Denko Co., Ltd. No. 9 No. 9 5. Subject of correction The “Detailed Description of the Invention” column of the specification.

6. Contents of amendment + 11 On page 2, line 13 of the specification, the phrase "I will explain." should be replaced with "I will explain. J. I am making the amendment."

(2) On page 5, lines 19 and 20 (lines 2 and 1 from the bottom), the phrase ``previously'' has been amended to read ``previously.''

(3) On page 6, line 11 of the same page, the phrase "previously" has been amended to read "previously."

(4) On page 7, line 6 of the same page, replace “before” with “
We have corrected this to "previously."

(5) On page 7, line 15, the phrase "before" has been amended to read "before."

(6) On page 19, line 6 of the same document, the words "alteratically" have been amended to read "substantially."

(7) On page 28, line 11 of the same, "Nippon B Chemical" has been corrected to "Nippon B Chemical."

Claims (1)

[Scope of Claims] (A) 100 parts by weight of an ethylene-vinyl acetate copolymer having a vinyl acetate copolymerization ratio of 3.0 to 40% by weight; (B) having one double bond; 0.1 to 20 parts by weight of an organic compound having a hydroxyl group, (C) 0.01 to 10 parts by weight of an organic peroxide, and (D) an organic tin compound and/or (E) 0.00 parts by weight of a tertiary amine compound. 1. A method for producing a modified ethylene polymer, comprising treating 0.005 to 10 parts by weight at 60 to 250°C.