JPS5884840A - Method for producing modified polypropylene composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention is polyolefin or nylon.

The present invention relates to a method for producing modified polypropylene that has good adhesion to polar substances such as polyester, saponified ethylene-vinyl acetate copolymer, glass, and metals.

In general, polypropylene has good mechanical properties and transparency.

It is used in a wide range of fields because of its excellent moldability and hygienic properties, but it has the disadvantage of poor adhesion with polar substances because it is non-polar.

Numerous proposals have been made to improve this adhesiveness.
One such method is a method in which a polymer made of an unsaturated carboxylic acid or a derivative thereof is grafted onto polypropylene. Examples of methods for grafting include a method of reacting in a soft part of a solution (for example, Japanese Patent Publication No. 15422/1972), and a method of reacting in a slurry state (for example, Japanese Patent Publication No. 18144/1989).
No.), reaction in molten state: jj decision (for example, Special Publication No. 4)
3-27421) etc.

Among these methods, the method of reacting in a molten state using an extruder is advantageous because it is easy to operate, but the resulting modification results in unreacted monomers remaining in the liprovirene, and if the amount is large, 111 It has drawbacks such as insufficient adhesion and generation of bubbles during molding of sheets, films, blow molding, etc.

Therefore, methods such as the dissolution-reprecipitation method and the solvent extraction method (Japanese Patent Application Laid-open No. 54-99193) have been proposed as methods for removing unreacted residual substances, but these methods require the use of a large amount of solvent or poor solvent. In addition to the complicated operations,
The disadvantage is that the cost is high.

The present inventors previously investigated unreacted monomers remaining in modified polypropylene obtained by a melt-kneading method using unsaturated carbon alt or its derivatives. We conducted various studies on the removal method of - and found that by heating edible polypropylene obtained by melt-kneading at 60°C or higher, unreacted residual material was significantly reduced. It was discovered that the foaming phenomenon of
issue).

On the other hand, in order to improve the adhesion of modified polypropylene grafted with unsaturated carboxylic acids, a method has been proposed in which soft polymers such as low-density polyethylene and rubber substances are added (for example, Japanese Patent Publication No. 40112/1983). Endurance w454
-40113.

JP-A-52-80334, JP-A-53-16781). However, since a large amount of unreacted monomer remains in the modified polypropylene produced by the melt-kneading method,
Simply adding a soft polymer to this will hardly improve the adhesion.

On the other hand, the grafting rate of modified polypropylene produced by the melt-kneading method is generally low, and in order to increase the grafting rate and improve adhesion, a method of adding a rubber-like substance in advance and carrying out a melt-mixing reaction is proposed. have been submitted (for example, Japanese Patent Publication No. 55-5766, Japanese Patent Publication No. 55-18251). However, edible polypropylene produced by the above melt-kneading reaction with the addition of a soft polymer in advance also contains unreacted monomers. A large amount remains, and not only does it not have sufficient adhesion, but it also has the disadvantage of generating air bubbles when forming films, sheets, blow molding, etc.In addition, if a soft polymer is added in advance, Modified polypropylene obtained by melt-kneading will not have sufficient adhesion to polar substances unless it contains about 0.15 moles or more of unsaturated carboxylic acid even if it is sufficiently heated and deaerated.Unsaturated carboxylic acid If the graft content of the carboxylic acid is about 0.15% or more, heating and degassing can suppress foaming due to unreacted upper particles during molding immediately after heating, but unsaturated carmenic acid has strong hygroscopicity. If left for a long time, it will absorb moisture in the air and cause foaming during molding. A modified polypropylene with good Q-adhesion to substances has been desired.

The inventor's school has previously conducted various studies on a method for producing modified polypropylene that is easy to operate, inexpensive, has a low amount of unsaturated carboxylic acid by melt-kneading, and has good adhesion to polar substances. After heating the modified polypropylene obtained by the melt-kneading method at a temperature of 60°C or higher, 90 to 50 parts by weight of the modified polypropylene is added with 1 part of ethylene-α-olefin copolymer or low-density polyethylene.
It was discovered and proposed that a modified polypropylene composition with a low grafting amount of unsaturated carboxylic acid and good adhesiveness can be produced by mixing 0 to 50 parts by weight (Japanese Patent Application No. 140592/1983). Gansho 55-157
No. 023). Alternatively, by mixing 90 to 50 parts by weight of modified niethylene-α-olefin copolymer obtained by a melt-kneading method or 10 to 50 parts by weight of low-density ethylene, and heating the mixture at a temperature of 60°C or higher. discovered that it is possible to produce a modified l-lip-tetrapyrene composition with a low grafting amount of unsaturated carboxylic acid and good adhesion (Japanese Patent Application No. 55-140593).
No. 55-157024 L0 However, the modified polypyrene compositions produced by these methods also require severe adhesive conditions, i.e., the adhesive layer and the deposited layer are thin and are rapidly cooled after melt lamination. Under these conditions, the adhesive strength is still insufficient.

The present inventors have conducted various studies on a method for producing modified polypropylene that uses a melt-kneading method to produce a modified polypropylene that has a low graat content of unsaturated carmen #s and has even better adhesion to polar substances even under severe adhesion conditions. It was discovered that the intended purpose could be achieved by performing a staged heat treatment, and the present invention was achieved. That is, in the present invention, modified polypropylene obtained by melt-kneading a mixture of polypropylene, an unsaturated carboxylic acid or its derivative, and an organic peroxide is heated at 60°C.
After heat treatment at a humidity above, the modified propylene 9
This method of producing a modified polypropylene composition is characterized in that 5 to 50 parts by weight of an ethylene polymer is mixed with 5 to 50 parts by weight, melt-kneaded, and then heat-treated again at a temperature of 60° C. or higher.

The modified polypropylene composition obtained by the production method of the present invention is a modified polypropylene obtained by a melt-kneading method and simply heat-treated at a temperature of 60°C or higher, or a modified polypropylene obtained by simply adding an ethylene polymer to the modified polypropylene. , compared to both modified polypropylene heat-treated at a temperature of 60°C or higher and an ethylene polymer added, and modified polypropylene added an ethylene polymer and then heat-treated at a temperature of 60°C or higher. will be significantly improved. Regarding the effect of improving adhesion in the present invention, the mechanism of action cannot be clarified.
Modified meliptetrapyrene is heated at 60°C or higher,
Unreacted things! This is thought to be due to some kind of structural change as the - decreases.

The polypropylene used in the present invention is not particularly limited, and includes homopolypropylene, propylene-ethylene random copolymer, propylene-ethylene splitter copolymer, copolymer of propylene and α-olefin, and these. Mixtures, etc. are used.

In addition, examples of the unsaturated carboxylic acids used in the present invention include acrylic acid, methacrylic acid, maleic acid,
I, )! ruic acid, itaconic acid.

Derivatives of unsaturated carboxylic acids include acid anhydrides, esters, amides, acids, metal salts, etc., such as maleic anhydride, citraconic anhydride, itaconic anhydride, methyl acrylate, and methacrylate. Methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate.

Butyl methacrylate, glycidyl acrylate.

Glycidyl methacrylate, monoethyl maleate,! Leic acid diethyl ester, fumaric acid monomethyl ester, fumaric acid dimethyl ester, itaconic acid monomethyl ester, itaconic acid diethyl ester, acrylic acid.

Methacrylamide, maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-N, M-diethylamide.

maleic acid-ni-motuptilamide, maleic acid-M,
M-dibutylamide, 7-malic acid monoamide, 7-malic acid diacetate, 7-malic acid monoamide, 7-malic acid monoamide, 7-malic acid monoamide, 7-malic acid monoamide, 7-malic acid monoamide
M, H-diethylamide.

fumaric acid-y-motuptilamide, fumaric acid-y, m-
P-diptylamide, maleimide, M-butylmaleimide, N-phenylmaleimide, sodium acrylate, sodium methacrylate.

Potassium acrylate, potassium methacrylate, etc. can be mentioned. Among these, it is most preferable to use maleic anhydride.

The amount of unsaturated carboxylic acid #II to be added is not particularly limited, but is determined depending on the amount of unsaturated carboxylic acid added to polypropylene, and ultimately the amount of unsaturated carboxylic acid ms in the modified polypropylene composition. Usually 0.01 to 20 parts by weight per 100 parts by weight of polypropylene,
It is preferably added in an amount of 0.1 to 5 parts by weight.

Further, in the present invention, an organic peroxide is used to promote the reaction between polypropylene and unsaturated carboxylic acids. Examples of organic peroxides include benzoyl peroxide, laautetrayl peroxide, azobis-nitrile, dicumyl peroxide, α, α-bis(
-butylperoxydiisoprovir)benzene.

2,5-, dimethyl-2,5-di(t-butylperoxy), 2,5-dimethyl-2,5-di(1-
butylperoxy)hexine-3, di-t-butyl peroxide, cumene hydroperoxide, 1-butyl hydroperoxide, and the like. The amount of organic peroxide added is not particularly limited, but is usually 0.005 to 5 parts by weight, preferably 0.0005 to 5 parts by weight. 1 to 1 part by weight.

Furthermore, in the present invention, talc, calcium carbonate, gypsum, i! ! Fillers such as magnesium chloride.

Butylation and droxytoluene, butylation and do-tetracyanisole, tetrakis[methylene-3(3,5-di-t-
It may also contain a heat stabilizer such as butyl-4-hydoxy-7manyl propionate comethane, a weather stabilizer, a lubricant, an antistatic agent, a nucleating agent, a dye, an antiblocking agent, etc.

In the present invention, propylene, unsaturated carboxylic acids, and organic peroxide as shown above are thoroughly mixed in a tumbler, Henschel mixer, etc., and heated at a temperature above the melting point of polypropylene, generally above the melting point and below 280°C. The gelatinization reaction is performed by melt-kneading. The melt-kneading method is not particularly limited, and can be carried out using, for example, a screw extruder, a Banbury mixer, mixing rolls, etc., but a screw extruder is preferably used. The melt kneading temperature and time are convenient depending on the decomposition temperature of the organic peroxide used, but generally it is 160 to 280°C for 3 to 30 minutes, preferably 170 to 250°C for 1 to 10 minutes.
minutes is appropriate. Note that the melt-kneading may be performed in an inert gas stream.

In the present invention, the modified polypropylene produced as described above is heat-treated at a temperature of 60°C or higher, preferably 100°C or higher. If the heating temperature is below 60℃, de-
It takes a long time and is not practical. The upper limit of the heating temperature is not particularly limited, but it is preferably below the melting point of the modified polypropylene in order to prevent the modified polypropylene from fusing. The heat degassing means may be a conventionally known method, such as an aeration band type dryer, a material agitation type dryer, a fluidized bed dryer, or a flash dryer.

Bubble dryer 9 Paper can be made using a rotary dryer, a drum type dryer, a vacuum dryer, an infrared dryer, a far-infrared dryer, a microwave dryer, etc., but a hot air dryer is preferably used. be done. Note that the deaeration effect is further improved if heat drying is performed under reduced pressure.

The heat treatment time is not particularly limited, but if the heating temperature is low humidity and the modified propylene contains a large amount of unreacted monomers, it will take a long time; if the heating temperature is high and there are few unreacted monomers, It only takes a short time. Generally, it is preferable to heat and degas for 10 minutes to 10 hours, so that the amount of unreacted monomer becomes 0.1 mol % or less.

Next, in the present invention, an ethylene polymer is mixed with the modified polypropylene produced as described above. The ethylene polymer used in the present invention is, for example, a homopolymer of ethylene polymerized by a high-pressure method or a medium-low pressure method, or a polymerizable monopolymer of ethylene and other polymerizable monomers of 60% by weight or less, preferably 40% by weight or less. copolymers with ethylene and propylene, one type of α-olefin such as butene-1,3-methyl-butene-1, hexene-1,3-methyl-pentene-1,4-methyl-pentene-1, etc. Or a copolymer of two or more types, a copolymer of ethylene and a vinyl ester such as vinyl acetate or psepion vinyl, or a saponified product thereof, ethylene and acrylic, or methacrylic.

Unsaturated carmenic acids such as maleic acid or derivatives thereof,
For example, anhydrides, esters, amides, imides, succilides,
Copolymers with metal salts, etc., copolymers of ethylene with butadiene, dicyclopentadiene, ethylidene norbornene>abbreviated as conjugated or non-conjugated dienes, etc. ψ refers to a mixture of the above polymers. These polymers are oxidized and chlorinated.

Multiple modifications such as chlorosulfonation or grafting with an epoxy compound or a carboxyl group-containing compound may be performed. Among these, low density polyethylene, ethylene-propylene copolymer, ethylene-butene-
1 copolymers are preferably used. The ethylene polymer has a temperature of 0,1
A range of 501710 minutes is preferred.

The amount of the ethylene polymer in the modified polypropylene composition is 5 to 50 parts by weight based on 95 to 50 parts by weight of the modified polypropylene, preferably L<=9 parts by weight of the modified polypropylene.
The amount is 10 to 40 parts by weight relative to 0 to 60 parts by weight. If the amount of the ethylene polymer is less than 5 parts by weight, the effect of improving the binding property will be small, and if it exceeds 50 parts by weight, not only will the adhesion property decrease, but also the mechanical strength will decrease, which is not preferable. −.

Further, it is also possible to mix unmodified propylene in addition to modified polypropylene and ethylene polymer, and unmodified propylene in addition to ethylene polymer. The addition ratio of unmodified propylene is 100 to 5 IlL of modified propylene.
The amount is 0 to 95 parts by weight, preferably 10 to 90 parts by weight, based on 90 to 10 parts by weight of modified polypropylene.

Mixing of modified propylene, ethylene polymer or, if necessary, unmodified polypropylene is carried out in a tumbler,
This can be carried out using a Henschel mixer or the like, and the mixture is melt-kneaded using, for example, a screw extruder, a Banbury mixer, a mixing roll, or the like.

Next, the modified propylene composition obtained as described above is heat-treated again. The heat treatment method and conditions are the same as in the case of modified propylene in the first stage, and it is desirable that the heat treatment be performed so that the amount of unreacted monomer in the modified polypropylene composition is 0.05 mole or less. . However, in order to improve the adhesion of the resulting modified polypropylene composition, the above-mentioned unreacted components must be used! It is also preferable to perform a heat treatment of 8 or more to remove -.

The wheat-based polyp-pyrene composition of the present invention obtained by such two-stage heat treatment has significantly improved adhesion. In particular, the modified polypyrene composition of the present invention exhibits good adhesion even when the amount of unsaturated carboxylic acid is about 0.15 mol≦ or less, particularly 0.12 mol or less, which does not cause foaming during molding.

Therefore, the present invention provides a modified lipropylene composition with good adhesion that does not cause shrinkage or foaming during molding.

The modified polypropylene composition obtained in the present invention not only has good adhesion to unmodified polypropylene, but also has good adhesion to polar substances such as metals, glass, nylon, polyester, and saponified ethylene-vinyl acetate copolymers. Shows adhesion.

Therefore, for example, (1) polar resin/modified polypropylene composition/polypropylene, (2-modified polypropylene composition/polar resin/modified polypropylene composition/polypropylene, (3) polypropylene/modified polypropylene composition/ It is possible to provide a laminate of polar resin/modified polypropylene composition/polypropylene with good adhesion.

When these laminates are stretched, a composite stretched polypropylene film having excellent gas barrier properties, oil resistance, water impermeability and heat sealability is obtained.

The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.The various physical properties in this specification were measured by the following methods.

φ MIFI A8TM D 1238-52'l'l,: fs2
The paper was measured at 30° C. under a load of 21601.

・Amount of maleic anhydride A film with a paper thickness of approximately 0.1111 was formed using a hot press, the infrared lI @ absorption spectrum was measured, and the amount of maleic anhydride was determined from the absorption peak intensity of anhydrous!leic acid at 1780 cm. The amount of maleic anhydride (the amount of inic acid was taken as the amount of maleic anhydride in the sample obtained by extracting a film with a thickness of about 0.1 M for 6 hours with acetone and then vacuum drying at a temperature of 50°C for 24 hours). .

No residual water! The amount of rhein was determined by subtracting the amount of reacted maleic anhydride (graph) from the total amount of maleic anhydride.

・Adhesive strength: For adhesion with saponified ethylene-vinyl acetate copolymer, N-4, and polyethylene terephthalate, co-extrude the two, cool and solidify, then cut into pieces with a diameter of 2 cm in the longitudinal direction.
Peel strength was measured.

・4c) TSL extruder with tensile modulus L/D-20 is equipped with a T-die and extruded into a sheet with a thickness of 0.511 ff at 200p, and the obtained sheet is cut into strips with a width in the MD force direction of IC11. The distance between the chucks is 501
．． A tensile test was conducted at a tensile speed of 20 M/min, and the tensile modulus was calculated from the initial slope.

Examples 1 to 6 and Comparative Examples 1 to 3 M71-o, sf/lo content, 100 parts by weight of a propylene-ethylene random copolymer with an ethylene content of 2.0 parts by weight, 2 parts by weight of anhydrous maleic glass, 2.5 parts by weight -dimethyl-2,5
- 0.3 parts by weight of di(1-butylperoxy)hexane,
0.1 part by weight of butylated hydroxysilene (maIll) and 1 part by weight of calcium stearate O0 were mixed for 5 minutes in a Henschel mixer, and melt-mixed pelletization was performed at 220 °C using a 4゛0 cod f extruder with L/D = 24. MytX-75, 3 f/10 min, total anhydrous Yk4 #M0920 mol, graft reaction maleic anhydride amount 0
．． Modified propylene (hereinafter also abbreviated as modified PP) containing 485 mol % and an amount of unreacted maleic anhydride of 0.435 mol was obtained. Next, heat treatment was performed at 1415° C. for 4 hours using a constant temperature dryer (hereinafter referred to as first-stage heat treatment) to obtain heat-treated modified polypropylene. This heat-treated modified polypropylene had MνX-52, 7 f/10 minutes, total maleic anhydride amount was 0.527 mol, gelafushi reaction maleic anhydride amount was 0.475 mol, and unreacted maleic anhydride (leic acid was 0.052 mol). It was mol%.

Furthermore, 15 parts by weight of the first heat-treated modified PP was added with M? in the proportion shown in Table 1. X-4, OI 710 min unmodified homopolypropylene, ethylene content 80 wt-, MP!
-6,4f 710 minutes of ethylene-butene-1 random copolymer was mixed, melt-kneaded and pelletized at 220℃ using L/D-24 40 tap extrusion, and then heated in a constant temperature dryer at 19145℃ for 4 hours. Treatment (hereinafter also referred to as second-stage heat treatment) was carried out to obtain a modified 1-lipropylene composition.

Mv engineering of the obtained modified polypropylene composition.

Table 1 shows the relationship between the maleic anhydride content, saponified ethylene-vinyl acetate copolymer (hereinafter also referred to as silicified mv), paper adhesion strength, and tensile elasticity. The adhesive strength with the saponified ethylene-vinyl copolymer was determined as follows. That is, the modified polypropylene composition II/D
A saponified ethylene-vinyl acetate copolymer (MF Eny 4111O
min, ethylene content 25 mol%, saponification degree 99 or higher) L / D = 24 of 30111 / extrusion mode to 210
Co-extruded at ℃! - Extrusion through a die, thickness of modified polypropylene composition 0.2M.

Thickness of saponified ethylene-vinyl acetate copolymer: 0, 11
A coextruded sinite of fil was molded and the T-peel strength was measured. Note that these modified polypropylene compositions did not foam during molding even when left for a long period of time. Comparative Example 4 Except for the fact that the first heat treatment was carried out for 8 hours in the Example Tei, and the second heat treatment was not carried out. The same procedure as in Example 3 was carried out.

The obtained modified polypropylene composition (DM?I-6,4
#710 minutes, total maleic anhydride amount is 0.076 mol,
The amount of graft-reacted maleic anhydride was 0.060 mol≦, the amount of unreacted maleic anhydride was 0.016 mol, and the adhesive strength with the saponified rubber was 3001/2611.

Comparative Example 5 The same procedure as in Example 3 was conducted except that the first heat treatment was not performed and the second heat treatment was performed for 8 hours. The obtained modified polyp V pyrene composition (D M IF
X -6,71710 minutes, completely anhydrous! The amount of leic acid is 007
4 mol≦, the amount of maleic anhydride in the graft reaction is 0.059
The amount of unreacted maleic anhydride was 0.015 mol≦, and the adhesive strength with the saponified aluminum Vum was 800 f/10 minutes.

Comparative Example 6 The same procedure as in Example 3 was carried out except that neither the whiplash heat treatment nor the second heat treatment was performed. 1
0 minutes, the amount of total maleic anhydride 11 was 110.135 mol, graph) The amount of reacted maleic anhydride was 0.068 mol, and the amount of unreacted maleic anhydride was 0.067 mol. The intensity was 0. Also, foaming occurred during molding.

Example 7 Homogiri propylene 100 in x-o, sf/10 minutes
Part by weight, 0.5 part by weight of Anhydrous Malein Fist.

11 parts by weight of Cytamyl peroxy FO, 1 part by weight of BITo, and 0.1 part by weight of calcium stearate were mixed for 5 minutes in a Henshi luminescent mixer, and 40 parts by weight of xA/D-24
Melt-kneading pelletization was carried out at 250° C. using an M# extruder. M of the resulting modified propylene 71-7.5
1710 minutes, completely anhydrous! The amount of leic acid is 0.203 moles,
The amount of graft-reacted maleic anhydride was 0.079 mol, and the amount of unreacted maleic anhydride was less than 0.124 mol.

This modified Boripudapyrene was dried using a constant temperature air dryer for 15 minutes.
Heat treatment at 5℃ for 3 hours (hereinafter referred to as first stage heat treatment)
did. MF Aero of the heat-treated modified polypropylene obtained, 4F/10 minutes, total maleic anhydride amount is 0.108 mol, graft reaction maleic anhydride amount is 0.074 mol≦, unreacted anhydride! The amount of leic acid was 0.034 mol%.

Next, 20 parts by weight of an ethylene-propylene random copolymer with an ethylene content of 70 parts by weight and a MF construction of 5.3 f/10 minutes was mixed with 80 parts by weight of the heat-treated modified poly(a-pyrene), and L/D-24 The mixture was melt-kneaded and pelletized at 220°C using a 40-yatl extruder, and heat-treated at 155°C for 3 hours using a constant-temperature dryer (hereinafter also referred to as second-stage heat treatment) to obtain a modified polypyrene composition. Ta.

MFI-6 of the obtained modified polypropylene composition, 1 weight 710 minutes, total maleic anhydride amount is 0, oso mole, graft reaction maleic anhydride amount is 0.058 mol, unreacted maceanic anhydride is 0 It was a whisper of .022 mole. This modified polypyrene composition L/D = 4 of 20
From the 0flψ extruder at 210°C, the nylon 6 was
/ D-24-3 (each coextruded from a BJ5' extruder at 250 °C! - Coextruded through a die, the thickness of the modified propylene composition layer was 9.21 ff, and the thickness of the 6 layers of Nai-4 was 0.1 ff) A coextruded sheet was molded.The adhesive strength was 41001/2 Cva.

Comparative Example 7 The same procedure as in Example 7 was conducted except that the first heat treatment was carried out for 6 hours and the second heat treatment was not performed.

M1 Aero of the obtained modified polypropylene composite, (1
10 minutes, completely waterless! The amount of leic acid is 0.079 molar arc, and the graft reaction is anhydrous! The amount of leic acid was 0.056 mol%, the amount of unreacted maleic anhydride was 0.023 mol%, and the adhesive strength with Naidan 6 was 2300 f/2 cm.

Comparative Example 8 The same procedure as in Example 7 was conducted except that the first heat treatment was not performed and the second heat treatment was performed for 6 hours. MIF x-6 of the resulting modified l-lipropylene composition
, 31710 minutes, total amount of maleic anhydride 0.082 mol-
The amount of graft-reacted maleic anhydride was 0.060 mol %, the amount of unreacted maleic anhydride was 0.022 mol %, and the adhesive strength with nylon 6 was 2700172 cm.

Comparative Example 9 The same procedure as in Example 7 was conducted except that neither the first heat treatment nor the second heat treatment was performed. The obtained modified polypropylene was subjected to MIFX-7,5F/10 minutes, the total amount of maleic anhydride was 0.152 mol, the amount of graft-reacted maleic anhydride was 0.062 mol, the amount of unreacted maleic anhydride was o, oso mol. The adhesive strength with Knife 6 was 0. Also, foaming occurred during molding.

Comparative Example 1G MIF I = 0.5 f/10 minutes, 80 parts superimposed of pyrene, ethylene content 70% by weight, MFN-5
, 3F/1 (l) 20 parts by weight of ethylene-propylene random copolymer, 0.3 parts by weight of anhydrous maleic #, 1 part by weight of diluted rubber oxide O.

B1! TO11 weight 701 and calcium stearate 0.
Mix 1 part and 11 parts in a Henschel mixer for 5 minutes, and
/ 4oxyxf of D-24> Perform melt cross-wire pelletization with an extruder, and M? Any, 5F/10 minutes total anhydrous maleic acid amount 0.175 mol%, graft reaction anhydrous! Amount of leic acid: 0120 mol%, amount of unreacted maleic anhydride: 0.05
A 5 mol % modified propylene composition was obtained. Then,
This modified polypropylene composition was heated and degassed at 155° C. for 3 hours using a constant temperature hot air dryer to achieve -1MIF+! -4.
3f710 minutes, total maleic anhydride JI 0.135 mol attack, graft reaction maleic anhydride i! A modified polypropylene composition containing 117 mol % of unreacted anhydrous maleic [iiO, 018 mol %] was obtained. The adhesive strength between this modified 1-lipropylene composition and nylon 6 was 110 (1/2 cm).

Example 8 M IF X -1, 21710 minutes, ethylene containing ff1
2.6 parts by weight of propylene-ethylene block copolymer 100 parts by weight, maleic anhydride 0.5 parts by weight.

0.2 parts by weight of benzoyl peroxide, 1 part by weight of BIT0, and 0.1 parts by weight of calcium stearate were mixed in a Henschel ζ mixer for 5 minutes, and L/D-24CD40Hi was mixed.
Melt cross-wire pelletization was carried out at 190° C. using an extruder. The obtained modified body 9 fo t' k > (D M
F
It was the 41st mole.

This modified polypylene was dried in a constant temperature air dryer for 15 minutes.
Heat treatment at 0℃ for 4 hours (hereinafter referred to as first stage heat treatment)
LMIF X-18, 5f/10 minutes.

A modified polypropylene was obtained in which the total amount of maleic anhydride was 0.110 mol, the amount of maleic anhydride after graat reaction was o, oso mol≦, and the amount of unreacted maleic anhydride was 0.030 mol. Next, 80 parts by weight of this heat-treated modified melipribylene was added with a specific gravity of 0.920. Mix 20 parts by weight of low density polyethylene of MIFI-2,7f710,
Melt mixed wire pelletization was performed at 220°C using a 0wxi extruder, and heat treatment (hereinafter also referred to as second heat treatment) was performed at 150°C for 4 hours using a constant temperature dryer to obtain a modified polypropylene composition. . The obtained modified melibrobylene composition was cowyp x-11,7F/10 minutes, the total amount of maleic anhydride was 0.085 mol arc, and the amount of maleic anhydride in Gerafushi reaction was 0.068 mol %.

The amount of unreacted anhydrous maleic acid was 0.017 mol. Coextruded at 270°C from a 0306ψ extruder and extruded through a die, the thickness of the modified pyrene layer was 0.21fl,
When a coextruded sheet with a polyethylene terephthalate layer thickness of 0.11@ was made and the adhesive strength was measured, it was 500 f.
Comparison @ 11 The same procedure as in Example 8 was carried out except that the first heat treatment was carried out for 8 hours and the second heat treatment was not carried out.

The resulting modified polypyrene composition (DM7 x-12
,0f710min, total amount of maleic anhydride is less than 0.084 mol, graft reaction anhydrous! The amount of leic acid is 0.068 mol%
, the amount of unreacted maleic anhydride is 0.016 mol, and the adhesive strength with polyethylene terephthalate is 20 (1/2
It was CII.

Comparative Example 12 The same procedure as in Example 8 was conducted except that the first heat treatment was not performed and the second heat treatment was performed for 8 hours. Obtained modified l-lipropylene composition ex>m=x−x
s, 5tty1o, completely anhydrous! The amount of leic acid is o, oss
Graft reaction anhydrous! The amount of leic acid is 0.070
Mormasu, unreacted anhydrous! The amount of leic acid is 0.018 mol, and the adhesive strength with polyethylene terephthalate is 30.
It was 01710 minutes.

Comparative Example 13 The same procedure as in Example 8 was conducted except that neither the first heat treatment nor the second heat treatment was performed. Obtained modified polypropylene composition g) My x-20, 1f
/10 minutes, total maleic anhydride am is 0.182 mol-,
The amount of graft-reacted maleic anhydride was 0.068 mol %, the amount of unreacted maleic anhydride was 0.072 mol %, and the adhesive strength with polyethylene terephthalate was 0.

Also, foaming occurs during molding.

Comparative Example 14 M? I-t, 2F/10 minutes, 80 parts by weight of propylene-ethylene block copolymer with ethylene content of 2.6%, specific gravity 0.920. MIF knee 2.7f/10min low density polyethylene 20 parts, anhydrous! 0.3 parts by weight of leic acid, 0.2 parts by weight of penzoyl peroxide, 1 part by weight of BITo, and 0.1 part by weight of calcium stearate were mixed in a Henschel ζ mixer for 5 minutes, and mixed with TJ/D-24 ( 7)4
Melt kneading pelletization was performed at 190°C using an otml extruder, MvX-12.8F/10 minutes, total anhydrous maleic content 0.206 molar arc, graft reaction anhydrous maleic content 0.
A modified Merippyrene composition containing 150 moles of unreacted maleic anhydride and 0.056 moles of unreacted maleic anhydride was obtained. Next, this modified propylene composition was dried at 150°C using a constant temperature air dryer.
Heat treatment was performed for 4 hours at MIF X-10, 1f/1.
0 minutes, completely waterless! A modified polypropylene composition was obtained in which the amount of leic acid was 0.1634 moles, the amount of graft-reacted maleic anhydride was 0.148 moles, and the amount of unreacted maleic anhydride was 0.0157 moles. The adhesive strength of this modified propylene composition with ethylene terephthalate was 501/2s and qf.
t.

Comparative Example 15 The modified propylene obtained in Examples 1 to 6 was dissolved in xylene by boiling, and after cooling, it was precipitated with acetone in a large lid, filtered, and then dried under reduced pressure at 50° C. for 24 hours. MPI-567f of this modified polypropylene (4) for 710 minutes, total maleic anhydride was 0.571 mol, graph) Reacted maleic anhydride amount was 0, 4807 l≦, unreacted maleic anhydride amount was 0.091 It was a mole attack. Next, 315 parts by weight of modified polypropylene Ca, 65 parts by weight of unmodified homogiri propylene of MF I-4,01710 minutes, and ethylene-butene-1 random copolymer with an ethylene content of 80% by weight and 6.4 f/10 minutes of ethylene-butene-1 random copolymer. 20 parts by weight! IH! 0.1
1 part by weight and 0.1 part by weight of calcium stearate were mixed for 5 minutes in a henshimel mixer, and then mixed with L/D-24tv.
Pelletizing was carried out at 220 °C by the aotxp extrusion side,
M] Fl.

6.31!710 minutes, total amount of maleic anhydride 0.085 mol-, amount of graft reaction maleic anhydride deposited 0.070 mol-
1 A modified polypropylene composition having an amount of unreacted maleic anhydride of 0.015 moles or less was obtained. It was determined in the same manner as in Example 3. The adhesive strength between this composition and Nanned XV rubber was 501/
It was 2 cm.

Comparative Example 16 The modified polypropylene (4) obtained in Comparative Example 15 was extracted with acetone using a Soxhlet extractor for 8 hours, and then extracted at 50°C for 2 hours.
After drying under reduced pressure for 4 hours, MPI-51,6#710 minutes, total maleic anhydride was removed by 0.500 mol, graft reaction amount of maleic anhydride was 0.463 mol, and unreacted anhydride! Modified propylene (B) with a leic acid content of 0.0377 l≦ was obtained.

Next, 15 parts by weight of modified polypropylene CB) was added to MF.
4,0f710min homopolypropylene 65 parts by weight, ethylene content 80% by weight 1M P X-64f// 10
ethylene-butene-1 random copolymer 20 weight I
1. 0.05 parts by weight of anhydrous malein, 1 part by weight of BIT 0, and 1 part by weight of stearic calcium were mixed for 5 minutes in a Henschel mixer, and L/! Pelletizing was carried out at 220°C using a 4oval extruder of l-24,
MνX-6,7f710 minutes.

Completely anhydrous! A modified polypropylene composition was obtained in which the amount of leic acid was 0.083 mol %, the amount of graft-reacted maleic anhydride was 0.069 mol, and the amount of unreacted maleic anhydride was 0.014 mol. It was determined in the same manner as in Example 3. The adhesive strength between this composition and saponified xvh was 0.

Comparative Example 17 The same procedure as Comparative Example 16 was conducted except that maleic anhydride was not added.

MPZ-6,4f of the obtained modified polypropylene composition
710 minutes, the total amount of maleic anhydride was 0.080 mol, the amount of graft-reacted maleic anhydride was 0.075 mol, and the amount of unreacted maleic anhydride was 0.005 mol. I asked for it. The adhesive strength between this composition and saponified VA was 200172 cm.

The results of Example 3 and Comparative Examples 4.5.15.16 and 17 are also shown in Table 2 below.

Claims (6)

[Claims] (1) Modified polypropylene obtained by bath-melting a mixture of polypropylene, unsaturated carboxylates 1 to 11, and an organic peroxide is heat-treated at a temperature of 60°C or higher, and then the modified polypropylene 95-50 Method 0 for producing a modified l-ribcypyrene composition, characterized in that 5 to 50 parts by weight of an ethylene polymer is mixed with the parts by weight, mixed in a bath melt, and then heat-treated again at a temperature of 60°C or higher. (2) The method according to claim (1), wherein the #S conductor of the unsaturated carboxylic acid is maleic anhydride. (3) The method according to claim (1), wherein the heating temperature is 100° C. or higher and lower than the melting point of the modified polypropylene. (4) The method according to claim IJA (1), in which the modified polypropylene composition is heated and degassed so that the amount of residual unreacted sulfur in the modified polypropylene composition is 0.05 mol % or less. (5) The method according to claim IiJ, paragraph (1), wherein the ethylene polymer is at least one selected from ethylene-butene-1 copolymer, ethylene-propylene copolymer, and low-density ethylene. . (6) Modified final lipropylene contains 100 parts by weight of polypropylene, 0.05 to 5 parts by weight of an unsaturated carboxylic acid or its derivative, and 0.01 to 11 parts by weight of an organic peroxide! The method according to claim 1, wherein the modified polypropylene is obtained by melt-kneading a mixture consisting of L parts in a scraper extruder.