JPS5867743A - Modified polypropylene composition - Google Patents

Abstract

PURPOSE:A composition that is prepared by adding a crosslinking assistant and a specific organic peroxide to a modified polypropylene, thus showing eminently improved adhesion to metal and giving laminatings with resistance to high temperature. CONSTITUTION:The objective composition comprises (A) a modified polypropylene that is prepared by grafting an unsaturated carboxylic acid to a part or the whole of polypropylene, (B) a crosslinking assistant, (C) an organic peroxide with a half-value temperature in one minute being more than 10 deg.C higher than the melting point of component A. The unsaturated carboxylic acid in component A is preferably maleic anhydride and the graft content is preferably 0.005-5wt%. As the component B, is used liquid 1,3-polybutadiene or divinylbenzene. 100pts. wt. of component A are mixed with 1-50pts.wt. of component B and 0.1- 10pts.wt. of component C with a mixer and made into, e.g., a sheet at a temperature lower than the one-minute half-value temperature of component C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a modified polyp-pyrene composition particularly for lamination, which has good adhesion to metals and high temperature heat resistance.

Polypropylene is non-polar, so it does not show any adhesion to metals. Conventionally, in order to improve adhesion,
■Discharge treatment applied to polypropylene or (and) metal surfaces.

A method of applying am treatment such as black-and-white treatment, flame treatment, etching, ■ A method of using a modified polyolefin obtained by grafting maleic anhydride onto a polyolefin (for example, Japanese Patent Publication No. 10757/1983 and No. 47-4822), ■ Acid A method using a composition in which a modified polyolefin is blended with a synthetic hydrogen-based elastomer or an ethylene-based polymer (for example,
JP-A-52-80334 and JP-A-56-21850 are well known. However, when the polybupyrene produced by these methods is laminated with metal or the like, there are problems in that it easily deforms due to its own weight or external force when the temperature exceeds the melting point of the wrinkled polypropylene, and it has poor high-temperature heat resistance.

Generally, it is well known that crosslinking of polymeric substances significantly improves their melt resistance and improves their high-temperature heat resistance. However, polypropylene is a pyrolyzable polymer, and when mixed with an organic peroxide and heated, crosslinking does not occur, but on the contrary, it decomposes and its viscosity decreases.

Therefore, in order to thermally crosslink polybupylene, a method has been adopted in which a crosslinking aid such as divinylbenzene or liquid 1,2 polybutadiene is mixed with a radical generator and heated.

However, the crosslinked polypropylene obtained in this manner not only does not adhere to metals at all, but it is extremely difficult to form it into, for example, films or sheets.

As a result of various studies on polypropylene that has good adhesion to metals, the present inventors found that modified polypropylene partially or completely grafted with unsaturated carboxylic acids was used as a crosslinking aid, and modified polypropylene with a 1-minute half-life temperature of The modified polypropylene composition of the present invention was completed by blending an organic peroxide with a melting point of 10°C or more higher than the melting point of pyrene. That is, the present invention relates to a modified polybupylene partially or entirely grafted with unsaturated carboxylic acids.

This is a modified polypropylene composition comprising a crosslinking auxiliary agent and an organic peroxide whose 1-minute boiling temperature is 10° C. or more higher than the melting point of the modified polypropylene.

The modified polybupylene composition of the present invention exhibits good adhesion at a temperature higher than the melting point of the modified polybupyrene and lower than the one-minute reduction temperature of the organic peroxide contained therein, particularly when obtaining a laminate with a metal. By heating the organic peroxide for 1 minute to a temperature higher than the cow's annihilation temperature, a laminate with good heat resistance that does not deform at high temperatures can be obtained.

The modified polypropylene used in the present invention can be obtained by grafting unsaturated carboxylic acids onto polypropylene by any method. The graft content of unsaturated carboxylic acids in modified polybupylene is generally 1c O
,005 to 5% by weight. Methods for producing such modified polypropylene include, for example, a method of reacting in a molten state (for example, Japanese Patent Publication No. 43-27421);
A method of reacting in a solution state (for example, Japanese Patent Publication No. 44-154)
No. 22), a method of reacting in a slurry state (for example, Japanese Patent Publication No. 18144/1983), a method of reacting in a gas phase (
For example, JP-A-50-77493) is known, and among these methods, the melt-kneading method using an extruder is preferably used because it is easy to operate.

The polypropylene used to produce modified polybupylene is particularly limited, and includes homopolybupylene, propylene-ethylene polymer copolymer, propylene-ethylene random copolymer, and propylene and α-olefin copolymers. Copolymers, mixtures thereof, and the like are used. Among these, propylene-ethylene random copolymers and propylene-ethylene copolymers are particularly preferably used. The melting point of these polypropylenes varies depending on the tacticity and fumonomer content, but generally 1.
c130~170℃ range 1! There is IK.

Examples of unsaturated carboxylic acids used to produce modified polypropylene include acrylic acid, methacrylic acid, maleic acid, 7-acrylic acid, citraconic acid, and their acid anhydrides and esters. Imidof metal salts, etc., such as malemono anhydride, citraconic anhydride, itaconic anhydride, methyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, glycidyl acrylate, glycidyl methacrylate, monoethyl maleate, Maleic acid diethyl ester, 7malic acid monomethyl ester.

Fumaric acid dimethyl ester, itacon monomethyl ester, itaconic acid diethyl ester! acrylamide 9
Methacrylamide, maleic acid diamide, maleic acid diamide.

Malein Il-N-monoethylamide, Malein Il-
N,N-diethyl 7mide, maleic acid-N-mottyl 7mide, maleic acid-N-N, N-dibutylamide, fumaric acid monoamide, fumaric acid diamide, fumaric acid-N-
Monoethylamide, fumaric acid-N, N-diethylamide, fumarl1-N-motuptil 7mide, fumaric acid-N,
N-dibutylamide, maleimide, N-butylmaleimide 9N-phenylmaleimide.

Examples include sodium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate, and the like. Among these, it is most preferable to use maleic anhydride as O.sub.2 modified polybupylene, which includes various unmodified polypropylenes as described above, polymeric substances other than the commonly used polybupylene, and inorganic materials.

Organic fillers, heat stabilizers, weather stabilizers, lubricants.

It may contain antistatic agents, nucleating agents, pigments, dyes, refueling agents, antiblocking agents, and the like.

The content of graft unsaturated carboxylic acids in the modified polybupylene is preferably from o, o o s to 5% by weight.

The crosslinking aid used in the present invention is a compound having two or more double bonds in one molecule, and examples thereof include evadivinylbenzene, diallyl phthalate, triallyl glycerate, and a number-average molecular weight compound whose main component is a diene monomer. 5oo~10,
000 liquid rubbers, such as 1,2-polybutadiene.

1.4-polybutadiene, styrene-butadiene copolymer, 7-crynitriloptadiene copolymer, or carboxyl group, hydroxyl group, mercapto group in the molecule,
1,2-polybutadiene, 1,4- with functional groups such as amino group, aziridino group, and epoxy group
polybutadiene, polyisoprene, borikpρrene,
Examples include 1.2-polypentadiene, styrene-butadiene copolymer, 7-nitrile-butadiene copolymer, butadiene-isoprene copolymer, butadiene-pentadiene copolymer, and divinylbenzene and liquid 1,2-polybutadiene are preferably used. be done. The amount of the crosslinking aid added is 1 to 50 parts by weight per 100 parts by weight of modified polypropylene, preferably 3 to 30 parts by weight per 100 parts by weight of modified polypropylene.

If the amount of the crosslinking aid added is less than 1 part by weight, the effect of improving high temperature heat resistance will be small, and if it exceeds 50 parts by weight, the rigidity at temperatures below the melting point of the modified polypropylene will be significantly lowered, which is undesirable.

Next, the organic peroxide used in the present invention has a one-minute decomposition temperature (temperature at which it decomposes by half in one minute) and a melting point of modified polypropylene (measured at a heating rate of 10°C/min with a differential scanning calorimetry needle). 10°C or more higher than the peak temperature of the endothermic curve. The melting point of modified polypropylene is 130-170
Since the temperature is in the temperature range of 140° C., organic peroxides having a one-minute decay temperature of 140° C. or higher can be used. Examples of organic peroxides used in this development v4 are L4*4)
! J Methylpentyl-2-hydride p peroxide.

Diimpropyl benzene hydride peroxide, cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylno-oxy)-hexane 91t3゛-bis -(t-butylperoxyisopropylene 1
)-benzene, t-butylcumyl peroxide,
Di-t-butyl/(-oxide.

2,5-dimethyl-2,5-di(t-butylperoxy)-hexyne-3,1,1-di-t-butylperoxy-3,3,5-)limethylcyclohexane, violet, 1-
Di-t-butylperoxycyclohexane, 2,2-di(t-butylperoxy)-butane, 4,4-di-t
-butyl peroxyvaleric 7)-n-butyl ester, di-t-butyl peroxy-hexahydroterephthalate, di-t-butyl peroxy azelate,
t-butylperoxy-3,5,5-trimethylhexolet) It-butylperoxyacetate, t-butylperoxybenzony) t-butylperoxyisopropylene carbonate, succinic 7-side peroxide, vinyltris-( t-butylperoxy)silane, etc.

The amount of organic peroxide added varies depending on the amount of crosslinking aid added, but is generally preferably 0.1 to 10 parts by weight per 1 GG part by weight of the modified polypropylene. When the amount of organic peroxide added is less than 0.1 part by weight, the degree of crosslinking is low, and
If it exceeds 1 part by weight, decomposition will occur and the effect of improving high temperature heat resistance will be small, which is not preferable.

In the present invention, modified polypropylene.

Depending on the crosslinking aid and organic peroxide-9, other polymeric substances other than unmodified polypropylene and polypropylene, fillers, and other additives may be mixed. For mixing, use a Zulendar tumbler, a ■Ran blender, and a Henschel mixer.

This is done using a ribbon mixer or the like. In some cases, these mixtures may be processed by slurry extrusion or mixing p-
It is also possible to melt and knead the modified polypropylene at a temperature higher than the melting point of the modified polypropylene and lower than the one-minute half-life temperature of the organic peroxide using a Lebanese mixer or the like. Furthermore, it is also possible to form, for example, a film or a sheet (hereinafter collectively referred to as a sheet-like material) from the melt-kneaded modified polyp-pyrene composition.

The modified polyp-pyrene composition of the present invention produced as described above has good adhesion when laminated with a metal as it is or in the form of a sheet, and has good adhesion when laminated with a metal.
A laminate with excellent high-temperature heat resistance can be obtained by heat treatment at a temperature equal to or higher than the half-life temperature for minutes.

Hereinafter, examples of the present invention will be given and the mode of use as a laminate will be shown, but the present invention is not limited thereto.

In the examples, the adhesive strength and high temperature heat resistance of the obtained laminates were measured by the following methods.

The adhesive strength is 0.1 between two Qcx width metal sheets.
It is expressed as the T-peel strength of a three-layer laminate having a layer of modified polypropylene composition of (1) thickness. Measurement was performed at 23°C, 50%R
The test was carried out at H with a pulling rate of 2011 Il/min.

The measurement of high temperature resistance was carried out using a 3-layer laminate having a 0.1 M thick layer of the modified polybupylene composition between two parallel opposed metal sheets with an overlap length of 23 mm.
The sample was placed in an open chamber at 0° C., one of the metal sheets was suspended with a wire, and after 10 minutes, a load was applied to the lower metal sheet (K200JI), and the time required for the two metal sheets to separate was expressed as the time. The thickness of the metal sheet is 0.2 fi (iron sheet) and 0.1 fi (aluminum sheet), and these are sufficiently degreased.

Example I MFI depth 0.6! i/10 min, 100 parts by weight of propylene-ethylene random copolymer with an ethylene content of 2.0% by weight, 2 parts by weight of maleic anhydride.

0.12 parts by weight of 2,5-dimethyl-2,5-di(t-butylperoxy)-hexane, 0.1 parts by weight of butylated hydro+citoluene, and 0.1 parts by weight of calcium stearate were mixed for S minutes in a Henschel mixer. Mix, L/D Proverbs 24
The mixture was subjected to melt cross-wire pelletization at 220°C using a 040W extruder, and then heat-treated at 145°C for 4 hours using a constant temperature dryer to obtain modified polypropylene. This modified polypropylene contained 0.5% by weight of anhydrous i-Rain grafted.

15 parts by weight of this modified polypro 22, MFI-4.0p
/10 minutes, 85 parts by weight of unmodified boopylene-ethylene random copolymer with ethylene content of 3.0% by weight (melting point 140°C), 101 parts by weight of divinylbenzene, dicumyl peroxide (1 minute cow slaughter temperature 179°C) 2 .0 parts by weight.

The composition of the present invention consisting of 0.1 part by weight of butylated human-xytoluene and 0.1 part by weight of calcium stearate was mixed for 5 minutes in a Henschel mixer and heated to a thickness of 0.1 part by weight at 165°C using an extruder with a T-die. A sheet was formed.

This sheet was sandwiched between aluminum sheets having a width of 2c11 and pressed together at a temperature of 170°C and a pressure of 10 r#/- for 5 minutes, and then heated at 220°C for 5 minutes. In this way, the adhesive strength of the obtained laminate was 7.5 KF/
2j1m, high temperature heat resistance was 1 hour or more.

Comparative Example 1 The same procedure as in Example 1 was carried out except that benzoyl peroxide (1 minute half-reduction intensity: 130° C.) was used instead of dicumyl peroxide. When extruding into a sheet, the extrudate became flaky and no sheet could be obtained.

Comparative Example 2 The same procedure as in Example 1 was conducted except that the modified polybupylene was not added and the unmodified propylene-ethylene random copolymer was used in an amount of 100 parts by weight. The adhesive strength of the obtained laminate was O.

Comparative Example 3 No dicumyl peroxide was added in any number of experiments.
Other than that, the same procedure as in Example 1 was carried out. The adhesive strength of the obtained laminate is 0.5r#/20111 high temperature heat resistance is 5
It was 0 seconds.

Comparative Example 4 The same procedure as in Example 1 was carried out except that divinylbenzene and dicumyl peroxide were not added. The adhesive strength of the obtained laminate was 1.8 Kp/
2 am + high temperature heat resistance was 90 seconds.

Example 2 15 parts by weight of the modified polyp pyrene obtained in Example 1,
MFI=1.5 g/10 min, unmodified propylene-ethylene block copolymer with ethylene content of 27% by weight (melting point 1
60°C) 85 parts by weight, 40 parts by weight of calcium carbonate with an average particle diameter of 1.2μ, liquid quality 1,2- with a number average molecular weight of 1000
20 parts by weight of polyztadiene, 2,5-dimethyl-2,5
-Di(t-butylperoxy)-hexyne-3 (1 minute half-life temperature 193°C) 3 parts by weight, methylated hydroxytoluene 0.1 part by weight, and calcium stearate 0.1 part by weight. The composition was mixed in a Henschel mixer for 5 minutes and then mixed in a CCM extruder for 170 min.
Melt-kneading pelletization was performed at ℃. The obtained polypropylene composition pellets were processed using an extruder equipped with a T-die.
A sheet with a thickness of 0.1 mm was formed at 5°C.

Sandwich this sheet between 2aI1 width iron sheets, 22
Pressure bonding was carried out for 10 minutes at a temperature of 0° C. and a pressure of 10 KIP/d. The adhesive strength of the laminate thus obtained was 13.
5"I/2 C1l *High temperature heat resistance was - for 1 hour or more.

Comparative Example 5 In Example 2, 2,5-dimethyl-2,5-di(
The same procedure as in Example 2 was carried out except that benzoyl peroxide was used instead of t-butylperoxy)-hexyne-30. When pelletizing by CCM extrusion, the extrudate became flaky and good pellets could not be obtained.

Comparative Example 6 The same procedure as in Example 2 was carried out except that the modified polypropylene was not added in Example 2, and 100 parts by weight of the unmodified propylene-ethylene chloride copolymer was used. The adhesive strength of the obtained laminate was O.

Comparative Example 7 In Example 2, 2,5-dimethyl-2,5-C (t
The same procedure as in Example 2 was carried out except that -7'-tylperoxy)-hexyne-3 was not added. The resulting laminated layer had an adhesive strength of 0.3, KP/2 C1l, and a high temperature heat resistance of 30 seconds.

Comparative Example 8 Liquid 1,2-polyptage/and 2 in Example 2
, 5-dimethyl-2,5-di(1-butylperoxy)-hexyne-3 was not added, but the same procedure as in Example 2 was performed except for the addition of .

The adhesive strength of the resulting laminate was 9-7 KF/2 am
.

High temperature heat resistance was 120 seconds.

patent applicant Tokuyama Blind Difference Co., Ltd.

Claims (1)

[Scope of Claims] (Modified polypropylene partially or wholly grafted with unsaturated carboxylic acids, crosslinking aid; and organic peroxide whose 1-minute half-life temperature is 10°C or more higher than the melting point of wrinkle-modified polypropylene. (2) A modified polybutyrene composition (3) according to claim 1, wherein the unsaturated carboxylic acid is maleic anhydride (3) The bridge II# agent is liquid 1,2-polybutadiene or divinylbenzene (3) The modified polypropylene composition according to claim 1 is a sheet-like product formed at a temperature lower than the 1-minute half-life temperature of organic peroxide. Composition according to scope 1