JPS5867447A - Polypropylene sheet for laminating - 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 relates to a polypropylene sheet for lamination that has good adhesion to metals and high temperature heat resistance.

/IJ7" Lopyrene is a non-polar metal, etc.
It hardly shows any layering property. Conventionally, in order to improve adhesion, ■I surface treatments such as corona discharge treatment, chromic acid treatment, flame treatment, and etching are applied to the surface of polypropylene or (and) metal; ■- Maleic anhydride applied to lyolefin; A method using modified / reolefin / grafted with
7-Guza No. 22), ■ A method using a composition in which WIF polyolefin is blended with carbonized ice cream synthetic elast 1- or an ethylene polymer (for example, JP-A No. 5-80339,
56-co/13; No. 0) are known. However, when the cortical polypropylene produced by these methods is laminated with metal, it easily deforms due to its own weight and outwards when the temperature exceeds one point of LTF/liglopylene, and it has poor high temperature resistance. There is a problem.

It is generally well known that by crosslinking polymer materials, the melting resistance and formation resistance are greatly improved and the high m heat resistance is improved. However, since propylene is a thermally decomposable polymer, when mixed with a highly sensitive substance and heated, crosslinking does not occur, but rather decomposition occurs and the viscosity decreases. Therefore, II) in order to thermally crosslink propylene, a method has been adopted in which a crosslinking aid such as divinylbenzene or liquid 7.2/liptadiene is mixed with a radical generator and heated. However, the crosslinked polypropylene obtained in this way not only does not adhere to metal at all, but it is extremely difficult to form it into, for example, a film or sheet.

As a result of extensive research into polypropylene, which has good adhesion to metals and excellent high-temperature heat resistance, the inventors found that /I
A desired laminate with metal etc. can be obtained by using a sheet molded at a specific temperature from a composition made by adding a specific organic peroxide to J7" Robyrene, an unsaturated carboxylic acid, and a specific organic peroxide. It is with this in mind that we propose the present invention.That is, the present defense is based on polypropylene, unsaturated carbon #R, a crosslinking agent, and polypropylene whose half-life temperature per minute is A laminated polypropylene sheet formed by molding a composition consisting of a single peroxide having a melting point of 70° C. or more above the melting point of the polypropylene at a temperature lower than the temperature of the oxidation frame 1 per minute at a temperature above the melting point of the polypropylene. Yes.In addition,
The term "sheet" used in the present invention refers to a material that cannot be used to form an adhesive layer or a laminate with a metal or the like, and includes general sheet-like materials and film-like materials.

The polypropylene conveniently used in the present invention is %
but not limited to, small mopolynolobylene, zolopyrene-ethylene block copolymer, zolopyrene-ethylene random copolymer, copolymer of propylene and α-olefin,
Mixtures of and et al. are used. Among these, a special VC propylene-ethylene random copolymer and a propylene-ethylene block copolymer are preferably used.

The melting point of these polypropylenes varies depending on the tacticity and comonomer, but generally the melting point is between 730 and 7.
It is in an area of 70°C.

Examples of unsaturated carboxylic acids used in the present invention include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and their acid anhydrides, esters, amides, imides, gold maple salts, etc. For example, maleic anhydride, citraconic anhydride, itaconic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, glycisol acrylate, glycidyl methacrylate, monomaleic acid. Ethyl ester, maleic acid diethyl ester, fumaric acid monomethyl ester,
Fumaric acid dimethyl ester, (taconic acid monomethyl ester, itaconic acid diethyl ester, acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, malei; 4t-NtN-diethylamide, maleic acid) acid-N-
Monobutyramide, maleic acid-N, N-sibutyramide, fumaric acid monoamide, fumaric acid noamide, fumar f
i-N-monoethylamide, fumaric acid-N, N-diethylamide, fumaric acid-N, N-butyramide, fumaric acid-N, N-butyramide, maleimide, N-butylmaleimide, N-phenylmaleimide, sodium acrylate , Sodium methacrylate, Potassium acrylate, Potassium methacrylate s7 - can be 3, Among these, maleic anhydride and unsaturated carboxylic acid gold jl! Places such as places are preferably used. Although the amount of unsaturated carboxylic acids used may be limited, it is generally preferred to use 0.07 to 20 parts by weight based on the weight of polypropylene/θO in order to obtain a laminate with good adhesion. It is necessary to add θ, / to 70 parts by weight.

The crosslinking aid used in the present invention is a compound having one or more double bonds in one molecule, such as a number-average molecule containing novinylbenzene, noazol phthalate, triallylglycerate, or diene monomer as a main component. *SOO~10.
Liquid rubber of θ00, e.g. /, 2-polybutadiene, /
, 'l-polyp1)ene, styrene-butadiene coyf
! IJ Mar, 7crylonitrile-butadienco I
Limer, or in the molecule, there are xyl groups, hydroxyl groups, mercapto groups, halodane atoms, amine groups, aziridino groups,
Engineering? i, t-rt liptadiene, /, 4'--liptadiene, I ringlen, y with an official rainbow group such as xy group
f? lJ chlorogren, /, 2-2 reintazoene,
Styrene-butadiene codelimer/177-, acrylonitrile-butadiene codelimer, butadiene-isoprene codelimer, butadiene-intadiene codelimer, j? +77
- etc., divinylbenzene and liquid /, -
-I liptadiene is preferably used. The amount of crosslinking aid added is 7 parts by weight of modified & 9f propylene 10θ.
~50 parts by weight, preferably 3 to 30 parts by weight per 100 parts by weight of propylene. If the amount of crosslinking aid added is less than 1 part, the effect of improving high temperature heat resistance is small, and SO
If the amount exceeds 1 part by weight, the temperature will drop below the melting point of polypropylene, resulting in a significant decrease in rigidity, which is undesirable.

In the present invention, as an organic peroxide, the 1 minute half-life temperature (
The temperature at which half decomposes in 7 minutes) is 70°C or more higher than the melting point of pyrene (the peak temperature of the endothermic curve measured at a temperature increase rate of 10°C/min with a differential erosion calorimeter). That's 'ttL.

The melting point of polypropylene is as mentioned above (generally 730~
Since the temperature range is 770°C, an organic peroxide having a per minute cow reduction temperature of generally #Cl1IO°C or higher is used. Examples of such single-unit peroxides include:

11t, 4t-) IJ methylbenzene-co-hydrono-4-oxide, noiso≠lovirpenzene hydroperoxide, cumene hydroperoxide, t-
Butyl ha-1 doronoya monooxide, tsucumil/ya monooxide, co,5-dimethyl-co, 5-no(t-butylperoxy)-hexane, i,3-bis-(t-butyl/4'-oxy-inglovir) -benzene, t-butylcumyl peroxide, di-t-butylno-4-oxide, co, S-zomethyl-co, S-no(t-butylno-4'-,txy)-hexyne-3,/,/-di-t -Butylperoxy-3,3,! ;-trimethylcyclohexane, /, l-not-ffluno or monooxine cyclohexane, 2, . 2-No(t-butyl-monooxy)-butane, <2. +-Di-t-butyl/f-oxynitrate n-butyl ester, di-t-butyl/
4'-oxyhexano\hydrotere7thalet, g-t-butylno-ya-oxyazelate, t-decylno-ya-ichioki'/-3, 5,! ;-) methyl 11':/!
-t, t-butyl glossoxyacetate, t-butyl nona-oxybenzoate, t-butylnocouoxyinzolobyl carnoate, succinic acid f-
oxide, vinyltris-(t-butyl/arm-oxy)silane, and the like. The addition lid for the organic peroxide varies depending on the addition lid for the crosslinking aid, but generally I-lipropylene/
The amount is preferably 0.7 to 10 parts by weight relative to θ0 parts by weight. If the amount of organic peroxide added is less than θ,/''iL parts, the degree of crosslinking in the hot water section is low, and if it exceeds 10 parts by weight, complete decomposition occurs and the effect of improving high temperature heat resistance is small, which is not preferred.

In the present invention, the above-mentioned t-polyzolopylene, a crosslinking aid, an organic peroxide, and, if necessary, polymeric substances other than 1-lipropylene, fillers, and other additives are mixed to obtain a 1-lipropylene composition. For mixing, use a tumbler blender, V-type blender, Henschel mixer, or Su? This is done using a mixer, etc. In some cases, the mixture of straw and straw may be melt kneaded in a bath using a 1t1m screw press, a mixing roll, a Noyan drill mixer, etc. at an fM# that is above the melting point of polypropylene and below the half-life temperature of organic peroxide per minute. I can do it. Next, the present invention obtains a desired sheet from the above-described polypropylene composition at a temperature higher than the melting point of the polypropylene and lower than the half-life temperature per minute of the organic peroxide contained therein.

The thus obtained polypropylene Z-sheet of the present invention can be pressed with gold maple or the like at a temperature higher than the 1-minute half-life temperature of the organic peroxide contained in the sheet to form a laminate with good adhesion and excellent high-temperature heat resistance. can be obtained. There are no restrictions on the metal used for well logging, and examples include iron, aluminum, chromium, nickel, gold, silver, copper, magnesium, zinc, tin, lead, steel, stainless steel, galvanized iron, and tin. , iron and aluminum are preferably used.

The polypropylene/metal laminate obtained in the above manner has strong adhesive strength between the two, excellent high-temperature heat resistance, and has both the excellent characteristics of polypropylene and the excellent characteristics of metal. Because it has excellent new features that neither metals nor metals have, it can be effectively used as packaging materials for automobiles, industrial materials, building materials, beverage cans, and various foods.

Examples of the laminate of the present invention are shown below, but the present invention is not limited thereto.

The adhesive strength and high temperature heat resistance of the laminates in Examples were measured by the following methods.

The adhesive strength is KO between two 2m wide metal sheets, /■
It is expressed as T-peel strength of a three-layer stack having a layer of modified polypropylene composition of thickness. Measurements were taken at 3°C and SO bag RH.
The test was carried out at a tensile rate of Om/min.

The m1 constant of high temperature heat resistance is 10 between two parallel metal sheets facing each other so that the overlapping length is one piece, and 20 for a three-layer laminate having a modified propylene composition layer with a thickness of /■.
It was placed in an oven at 0°C, one metal sheet was suspended with a wire, and after 7.70 minutes, a load of 2002 was applied to the lower metal sheet, and the time was expressed as the time until the two metal sheets separated. In addition, the thickness of the iron sheet is 0°, 2 m
, aluminum sheet 0.1 m long, and the straw has been optically degreased.

Procedures Amendment Book November 1980 ψ Japan Patent Office Commissioner Haruki Shimada 1 Indication of the case A/if C 2 Patent application filed on October 19, 1980 (4) 2, Name of invention for lamination Polypropylene Sheet S Relationship to the case of the person making the amendment Patent applicant address 1-1 Mikage-cho, Tokuyama City, Yamaguchi Prefecture & Number of inventions increased by the amendment None & “Detailed description of the invention” of the specification subject to the amendment Columns 7 and 4 Correct contents (1) Insert the following sentence from line 8 on page 12 of the specification.

"The polypropylene/metal laminate with one or more layers obtained as described above has strong adhesive strength between the two, excellent high-temperature heat resistance, and combines the nine excellent characteristics of polypropylene with the excellent characteristics of metal. In addition, it has excellent new features such as not having polypropylene or metal, so it can be effectively used as automobile materials, industrial materials, building materials, beverage cans, packaging materials for various foods, etc.

Examples of the present invention will be listed below, and the mode of use as a laminate will be shown, but the present invention is not limited thereto.

The adhesive strength and high temperature heat resistance of the laminates obtained in Examples were measured by the following methods.

The bonding strength is 0.000.
It is expressed as the T-peel strength of a three-layer laminate having a layer of polypropylene composition 1 inch thick.

Measurement is 2SC, 50X RHjmJP Ite 20x
This was done with a pulling speed of 7 minutes.

The heat resistance was measured using a 5-layer laminate having a polypropylene composition layer with a thickness of 0.1 mm between two parallel metal sheets facing each other with an overlap length of 251 cm at 200°C.
One of the metal sheets was suspended with a wire, and a load of 200 t was applied to the lower metal sheet for 10 minutes, and the time was expressed as the time until the two metal sheets separated. The thickness of the metal sheet was 0.2 mm for the iron sheet and 0.1 mm for the aluminum sheet, and these were sufficiently degreased.

Example 1 Propylene-ethylene random copolymer with uFI=0.6F/10 min and ethylene content of 3.0% (melting point 140°C)
100 parts by weight, methacrylic acid, 5 parts by weight of sium, 10 parts by weight of divinylbenzene, dicumyl peroxide (
2.0 parts by weight of 179 C), 0.1 parts by weight of butylated hydroxytoluene, and 0.1 parts by weight of Stair IJ calcium heptate were mixed in a Henschel mixer for 5 minutes, and then mixed in an extruder with a T-die. Thickness 0.1- at 165℃
A laminating sheet of the present invention was formed into a film. This sheet is 2a
Place the scissors between the aluminum sheets of lI width at 170℃.
l & .

Pressing was carried out for 5 minutes at a pressure of 10 mm/-, followed by heating for 5 minutes at 220°C. The adhesive strength of the thus obtained laminate was 15.311/2 cm*High temperature heat resistance #i 1 hour or more.

Comparative Example 1 The same procedure as in Example 1 was conducted except that benzoyl peroxide (1 minute aging temperature: 130 C) was used instead of dicumyl peroxide. In the case of sheet molding, the extrudate became flaky and no sheet could be obtained.

Comparative Example 2 The same procedure as in Example 1 was carried out except that the sheet extrusion temperature was changed to 220°C.

The extrudate became flaky and no sheet was obtained.

Comparative Example 3 The same procedure as in Example 1 was conducted except that calcium methacrylate was not added. The adhesive strength of the obtained laminate was 0.

Comparative Example 4 The same procedure as in Example 1 was conducted except that divinylbenzene was not added. The adhesive strength of the obtained laminate was 1.1 Ill/2 as, and the high temperature heat resistance was #'i1.
It was less than 0 seconds.

Comparative Example-5 The same procedure as in Example 1 was carried out except that dicumyl peroxide was not added. The adhesive strength of the obtained laminate was 0.41/26 IIm high temperature heat resistant FiSO
It was seconds.

Example 2 MFI=1.5F/10min, j-chi L/7 content 2.
100 parts by weight of a 7% by weight propylene-ethylene block copolymer (melting point 1<SO[:), 40 parts by weight of calcium carbonate with an average particle size of 1.2μ, 0.5 parts by weight of maleic anhydride, a number average molecular weight of 1000. Liquid 1,2-polybutadiene 2011 amount IS.

2.5-dimethyl-2,5-di(t-butylperoxy)-hexyne-3 (1 minute half-life 193°C) 3 parts by weight, butylated hydroxytoluef 0-1 parts by weight m stearin soap 0.1 part by weight of calcium was added to Henschel 5at-
The mixture was blended for -cs minutes, and then melt mixed and S pelletized using a CCM extruder at 170°C. A sheet for lamination of the present invention having a thickness of 0.1 mm was formed from the obtained polypropylene composition pellets at 175 DEG C. using an extruder equipped with a . This sheet was sandwiched between 2ts wide iron sheets at 220°C.
Pressing was carried out for 10 minutes at a pressure of 10/-. The adhesive strength of the nine laminate thus obtained was 10.8 ft/21, and the high temperature heat resistance was 1 hour or more.

Comparative Example 6 The same procedure as in Example 2 was carried out except that mf12 was used and benzoyl peroxide was used instead of 2,5-dimethyl-2,5-di(t-butylperoxy)-hexyne-30. When pelletizing using a CCM extruder, the extrudate became flaky and clean pellets could not be obtained.

Comparative Example 7 The same procedure as in Example 2 was carried out except that the sheet extrusion temperature was changed to 220°C. The extrudate became flaky and no sheet was obtained.

Comparative Example 8 The same procedure as in Example 2 was conducted except that maleic anhydride was not added.

The adhesive strength of the obtained laminate was 0.

Comparative Example 9 The same procedure as in Example 2 was conducted except that liquid 1,2-polybutadiene was not added. The resulting laminate had an adhesive strength of 5.5 Kt/23 and a high temperature heat resistance of 10 seconds or less.

Comparative Example 10 The same procedure as in Example 2 was conducted except that 2,5-dimethyl-2,5-3 was not added. Adhesive strength of the obtained laminate lIL#iα2/251. The high temperature heat resistance was 260 seconds.

patent applicant Tokuyama Soda Co., Ltd.

that's all

Claims (1)

[Claims] (1) A composition comprising: (1) /lipropylene, an unsaturated carboxylic acid, a crosslinking aid, and an organic peroxide whose half-life temperature per minute is 10°C or more higher than the melting point of II/IJ propylene. from,
A polypropylene sheet for lamination (2) formed by molding at a temperature above the melting point of the polypropylene and lower than the organic peroxide for 1 minute, wherein the unsaturated carboxylic acids are maleic anhydride or unsaturated carboxylic acid metal The sheet (3) according to claim (1) of the patent IR+, which is suitable for use in patents, and the sheet (4) according to claim (1) in which the crosslinking auxiliary agent is liquid coco-ributadiene or phosphorylbenzene. The organic peroxide is dicumyl p4-oxide or U,S-dimethyl-2. % claim that is S-di(t-butyl/m-oxy)-hexyne-3! Sheet described in Section 81 Section 0)