JPS5845051A - Laminate - 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 1. The present invention relates to a laminate comprising a polypropylene composition and a metal.

Laminates of synthetic resins and metals are widely used, taking advantage of their respective characteristics. For example, metal corrosion and rust can be prevented by coating the surface of a metal molded article with a synthetic resin thin film. In addition, metal sandwich panels, which have a synthetic resin sheet between two metal thin films, have the surface appearance of metal, are light as synthetic resin, and have far superior mechanical properties than molded products made of synthetic resin alone. It has heat resistance and heat resistance, making it possible to reduce weight and cost by using it as, for example, automobile parts. Polypropylene has the lowest specific gravity among synthetic resins, has excellent mechanical properties such as rigidity and heat resistance, and is inexpensive. Studies are underway as an intermediate layer resin. However, since polypropylene is non-polar, it rarely exhibits adhesion to metals, and it is not possible to obtain laminates that firmly adhere to metals. ■Corona discharge treatment and chrome border treatment on polypropylene and metal surfaces.

A method in which surface treatments such as flame treatment and etching are applied;
No. 57, No. 47-4822), ■ A method in which a hydrocarbon-based synthetic elastomer or an ethylene polymer is completely blended with a modified polyolefin (for example, JP-A No. 52-80)
No. 334 and No. 56-21850) are known.

However, these methods require a surface treatment step, and the adhesion to metals is not sufficient.

As a result of various studies on polypropylene with good adhesion to metals, the present inventors found that by blending a finely powdered inorganic filler and preferably further an ethylene polymer into a modified polypropylene containing a propylene-ethylene block copolymer, The inventors have discovered that the intended purpose can be achieved and have arrived at the present invention.

The present invention uses propylene-ethylene block copolymer
A modified polypropylene comprising a modified polypropylene (A) partially or entirely grafted with an unsaturated carboxylic acid containing 0% by weight or more and a finely powdered inorganic filler (B), preferably further an ethylene polymer (0). Composition layer (
It is a laminate consisting of a metal layer (Y) or an unmodified polypyrene layer (Z).

In order to specifically explain the present invention, first, a method for producing a modified 1-lipropylene composition (X or XI) will be explained.

The modified propylene used in the present invention can be obtained by grafting unsaturated carlinic acids onto polypropylene by any method. Methods for producing 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. 44-15422), and a method of reacting in a slurry state (for example, Japanese Patent Publication No. 44-15422). Kosho 43-19144
No.), a method of reacting in a gas phase (e.g., JP-A No. 5 O-
774939), among these methods, the melt-kneading method using an extruder is preferred because of its operational simplicity.

Therefore, the In method for producing modified polypropylene using the melt-kneading method will be described in detail. The polypropylene used to produce modified polypropylene is usually a propylene-ethylene block copolymer, but if it is later diluted with an unmodified propylene-ethylene block copolymer, it can be used as a homopolypropylene or brobylene block copolymer. A copolymer of ethylene silanda A, a copolymer of propylene and α-olefin, etc. can also be used. Propylene used in the present invention -
The ethylene block copolymer is not particularly limited, but M'
P process is 0.1~50g710min, preferably 05~30g
11,710 minutes and an ethylene content of 1 to 30 parts by weight, preferably 2 to 15 parts by weight. The method for producing the propylene-ethylene block copolymer is not particularly limited, and for example, propylene is polymerized in the presence of a catalyst containing titanium trichloride and an organoaluminum compound, and then propylene is polymerized in the presence of the polymer containing the catalyst obtained in the first step. Additionally, there is a bifurcated F# polymerization method in which ethylene alone or a mixed monomer of engineered ethylene and □′ □111° propylene are subjected to push copolymerization.

Examples of the unsaturated monocarboxylic acids used in the present invention include acrylic acid, methacrylic acid, maleic acid, heptadmaric acid, and itaconic acid.

Citraconic acid, anhydrides and esters.

Amides, imides, metal salts, etc., such as maleic anhydride, citraconic anhydride, itaconic anhydride.

Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, glycidyl acrylate, glycidyl methacrylate, monoethyl maleate, diethyl maleate, monomethyl heptalate ,7
Malic acid dimethyl ester, itaconic acid monomethyl ester, itaconic acid diethyl ester, acylamide,
methacrylamide, maleic acid monoamide, maleic diamide, maleic acid-N-monoethylamide, maleic acid-N,N-diethylamide, maleic acid-N-motuptilamide, maleic acid-N,N-dibutylamide,
7. Marumaric monoamide, 7maric acid diamide, fumaric acid-
ni-monoethylamide, 7maric acid-N,N-diethylamide, 7malic acid-N-monobutyramide, 7maric acid-N-s
Examples include ew-dibutylamide, maleimide, N-butylmaleimide, N-phenylmaleimide, sodium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate, and the like. Among these, it is most preferable to use maleic anhydride. The amount of such unsaturated carboxylic acids used is not particularly limited, but in order to obtain good modified polypropylene, polypropylene
It is generally necessary to add 1 to 20 parts by weight of O and C, preferably 5 parts by weight to 00 parts by weight.

Organic peroxides are used to promote the reaction between propylene and unsaturated carboxylic acids. Examples of organic peroxides include benzoyl peroxide and lauroyl peroxide.

Azobisisobutylnitrile, dicumyl peroxide, α,α-bis(t-butylperoxy(10) diisopropyl)benzene, 2,5-dimethyl-2,5
-di(t-butylperoxy)hexane.

Examples include 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, di-t-butyl peroxide, cumene hydroperoxide, and t-butyl hydroperoxide. The addition lid of the organic peroxide is not particularly limited, but it is usually o, oos to 5 parts by weight, preferably 0.01 to 1 per 100 parts of volippyrene.
fi amount part.

Next, the polypropylene, unsaturated carboxylic acids, and organic peroxide shown above are thoroughly mixed in a tumbler, Henschel mixer, etc., and melt-kneaded at a temperature above the melting point of polypropylene, generally above the melting point and below 280°C. to carry out the grafting reaction. The method of melting and kneading is not particularly limited,
For example, screw extruder, Banbury mixer.

This can be carried out using a mixing roll or the like, but a screw extruder is preferably used for ease of operation. The temperature and time (11) of melt cross-talk will vary depending on the decomposition humidity of the organic peroxide used, but generally a temperature of 160 to 280°C for 3 to 30 minutes, preferably a temperature of 170 to 250°C for 1 to 10 minutes is appropriate. be. Note that the melt-kneading may be performed in an inert gas stream.

However, in the modified polypropylene produced as described above, even if unsaturated carboxylate 8 is used in a predetermined ratio as described above, unreacted monomers inevitably remain. Therefore, in order to obtain the desired purpose, it is desirable to further heat-treat the modified polypropylene at a temperature of 60°C or higher, preferably 100°C or higher. Heating temperature is 6
If the temperature is 0° C. or lower, the treatment 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 melting. The heat treatment means may be a conventionally known method, such as an aeration band type dryer, a material stirring type dryer, a fluidized bed dryer, a flash dryer, a jet dryer, a single rotation dryer, or a drum type dryer (12). , a vacuum dryer, an infrared dryer, a far-infrared dryer, a microwave dryer, etc., but a hot air dryer is preferably used. Note that if the heat treatment is performed under reduced pressure, the treatment effect will be further improved.

The heat treatment time is not particularly limited, but if the heating temperature is low and the modified polypropylene contains a large amount of unreacted monomers of unsaturated carboxylic group 8, it will take a long time; If necessary, a short period of time is sufficient. Generally, it is preferable to carry out the heat treatment so that the amount of unreacted monomer residue is 0.1% by weight or less.

Modified polypropylene (6) produced as above
A finely powdered inorganic filler (1)), and preferably an ethylene polymer (0), and if necessary, an unmodified filler (0).
A modified l-ripropylene composition is obtained by mixing lip-tetrapyrene.

Although the propylene-ethylene block copolymer does not necessarily have to be graft-modified with unsaturated carboxylic acids,
It is necessary that the modified propylene (A) contains (13) at least 30 wt% or more of the brobylene-ethylene plastic copolymer component.

That is, when the propylene-ethylene block copolymer component in the modified polypropylene is less than 30 at%, the modified polypropylene composition containing the finely divided inorganic filler has good adhesion to metal; .

Fine powder inorganic filler (B) used in the present invention +! Although not particularly limited, it is preferable that the average particle diameter is 50 μm or less. Examples of the fine powder inorganic filler (B) include calcium carbonate, talc, clay, silica, diatomaceous earth, alumina, zinc white, i! ! Magnesium chloride.

, mica, calcium silicate, calcilla sulfate, calcium sulfite, magnesium carbonate, aluminum hydroxide,
Examples include calcium hydroxide, glass powder, asbeth), etc. Among these, calcium carbonate is preferably used. The blending amount of the fine powder inorganic filler is 2 to 200 parts by weight per 100 parts by weight of the modified polypropylene (A).
Weight part.

Preferably it is 5 to 100 parts by weight. When the amount added is less than (14) 2 parts by weight, the effect of improving adhesion is small, and 200
On the contrary, the adhesiveness decreases beyond the heavy lid part.

Incidentally, the fine powder inorganic filler (B) may be added at the same time as the grafting reaction of unsaturated carboxylic acids to polypropylene.

The ethylene polymer used in the present invention is, for example, an ethylene homopolymer polymerized by a high-pressure method or a medium-low pressure method, ethylene and other polymerizable monopolymers of 60% by weight or less, preferably 40% by weight or less. Copolymers with ethylene and propylene, such as ethylene and propylene,
Butene-11hexene-1,3-methyl-pentene-1
゜One or two α-olefins such as 4-methyl-pentene-1! Copolymers of ethylene and vinyl esters such as vinyl acetate and vinyl propionate, copolymers of ethylene and vinyl esters such as vinyl propionate, ethylene and acrylic acid, methacrylic a! , unsaturated carboxylic acids such as maleic acid or their derivatives, such as anhydrides, esters, amides, imides, chlorides, metal salts, etc., copolymers of ethylene and
15) It refers to a copolymer of tadiene, dicyclopentadiene, ethylidenenorbornene, etc. with a conjugated or non-conjugated diene, or a mixture of the above polymers. These polymers may be subjected to various modifications such as oxidation, chlorination, chlorosulfonation, or grafting with epoxy compounds or carboxyl group-containing compounds. Among these, low density polyethylene, ethylene-propylene copolymer, and ethylene-butene-1 copolymer are preferably used. Ethylene polymer (0) is M7E (A8TM-D-1238,
230° C.) is preferably in the range of 0.1 to 50 f/10 minutes.

Ethylene polymer in modified polypropylene composition (
The blending amount of C) is 1 to 100 parts by weight, preferably 5 to 6 parts by weight, per 100 parts by weight of modified y + propylene yield).
It is 0 parts by weight. If the amount of paethylene-based iris aggregate (0) is less than 111 parts by weight, the effect of improving adhesion will be small, and if it exceeds 100 parts by weight, not only will the adhesion decrease, but the mechanical strength will decrease. This is not preferable because it lowers the temperature. Incidentally, the ethyl(16) lene polymer (0) may be added at the same time as the grafting reaction of the unsaturated carbones m to the polypropylene.

Modified polypropylene (4), fine powder inorganic filler (B).

Preferably, the ethylene polymer (0) or, if necessary, unmodified polypropylene is mixed in a tumbler,
This can be carried out using a Henschel mixer or the like, and melt-kneading is carried out using a screw extruder, Banbury mixer, mixing roll, or the like.

The modified propylene composition produced as described above desirably contains unsaturated carboxylic acids of 0005 to 5 by weight. The content of unsaturated carboxylic acids is 0.
When the amount is less than 00505 parts by weight, the effect of improving adhesion is small, and when it exceeds 5% by weight, not only does the manufacturing cost increase, but the effect of improving adhesion 1 becomes saturated. The modified polypropylene composition also contains heat-resistant stabilizers, weather-resistant stabilizers, lubricants, antistatic agents, and nucleating agents to the extent normally used.

It may contain pigments, dyes, flame retardants, anti-blocking agents, etc. (17)-0 The metals used in the present invention are not particularly limited, and include iron,
Aluminum, lithium, nickel, gold, silver.

#14. Magnesium, zinc, tin * Steel # Zfless.

Examples include galvanized iron, tinplate, etc., with iron and aluminum being preferably used.

The present invention also includes a modified propylene composition layer (X or X'), a metal layer (7) and an unmodified polypropylene layer (
A laminate consisting of Z) is also included. Unmodified polypropylene (there are no particular restrictions on the gradient, such as homopolypropylene, propylene-ethylene random copolymer, propylene-ethylene block copolymer, copolymers of propylene and other α-olefins, and mixtures thereof, In addition, the unmodified polypropylene (Z) contains commonly used polymeric substances other than ribropylene, inorganic or organic fillers, heat-resistant stabilizers, weather-resistant stabilizers, lubricants, antistatic agents,
It may also contain nucleating agents, pigments, dyes, flame retardants, antiblocking agents, and the like.

(18) The laminate of the present invention does not require the use of an adhesive or the like during lamination, the metal (7) is a plate, and the modified polypropylene composition (X or xl) or the unmodified polypropylene (Z) is A set of films or sheets consists of both (Y and X or xi > or three (y, x or X',
And 2) may be laminated into two or more layers and bonded under heat. Pressure bonding methods include compression molding, extrusion lamination, and other melt pressure bonding methods.
It can be carried out. Furthermore, when the metal is in the form of a plate or other processed product, the resin layer can be laminated onto the metal layer by applying powder coating or emulsion coating.

As an example of the structure of the laminate, metal layer thickness)/modified l libruby1
Polypropylene composition layer (X or X') / modified polypropylene composition layer (X or X') / metal layer, metal layer (
b)/Modified polypropylene composition layer (X or X')/
A three-layer structure such as an unmodified polypropylene composition layer (Z), a metal layer (7)/an envy polypropylene composition layer (X or
')/Unmodified polypropylene layer (2)/Modified poly(19
) A five-layer structure such as a propylene composition layer (X or

The polypropylene/kinkoshidan layer obtained in the above manner has a strong adhesive strength between the two, and has both the excellent characteristics of polypropylene and the excellent hazardous properties of metal. It also has excellent new features that are not available before, making it suitable for automobile materials, industrial materials, and building materials.

It can be effectively used as a packaging material for beverage cans and various types of food products.

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

In addition, the adhesive strength of the obtained laminate with metal is
It was measured by the following method. MIP knee 1,5 g/1
40 parts by weight of calcium carbonate with an average particle size of 1.2μ was mixed into a 100% heavy lid of a prepylene-ethylene block copolymer with a lid arc containing 27 feet and 1 f L/h, and then extruded using a 00M extruder with a vent. , (20) Melt-kneading pelletization was performed at 200°C to obtain an unmodified propylene composition. 0.1 n by extruder with T-die
Sheets of modified polypropylene compositions of thickness (force and 0
．． A sheet (Z) of unmodified polypropylene obtained above having a thickness of 2 ff was formed. Meanwhile, the metal sheet (7) is
The paper was cut into pieces with a width of 12 cm and a length of 12 cm. 3
For layer laminates, stack them in the order of y / x / y, or for 5-layer laminates, in the order of Y / x / z / x / y, and apply a pressure of 10 & 9 / C - at 200 ° C for 3 minutes. After crimping, the modified l-lipropylene composition was allowed to cool, and the protruding portion of the modified l-lipropylene composition protruding from the two metal sheets was neatly cut off with a knife at 23°C.

It was left in a constant temperature and humidity room at 50% RH for 24 hours.

The T-peel strength was measured by holding the ends of two metal sheets in the chuck of a tensile testing machine at a tensile speed of 2 o y/win. In addition, the thickness of the metal sheet is 0.
2 battles, aluminum sheet 0.11111.

(21) Example 1 and Comparative Example IM? Eny, 61/1o min, ethylene content 2.0
Heavy duty prepyrene-ethylene random copolymer Zoo
Parts by weight, maleic anhydride #2 parts by weight, 2,5-dimethyl-
03 parts by weight of 2,5-di(t-butylperoxy)hexane, 0.1 parts by weight of butylated human'roxytoluene
1 part by weight of calcium stearate was mixed for 5 minutes using a hexyluminizer and a lumixer, melted and mixed into pellets at 220°C using a 11/D-24 4ozml extruder, and then heat-treated at 145°C for 4 hours using a constant temperature dryer. Modified polypropylene (hereinafter also abbreviated as modified PP) was obtained. The modified polypropylene had a graft content of 0.51-m maleic anhydride.

The above modified polypropylene, unmodified polypropylene (P
P) and calcium carbonate (average particle size 1,2μ)
1 and melt-kneaded at 200 tl using a vented 00M extruder to obtain a modified polypyrene composition. The properties of unmodified PP shown in Table-fill are as follows.

(22) (1) Forecast P: M P I-1,
51710 minutes ethylene containing 112. % by weight (2)*%PP: MFl, -x, 51/xo min (
3) 5! A P P : M F I =
1.711 / 10 minutes Ethylene content 25 weight arc Sheets formed from each of the modified polypropylene compositions obtained above (the unmodified polypropylene sheet (2) and the aluminum sheet (7)) Akara 1 Laminates were manufactured under predetermined conditions.Table 1 shows the adhesive strength of each laminate.

(23) Example 2 and Comparative Example 2 In Example 1, an ethylene polymer was further added in a predetermined ratio shown in Table 2 to obtain a polypropylene composition. The properties of the ethylene polymer shown in Table 2 are shown below.

(1) Ethylene 2-butene-1 copolymer: MIFI-
6,49/10 minutes Ethylene content 80% (2) Ethylene-propylene copolymer: MFI-5
, 1f/10min Ethylene content 70% by weight (3) Low density polyethylene: MFI-4. Of/1 Specific gravity 0.920 Each of the modified polypropylene compositions obtained above was used.
Then, in the same manner as in Example 1, a predetermined laminate was experimentally manufactured. Table 2 shows the adhesive strength of each laminate.

(25) Example 3 100 parts by weight of the propylene-ethylene brick copolymer used in Example 1, 20 parts by weight of talc with an average particle size of 0.3 μm, and 0.5 parts by weight of anhydrous maleic fi.

03 parts by weight of benzoyl peroxide, 1201 parts by weight of butylated hydroxyl, 0 parts by weight of calcium stearate
1 part by weight was mixed for 5 minutes in a Henschel mixer, melt-line pelletized at 200°C using a vented 00M extruder, and heat-treated at 145°C for 3 hours in a constant temperature dryer. Modified polypropylene composition obtained using this method
A three-layer laminate with iron was obtained in the same manner as in Example 1 using 1. Its adhesive strength was 8.7 to 9/2 C1l.

Example 4 The same procedure as in Example 3 was carried out except that 10 parts by weight of the ethylene-propylene copolymer used in Example 1 was further added to Example 3. The adhesive strength of the obtained three-layer laminate is xz, s&
It was p/2c+i.

Comparative Example 3 The same procedure as in Example 3 was carried out except that maleic anhydride was not added (27). The adhesive strength of the obtained three-layer laminate was O.

Comparative Example 4 The same procedure as in Example 3 was carried out except that talc was not added. The adhesive strength of the obtained 3N laminate is]
lky/2C++1.

Comparative Example 5 The same procedure as in Example 4 was carried out except that talc was not added. The degree of m enhancement of the obtained three-layer laminate was 4.
It was 1 kg/2 cm.

Comparative Example 6 The same procedure as in Example 3 was conducted except that the homopolypropylene used in Comparative Example 1 was used instead of the propylene-ethylene block copolymer. The resulting three-layer laminate had an adhesive strength of 1.5 to 9/2C.

Comparative Example 7 The same procedure as in Example 3 was carried out, except that in JilliN 3, the propylene-ethylene random copolymer used in Comparative Example 1 was used instead of the propylene-ethylene block copolymer. The adhesive strength of the obtained three-layer laminate was 2.2&p/2e*0 Patent applicant Tokuyama Soda Co., Ltd. (29)

Claims (1)

[Scope of Claims] (1) Propylene-ethylene block copolymer
A modified polypropylene composition layer CI) consisting of modified propylene partially or entirely grafted with unsaturated carboxylic acids (N and fine powder inorganic filler) containing 0% or more of heavy waves and a metal N-substituent. ) Laminate (2) The laminate consists of metal layer (Y)/modified polypropylene composition layer (Y)/metal layer (η).
The laminate (3) modified propylene composition described in section (l) is composed of a finely powdered inorganic filler (
B) Claim No. 1 containing 2 to 200 parts by weight
) The content of unsaturated carboxylic acids in the laminate (4) fully modified polypropylene composition is 0005 to 51%, Claim (1) XJl&! Brush laminate (5) Claim No. 1 in which the unsaturated carboxylic acid is maleic anhydride (
The laminate (6) according to claim 1) The laminate (7) according to claim 1, wherein the fine powder inorganic filler is calcium carbonate. (8) The laminate according to claim (1), which is l-ripropylene containing modified polypropylene grafted with an acid. The laminate (9) according to claim (1), which is heat-treated at a humidity below the melting point of the pyrene component (9) The metal (7) is iron or aluminum, according to claim (1) Laminate of 00 propylene-ethylene block copolymer 3
An interlayer of a modified polypropylene composition consisting of a modified polypropylene (A) partially or entirely grafted with unsaturated carboxylic acids, a finely powdered inorganic filler (B), and an ethylene polymer (0) containing over 00 parts by weight. and Gold II4M (
7) Laminated product (11) A laminate according to claim (lO), in which the laminate consists of metal layer (Y)/modified polypropylene composition interlayer/metal layer (7) (12) Modified melib The p-pylene composition contains a fine powder inorganic filler (
B) 2 to 200 parts by weight and ethylene polymer (0)
(13) The laminate according to claim 1 (13) in which ethylene, 1% polymer contains ethylene-butene-1 copolymer, ethylene-propylene copolymer, and The laminate according to Claim No. (lO)]lJI, which is at least one type derived from high-density polyethylene. (14) Partially or completely containing 30% by weight or more of a propylene-ethylene plastic copolymer. A modified polypropylene composition layer (3) consisting of a modified polypropylene (A) grafted with an unsaturated carboxylic acid and a finely powdered inorganic filler (B), a gold style layer (Y), and an unmodified polypropylene layer (Z). (15) A laminate consisting of a metal layer (2)/modified polypropylene composition layer (1)/unmodified polypropylene layer (2).
)/Modified propylene composition M(X)/Metal layer (7)
A laminate according to Claim No. (14)'fB consisting of: (16) Modified polypropylene containing 30% by weight or more of a propylene-ethylene plastic copolymer and partially or entirely grafted with an unsaturated carboxyl group (4);
A modified polypropylene composition layer (support) consisting of a fine powder inorganic filler body) and an ethylene polymer (0) and a metal layer (
7) and an unmodified polypropylene layer (Z). (17) The laminate consists of metal layer (Y)/modified polypropylene composition interlayer/unmodified polypropylene composition interlayer (2)/modified polypropylene composition interlayer/metal layer (Y) 16) The laminate described in item 16).