JPH08118568A - Laminate - Google Patents

Abstract

PURPOSE: To obtain a laminate having excellent transparency and heat resistance by incorporating modified polypropylene in which polypropylene is grafted with at least one type of unsaturated carboxylic acid or its derivative, the unsaturated carboxylic acid or its reactive compound, representing the relation between melting tension and MFR by the formula and specifying the MFR by a specific value. CONSTITUTION: A laminate comprises a layer containing a propylene polymer composition having an ingredient (1) containing modified polypropylene in which polypropylene is grafted with at least one type of unsaturated carboxylic acid or its derivative and an ingredient (2) containing reactive compound having two or more functional groups reacted with the unit based on unsaturated carboxylic acid or its derivative in the modified polypropylene in a molecule as indispensable ingredients in such a manner that the relation between the melting tension and MFR (melt flow index) and the MFR is in a range of 1 to 100g/10min, and a base material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate having a layer made of a propylene polymer composition and a substrate and having excellent transparency, heat resistance and scratch resistance, and particularly to a laminate obtained by extrusion lamination. Regarding

[0002]

2. Description of the Related Art A laminate comprising a propylene-based polymer and a base material has a small melt tension of the propylene-based polymer, so that when it is wound at a high speed, the uneven thickness of the melted film becomes large, and extrusion lamination molding is difficult. It was As a method for improving this drawback, a method of adding high-pressure low-density polyethylene is known, but this method impairs the original transparency, heat resistance, and scratch resistance of polypropylene, and thus provides good transparency. It was difficult to obtain a laminate having heat resistance and scratch resistance.

As a method for producing a propylene-based polymer having a high melt tension, a. Irradiation of radiation (high energy rays) b. Methods such as peroxide crosslinking may be mentioned. These are methods of increasing melt tension by partially cross-linking after polymerization and introducing long chain branching. However, since a requires large-scale equipment and b requires kneading, it is not desirable in terms of cost. Further, both a and b are deteriorated at the same time, which is not preferable in terms of physical properties. In addition, when a large amount of a bridge structure is introduced to obtain a high melt tension, the gel component is increased and the performance required for the laminate material is impaired, and a small amount causes a problem of insufficient melt tension.

[0004]

As described above, the propylene-based polymer has excellent properties of transparency, heat resistance and scratch resistance, but since it has a low melt tension, it can be extruded and laminated by itself. It was difficult to obtain a laminate. In view of such a situation, it is an object of the present invention to provide a laminate having excellent transparency, heat resistance, and scratch resistance that a propylene-based polymer originally has.

[0005]

As a result of intensive studies, the present inventors have found that after grafting an unsaturated carboxylic acid or a derivative thereof onto a propylene-based polymer, a plurality of groups which react with the grafted functional group are reacted. A laminate comprising a substrate and a propylene-based polymer composition layer having a certain relationship between melt tension and MFR, which is obtained by forming a bridged structure with a reactive compound having a functional group, is substantially The inventors have found that the above gel component is small and have excellent transparency, heat resistance, and scratch resistance, and have reached the present invention.

That is, the object of the present invention is to provide component (1): a modified polypropylene obtained by grafting polypropylene with at least one unsaturated carboxylic acid or a derivative thereof, and component (2): an unsaturated carboxylic acid in the modified polypropylene. Alternatively, a reactive compound having two or more functional groups that react with units derived from its derivative in the molecule is contained as an essential component, and the melt tension and melt flow index (MFR) are represented by the formula (1) log (melt tension). > -1.16 × log (MFR) +0.92 (1) and MFR in the range of 1 to 100 g / 10 min. This can be achieved by a laminate composed of a material. The present invention will be described in detail below.

The polypropylene used for producing the modified polypropylene of the component (1) in the present invention is a homopolymer of propylene or a so-called random copolymer of propylene with a small amount of ethylene and an α-olefin such as butene-1. It is possible to provide polypropylene, a so-called ethylene / propylene block copolymer produced by sequential polymerization using a plurality of reactors, or a combination thereof. Also, a small amount of dienes such as 1,9-decadiene,
It is also possible to use a copolymer obtained by adding 1,5-hexadiene, 1,4-hexadiene, isoprene, 1,3-butadiene, 1,3-pentadiene and the like.

The unsaturated carboxylic acid or its derivative used for obtaining the modified polypropylene of the component (1) in the present invention (the acid and the derivative may be used alone or simultaneously and hereinafter referred to as an unsaturated carboxylic acid compound). As, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, maleic anhydride, itaconic anhydride, endic acid anhydride, citraconic anhydride, 1-butene-3. , 4-
Examples thereof include dicarboxylic acid anhydrides and alkenyl succinic anhydrides having a double bond at the terminal having at most 18 carbon atoms. These may be used alone or in combination of two or more. Of these, maleic anhydride and itaconic anhydride are preferably used.

In the modified polypropylene of the component (1) in the present invention, the unit derived from the unsaturated carboxylic acid compound is generally 0.01 to 2.0% by weight, preferably 0.03 to 1.0% by weight. It is in the range, and more preferably in the range of 0.05 to 0.7% by weight. When the amount of the unit derived from the unsaturated carboxylic acid compound is less than 0.01% by weight, the melt tension is insufficiently improved, so that the sufficient effect of improving the moldability cannot be obtained. On the other hand, if it exceeds 2% by weight, a large amount of gel component is generated, and the appearance is greatly impaired.

In producing the modified polypropylene according to the present invention, various methods which are generally known can be used. That is, a solution of polyolefins dissolved in a solvent to prepare a solution, a solution grafting method of mixing and reacting a radical initiator and an unsaturated carboxylic acid compound, a melt grafting method of modifying in an extruder in the absence of a solvent, an electron beam, etc. The radiation grafting method to be used can be used. Further, in order to remove the unreacted unsaturated carboxylic acid compound, it is preferable to carry out a step of removing unreacted substances, reaction by-products and the like by washing with a solvent or warm water after the graft modification.

Melt flow rate of modified polyolefin relating to the present invention (JIS-K-7210, Table 1, Condition 1)
4), hereinafter referred to as MFR), is generally preferably 0.1 to 1000 g / 10 min, 1 to 200
g / 10 minutes is particularly preferred. Outside this range, a laminate meeting the object of the present invention cannot be obtained.

The functional group in the component (2), which is a constituent of the propylene-based polymer composition used in the present invention, reacts with the unit derived from the unsaturated carboxylic acid or its derivative in the component (1). It must be a thing.
Examples thereof include a hydroxyl group, an amino group, an epoxy group and an isocyanate group. Particularly preferred are a hydroxyl group, an amino group and an epoxy group.

Examples of the reactive compound having two or more hydroxyl groups in the molecule include glycols such as ethylene glycol, diethylene glycol and triethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1, Alcohol compounds such as 8-octanediol, 1,10-decanediol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, arbitol, sorbitol, xylose, arabinose, glucose, galactose,
Sugars such as sorbose, fructose, palatinose, maltotriose, and malezitose, saponification products of ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyolefin oligomers having a plurality of hydroxyl groups, ethylene-hydroxyethyl (meth) acrylate [(meth) Acrylate means methacrylate or acrylate. The same shall apply hereinafter] A copolymer having a plurality of hydroxyl groups in its molecule such as a copolymer may be mentioned.

It is also possible to use a polyoxyalkylene compound having a structure in which ethylene oxide or propylene oxide is added to a polyhydric alcohol compound, and a polyglycerin ester obtained by dehydration condensation of these and an organic carboxylic acid compound. . The polyoxyalkylene compound as described above is a compound obtained by adding propylene oxide to trimethylolpropane, a compound obtained by adding ethylene oxide to trimethylolpropane, a compound obtained by adding ethylene oxide to pentaerythritol, and a compound obtained by adding propylene oxide to diglycerin. , A compound obtained by adding ethylene oxide to tetraglycerin, a compound obtained by adding propylene oxide to decaglycerin, and the like.

Examples of these polyoxyalkylene compounds include 1,3-dihydroxypropane, 2,2-dimethyl-1,3-dihydroxypropane, trimethylolethane, 1,1,1-trimethylolpropane, 1, 1,1-trimethylolhexane, 1,1,1-trimethyloldodecane, 2-cyclohexyl-2-methylol-1,3-dihydroxypropane, 2- (p-methylphenyl) -2-methylol-1,3- Dihydroxypropane, pentaerythritol, glycerin,
Diglycerin, hexaglycerin, octaglycerin,
Examples thereof include compounds obtained by adding ethylene oxide or propylene oxide to decaglycerin and the like.

Examples of the polyglycerin ester as described above include glycerin monostearate, glycerin monooleate, glycerin monolaurate,
Glycerin monocaprylate, glycerin monohexanoate, glycerin monophenethyl ester, glycerin monopropionate, diglycerin monostearate, diglycerin distearate, diglycerin monooleate, diglycerin monohexanoate, diglycerin di Octanoate, tetraglycerin monostearate, tetraglycerin tristearate, tetraglycerin tetrastearate, tetraglycerin trihexanoate, tetraglycerin monophenethyl ester, hexaglycerin monostearate, hexaglycerin distearate, hexaglycerin penta Stearate, hexaglycerin trioleate, hexaglycerin monolaurate, hexaglycerin pentalaurate, decaglycerin molybdenum Stearate, decaglycerol octa stearate, decaglycerol pentaoleate, decaglycerol monolaurate, decaglycerol dilaurate, pentaerythritol decaglycerol distearate, pentaerythritol decaglycerol deca oleate, octadecanol glycerol tetrastearate, and the like.

Further, as the sorbitan alkyl ester, for example, sorbitan monostearate, sorbitan monooleate, sorbitan monolaurate, sorbitan monocaprylate, sorbitan monohexanoate, sorbitan monophenethyl ester, sorbitan monopropionate, Examples thereof include sorbitan tristearate and sorbitan tetrastearate. Among these, preferred ones have a valence (number of hydroxyl groups in one molecule) of 3 to
7

Examples of the reactive compound having two or more amino groups in the molecule include ethylenediamine, diaminopropane, diaminobutane and 1,2-dimethyl-1,3.
-Propaneamine, hexamethylenediamine, 2-methyl-1,5-pentadiamine, diaminoheptane, diaminooctane, 2,5-dimethyl-2,5-hexanediamine, diaminononane, diaminodecane, diaminododecane, diethylenetriamine, N- (Aminoethyl)
-1,3-methyldipropanediamine, 3,3'-diamino-N-methyldipropylamine, 3,3'-iminobispropylamine, triethylenetetramine, tris (2-aminoethyl) amine, tetraethylenepenta Min, 1,4-diaminocyclohexane, polyethyleneimine and the like.

Alternatively, a compound having both an amino group and a hydroxyl group can be used. For example, ethanolamine 2-hydroxyethylhydrazine, 3-amino-1-propanol, DL-2-amino-1-propanol, DL-1
-Amino-2-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 2-amino-1-
Pentanol, DL-2-amino-1-pentanol,
6-amino-1-hexanol, 2- (2-aminoethoxy) ethanol and the like are used.

Examples of the reactive compound having two or more epoxy groups in the molecule include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, hydroquinone diglycidyl ether, diglycidyl bisphenol A and water thereof. Additives, phthalic acid diglycidyl ester, trimethylolpropane triglycidyl ether, butanediol diglycidyl ether, epoxidized soybean oil, epoxidized linseed oil, cyclohexanedimethanol diglycidyl ether, hexanetriol glycidyl ether, alicyclic epoxy resin, Heterocyclic epoxy resin, brominated epoxy resin, bisphenol A-epichlorohydrin resin, polyfunctional epoxy resin, aliphatic epoxy resin, brominated Novolac type epoxy resins, brominated bisphenol A type epoxy resins, biphenyl type epoxy resins, polyglycidyl amine epoxy resins, ester type epoxy resin, ortho-cresol novolak type epoxy resin, phenol novolak type epoxy resin or the like.

Examples of the reactive compound having two or more isocyanate groups in the molecule include ethylene diisocyanate, diisocyanate butane, diisocyanate hexane, diisocyanato dodecane, diisocyanate-2-methylpentane. , M-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthylene diisocyanate, 4 ′,
4 ', 4 "-triphenylmethane triisocyanate, 4,4'-diphenylmethane triisocyanate,
3,3'-dimethyl-4,4'-diphenylene diisocyanate, m-xylylene-diisocyanate, p-xylylene-diisocyanate and the like can be mentioned.

The molecular weight of these components (2) is preferably 3000 or less. If the molecular weight exceeds 3000,
A large amount of gel component may be generated. The melting point of these compounds is preferably 300 ° C. or lower. Two or more kinds of these compounds may be used in combination at the same time.

The content of the component (2) of the present invention is such that the functional group of the reactive compound in (2) is based on the unit of the acid anhydride group derived from the unsaturated carboxylic acid or its derivative contained in the modified polypropylene. The ratio of the number of groups is preferably in the range of 1:10 to 10: 1, preferably in the range of 1: 7 to 7: 1, and 1:
5-5: 1 is particularly preferred. If it deviates from the range of 1:10 to 10: 1, an effective amount of the crosslinked structure cannot be introduced into the composition, and it becomes difficult to satisfy the above-mentioned relationship between the melt tension and the MFR, resulting in moldability. It becomes insufficient and a good laminate cannot be obtained.

In the propylene polymer composition according to the present invention, MFR (measurement condition: JIS-K-721
0, Table 1, condition 14) and melt tension (measurement condition: orifice inner diameter 2.095 ± 0.005 mm, orifice length 8,000 ± 0.025 mm, resin temperature 230 ° C., take-up speed 6.5 m / min, extrusion) It is important that the relationship of equation (1) exists between the speeds of 15 mm / min). log (melt tension)> − 1.16 × log (MFR) +0.92 (1) Usually, the melt tension of polypropylene and the MFR show a proportional relationship. The propylene-based polymer composition used for the laminate of the present invention shows a value larger than the melt tension that can be inferred from the straight line showing the normal proportional relationship with MFR. This MFR
Equation (1) shows the relationship between the melt tension and the melt tension. When the MFR and melt tension of the composition according to the present invention do not satisfy the formula (1), it cannot be said that the melt tension is improved and the moldability of the extrusion laminate is not improved. Where the MF of the composition
R is 1.0 to 100 g / 10 minutes, 5.0 to 50
g / 10 minutes is particularly preferred.

In the present invention, a reaction accelerator may be used. This activates the carbonyl group contained in the unsaturated carboxylic acid or its derivative, hydroxyl group, amino group,
It is a compound that promotes a reaction with an epoxy group and an isocyanate group. An example of such a reaction accelerator is a metal salt of an organic carboxylic acid. Examples of metal salts of organic carboxylic acids include carboxylic acids such as acetic acid, butyric acid octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and behenic acid, which are fatty acids having 1 to 30 carbon atoms. And IA, IIA, IIB of the periodic table
Group IIIB metal (eg Li, Na, K, Mg, C
a, Zn, Al, etc.).

Another example of the reaction accelerator is a tertiary amine compound. Specific examples of the tertiary amine compound used here include trimethylamine, triethylamine, triisopropylamine, trihexylamine, trioctylamine, trioctadecylamine, dimethylethylamine, methyldioctylamine,
Dimethyloctylamine, diethylcyclohexylamine, dimethylbenzylamine, N, N-diethyl-4-
Methylcyclohexylamine and the like can be mentioned.

As the reaction accelerator, a metal salt of an organic carboxylic acid or a tertiary amine compound may be used alone, or a metal salt of an organic carboxylic acid and a tertiary amine compound may be used in combination. Also, two or more kinds of metal salts of organic carboxylic acids and tertiary amine compounds may be used in combination.

The amount of the reaction accelerator used in the present invention is 0.1% by weight based on 100 parts by weight of the components (1) and (2).
A range of 001 to 10 parts by weight is desirable. More preferably, it is in the range of 0.005 to 8 parts by weight, more preferably 0.
It is in the range of 01 to 6 parts by weight. If the amount of the reaction accelerator is out of this range and the amount is small, the carbonyl group contained in the unit derived from the unsaturated carboxylic acid and its derivative in the component (1) cannot be activated. Further, when the amount of the reaction accelerator is out of the above range, the reaction is substantially meaningless in terms of activating the carbonyl group, and further, other physical properties of the composition of the present invention may be impaired. Not preferable.

The modified polypropylene as the component (1) used in the laminate of the present invention is essential, but not only the component (1) but also another unmodified polyolefin resin may be blended, and the effect of the present invention is obtained. Rather, it is economically preferable to mix it in a range that does not impair it. The unmodified polyolefin that may be blended is a polyethylene resin,
There are polypropylene resin, polybutene resin, etc.,
Especially, the polypropylene used for producing the modified polypropylene as exemplified above is preferable. In this case, the effect of the present invention is not hindered as long as the blending ratio of the unmodified polyolefin to the modified polypropylene does not exceed 50 times by weight. Further, in the propylene polymer composition according to the present invention, various additives, compounding agents and fillers can be used as long as the characteristics of the composition are not impaired. Specific examples of these are antioxidants (heat stabilizers), ultraviolet absorbers (light stabilizers), antistatic agents, antifogging agents, flame retardants, lubricants (slip agents, antiblocking agents), glass fillers, etc. Inorganic fillers, organic fillers, reinforcing agents, colorants (dyes, pigments), foaming agents, fragrances, and the like.

As a method for producing the propylene polymer composition, various commonly known resin mixing methods can be used. As a specific method, there can be mentioned a method of mixing the respective components in a molten state, that is, a method of using a pressure kneader, a roll, a Banbury mixer, a static mixer, a screw type extruder and the like which are generally used. .

It is also possible to melt mix the components during molding. That is, it is also possible to mix (dry blend) the respective components in the form of pellets or powder, and melt-mix using the step of producing a laminate using an extrusion laminate molding machine.

The laminate of the present invention can be obtained by extrusion laminating a propylene polymer composition on a substrate. Further, another synthetic resin film may be laminated on the layer made of the propylene polymer composition to form a multilayer laminate. A coextrusion method can also be used to form such a multilayer laminate.

The base material is selected according to the use, but is generally pure white paper, high-quality paper, coated paper, kraft paper, paperboard, etc., ordinary cellophane, cellophane such as moisture-proof cellophane, aluminum foil, iron foil, Metal foil such as tin foil, high pressure low density polyethylene film, low pressure low density polyethylene film, medium density polyethylene film, high density polyethylene film, ultra high molecular weight polyethylene film, polypropylene film, propylene-ethylene random copolymer film, propylene Ethylene block copolymer film, propylene / butene copolymer film, propylene / ethylene / butene copolymer film, ethylene /
Polyolefin films such as vinyl acetate copolymer film, ethylene acrylic acid copolymer film, ethylene / methacrylic acid copolymer film, vinylidene chloride,
Vinylidene chloride / acrylonitrile copolymer film,
Polyvinylidene chloride film such as vinylidene chloride / methacrylic acid copolymer film, polystyrene, polystyrene-based film such as polystyrene, styrene / acrylonitrile copolymer film, acrylonitrile / butadiene / styrene copolymer film, non-plastic polyvinyl alcohol film, Polyvinyl alcohol film such as plasticized polyvinyl alcohol film, saponified ethylene / vinyl acetate copolymer film, fluorine such as tetrafluoroethylene-6 fluoropropylene copolymer film, trifluoride / ethylene chloride copolymer film Resin films, polyester films such as polyethylene terephthalate film, polybutylene terephthalate, 1,4 cyclohexylene dimethylene terephthalate / isophthalate film, nylon 6, nylon Ron 6,6 polyamide films such as are selected as needed. The film may be biaxially stretched, uniaxially stretched, or non-stretched, and may be subjected to pretreatment such as printing, anchor coating and corona treatment.

Extrusion laminate as used herein generally means
The molten resin extruded by using a T-die is laminated between the two rolls by pressure bonding to the base material and is cooled and solidified. In this case, a cooled metal roll having a diameter of 300 mm to 1000 mm is used to rapidly cool and solidify the molten resin film. For the other roll, a rubber roll is generally used to complete the pressure bonding. In this way, a two-layer extrusion laminated film is made,
Insert another base material on the metal roll side of the molten resin film,
It is also possible to make a three-layer extruded laminated film at once. Further, a method of co-extruding the propylene-based polymer composition used in the present invention and another resin with a co-extrusion laminating apparatus and laminating it on a substrate is also possible.

The thickness of the layer made of the propylene polymer composition is preferably 5 to 100 μm, particularly preferably 10 to 40 μm. If it is 5 μm or less, it is difficult to laminate it on a substrate with a uniform thickness, which is not preferable from the viewpoint of product physical properties, and if it is 100 μm or more, it is necessary to slow down the molding speed in view of the balance with the discharge capacity of the extruder. However, it is not preferable in terms of productivity.

Such extrusion laminate molding is carried out by an ordinary extrusion laminate molding machine for polyolefin. The molding conditions at this time are not particularly limited, but generally, the resin temperature is 240 to 310 ° C., and the air gap is 60 to 2
00 mm, cooling roll temperature 10 to 50 ° C, molding temperature 50
~ 300 mm / min.

[0037]

EXAMPLES Next, the present invention will be specifically described by way of examples. However, the present invention is not limited by these examples. Melt tension is based on Toyo Seiki Co., Ltd.
Using a melt tension tester type II manufactured by Mfg. Co., Ltd., orifice inner diameter 2.095 ± 0.005 mm, orifice length 8.000 ± 0.025 mm, resin temperature 230 ° C., take-up speed 6.5 m / min, extrusion speed 15 mm / min. It is a value measured by the following and abbreviated as MT below. The heat resistance was evaluated by visually observing the gloss retention after the laminate was left in a 130 ° C. oven for 30 seconds. The scratch resistance was evaluated by a pencil scratch test according to JIS-K-5400. However, the load is 2
It was set to g.

Example 1 A modified polypropylene obtained by graft-modifying a propylene homopolymer with maleic anhydride was produced. The obtained modified polypropylene (1) has MF
R was 20 g / 10 minutes, and the unit derived from maleic anhydride was 0.23% by weight. The modified polypropylene 50
Parts by weight, 50 parts by weight of homopolypropylene (PP-A) having an MFR of 30 g / 10 minutes, trimethylolpropane triglycidyl ether as an epoxy compound (Epiclon 725 epoxy equivalent 141 manufactured by Dainippon Ink and Chemicals, Inc.)
0.165 parts by weight (epoxy group / maleic anhydride = 1.
3), 0.3 wt% of BHT (2,6-di-t-butyl-4-methylphenol) was mixed as an antioxidant. In mixing, after dry blending the three components with a tumbler, use a 30 mmφ twin-screw extruder to
The mixture was melt-kneaded at 0 ° C. and pelletized. The MFR of the mixture was 20.0 g / 10 minutes. MT was 0.31 g. Using this composition, a 90 mmφ extruder and a laminate molding machine were used to mold a biaxially stretched polypropylene film as a base material at a molding temperature of 280 ° C. and an air gap of 110 mm to obtain a laminate. The molding could be carried out without any problems. The obtained laminate had good appearance, transparency, heat resistance and scratch resistance.

(Examples 2 to 20) The same evaluation as in Example 1 was carried out by changing the types of modified polypropylene, polyolefin, reactive compound and substrate as shown in Table 1. The contents of each component used are shown in Tables 3-5. The results are shown in Table 1. All of the propylene-based polymer compositions used satisfied the relationship of the formula (1) and had good laminate moldability, and the obtained laminate had good appearance, transparency, heat resistance and scratch resistance. It was excellent.

(Example 21) The same procedure as in Example 1 was carried out except that 0.5 part by weight of calcium stearate was added as a reaction accelerator to the total parts by weight of the components (1) and (2). MFR was 18.0 g / 10 minutes and MT was 1.3 g. The relationship of Expression (1) was satisfied.

Example 22 N, N-as a reaction accelerator
The same composition as in Example 4 was evaluated except that 0.05 part by weight of dimethylbenzylamine was added to 100 parts by weight of the total amount of the components (1) and (2). MFR is 9.0g
/ 10 minutes, MT was 1.2 g / 10 minutes.

Example 23 Using the modified polypropylene (1), the composition shown in Table 1 was evaluated in the same manner as in Example 1. All the propylene-based polymer compositions used satisfied the formula (1). The moldability and appearance were also good, and the heat resistance and scratch resistance were excellent.

Comparative Example 1 The same evaluation as in Example 2 was performed using PP-A in Table 3 as it was. MFR is 30.
0 g / 10 minutes, MT was 0.10 g, and the formula (1) was not satisfied. In the case of molding by extrusion laminating, the molten film was surging, and molding could not be performed, so that a laminate could not be obtained.

Comparative Example 2 The same evaluation as in Example 2 was carried out except that no reactive compound was used. MFR is 32.
0 g / 10 minutes, MT was 0.11 g, and the formula (1) was not satisfied. In the case of molding by extrusion laminating, the molten film was surging, and molding could not be performed, so that a laminate could not be obtained.

Comparative Examples 3 and 4 Propylene polymer compositions were prepared by changing the ratio of the number of epoxy groups in the reactive compound to the units derived from the carboxylic acid group or its derivative in the modified polypropylene. Evaluation was performed in the same manner as in Example 1. Neither satisfied the formula (1). The moldability was not improved and the melt film was surging in the extrusion lamination molding, and a good laminate could not be obtained.

(Comparative Example 5) As a polyolefin, Table 3
Example 2 except that the high-pressure polyethylene PE-B in Example 1 was used and no modified polypropylene or reactive compound was used.
The same evaluation as was done. The moldability was good, but the laminate was opaque and was inferior in heat resistance and scratch resistance.

[0047]

[Table 1]

[0048]

[Table 2]

[0049]

[Table 3]

[0050]

[Table 4]

[0051]

[Table 5]

[0052]

According to the present invention, by effectively improving the melt tension of a propylene-based polymer, it is possible to obtain a highly transparent, high-gloss, heat-resistant material, which is composed of a propylene-based polymer composition particularly suitable for extrusion laminate molding. A laminate having excellent properties and scratch resistance was obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location B32B 27/10 9349-4F // C08L 23/26 LDA (72) Inventor Katsuji Ohira Kawasaki, Kanagawa Prefecture Akira Kawasaki-ku, Kawasaki-ku, Akira Kawasaki Plastics Research Laboratory (72) Inventor Satoshi Maruyama Satoshi-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Akira Kawasaki Plastics Research Laboratory

Claims (7)

[Claims] 1. Component (1): a modified polypropylene obtained by grafting at least one unsaturated carboxylic acid or its derivative onto polypropylene, and component (2): derived from the unsaturated carboxylic acid or its derivative in this modified polypropylene. Unit and a reactive compound having two or more functional groups that react with each other in the molecule as an essential component, and the melt tension and melt flow index (MFR) have the formula (1) log (melt tension)>-1.16. Xlog (MFR) +0.92 (1) and MFR is in the range of 1 to 100 g / 10 min. Laminate composed of a layer made of a propylene polymer composition and a substrate. body. 2. The laminate according to claim 1, wherein the functional group in the reactive compound as the component (2) is one or more groups selected from a hydroxyl group, an amino group and an epoxy group. . 3. The content of the unit derived from the unsaturated carboxylic acid or its derivative in the component (1) is 0.01 to.
It is 2.0 weight%, The laminated body in any one of Claim 1 or Claim 2 characterized by the above-mentioned. 4. The ratio of the units derived from the unsaturated carboxylic acid or the derivative thereof in the component (1) to the number of functional groups of the reactive compound in the component (2) is 1:10 to 10: 1. The laminated body according to any one of claims 1 to 3, which is characterized. 5. The components (1) and (2) are further supplemented with a metal salt of an organic carboxylic acid or a tertiary amine, and the components (1) and (2).
The amount of 0.001 to 10 parts by weight with respect to the total amount of 100 parts by weight is added in the range of 0.001 to 10 parts by weight. 6. The base material is paper, cellophane, metal foil, polyolefin film, polyvinylidene chloride film,
The laminate according to any one of claims 1 to 5, which is a polystyrene film, a polyvinyl alcohol film, a fluororesin film, a polyester film, or a polyamide film. 7. The laminate according to claim 1, wherein the layer made of the propylene-based polymer composition has a thickness of 5 to 100 μm.