JP2833823B2 - Laminate - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a laminate comprising a layer composed of a modified polyolefin resin, a layer composed of a polyester resin, and a layer composed of a specific resin for bonding these layers. About.

Among the laminates of the present invention, those having a layer made of a modified polyolefin-based resin on the surface have excellent adhesion to various metals. Further, the laminate of the present invention also includes a laminate having a structure in which both layers are bonded to each other and including a metal layer. Therefore, the laminate of the present invention is useful as an article having a laminated structure containing a metal layer such as a packaging material or an electroconductive film and a polyester resin layer, or a material for producing the same.

(Prior Art) Hitherto, a laminate including a layer made of a polyester resin and a layer made of a metal has been known to be useful as a packaging material, a conductive film, or the like. Further, since the adhesive force between the polyester resin and the metal is insufficient, the polyester is formed by interposing a layer of an adhesive between the layer of the polyester resin and the layer of the metal as the laminate. A laminate has been proposed in which the adhesive strength between the layer made of resin and the layer made of the metal is increased. For example, JP-A-53-144986 discloses a conductive laminate in which a metal thin film such as gold, silver, palladium, or aluminum is formed on a polyester film via an organopolysiloxane layer or a titanium oxide polymer layer. A film has been proposed. JP-A-53-149282 proposes a laminated film in which a uniaxially oriented polyester film and an aluminum layer are bonded via a layer formed of a curable solvent-type polyurethane adhesive. .

(Problems to be Solved by the Invention) However, even in a laminate having the above-described known adhesive layer interposed therebetween, the adhesive strength between a layer made of a polyester resin and a layer made of a metal is not necessarily sufficiently high. It is difficult to say that there is a demand for a laminate in which the adhesive strength between the two layers is further increased depending on the purpose of use.

Accordingly, an object of the present invention is to provide a laminate in which a layer made of a polyester resin and a layer made of a metal are firmly adhered to each other and a laminate used for manufacturing the laminate.

(Means for Solving the Problems) According to the present invention, the object is to provide a layer (A) made of a polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof, and a layer (B) made of a polyester resin. A) a layer comprising a cured product obtained by reacting a polyester-based polyurethane polyol having a nitrogen atom content of 3% by weight or less with an organic compound having an average of more than 2 isocyanato groups in the molecule. This is achieved by providing a laminate comprising the layer (A) and the layer (B) adhered via the layer (C).

First, the layer (A) composed of a polyolefin-based resin modified with an unsaturated carboxylic acid or a derivative thereof constituting the laminate of the present invention will be described below.

The polyolefin resin modified with the unsaturated carboxylic acid or a derivative thereof (hereinafter sometimes simply referred to as a modified polyolefin resin) refers to a polyolefin-based resin having a backbone composed of a polymer chain and an unsaturated carboxylic acid. Or a graft polymer having a branch made of a molecular chain of a polymer of a derivative such as an anhydride or a metal salt thereof. The modified polyolefin-based resin is obtained by graft-polymerizing an unsaturated carboxylic acid or an anhydride thereof to a polyolefin-based resin serving as a backbone, and further, if necessary, forming a free or anhydride form of a carboxyl group in the obtained graft polymer. It is prepared by converting at least a portion to a carboxyl group in the form of a metal salt.

Examples of the polyolefin resin used for producing the modified polyolefin resin include polypropylene, polyethylene, an ethylene-vinyl acetate copolymer or a saponified product thereof, and an ethylene- (meth) acrylate copolymer. Among them, ethylene-vinyl acetate copolymer or saponified product thereof, ethylene- (meth) acrylate copolymer and the like are preferable. The content of the vinyl acetate component in the ethylene-vinyl acetate copolymer or a saponified product thereof is preferably from 5 to 55% by weight, and among them, from 10 to 40% by weight in that moldability is particularly good. It is even more preferred. Examples of the ethylene- (meth) acrylate copolymer include ethylene- (meth) acrylate methyl ester copolymer, ethylene- (meth) acrylate ethyl ester copolymer, and ethylene- (meth) acrylic acid Butyl ester copolymer, ethylene- (meth) acrylic acid n
-Hexyl ester copolymer, ethylene- (meth) acrylic acid 2-methylhexyl ester copolymer and the like,
Among them, an ethylene-ethyl acrylate copolymer is preferably used. The content of the (meth) acrylate component of the ethylene- (meth) acrylate copolymer is preferably from 5 to 45% by weight, but the moldability and adhesion of the resin are particularly good. At 10-35
More preferably, it is by weight. These polyolefin resins have a melting coefficient (melt index, MI) in the range of 0.01 to 50 g / 10 minutes and a density of 0.1.
Those having a range of 92 to 0.97 g / cm ³ are preferably used.

Examples of the unsaturated carboxylic acid used as a monomer for graft polymerization for producing a modified polyolefin-based resin include alkene monocarboxylic acids such as acrylic acid and crotonic acid; alkenedicarboxylic acids such as maleic acid and itaconic acid And the anhydrides of unsaturated carboxylic acids include, for example, cyclic anhydrides of alkenedicarboxylic acids such as maleic anhydride and itaconic anhydride. Among these unsaturated carboxylic acids and their anhydrides, maleic anhydride is preferred. When maleic anhydride is used as a monomer for graft polymerization, ethylene, styrene, vinyl acetate, vinyl ether or the like may be used as a comonomer. Grafting amount of unsaturated carboxylic acid or its anhydride is relative to polyolefin resin.
The content is preferably 0.01 to 6% by weight, and more preferably 0.1 to 5% by weight because the adhesiveness and processability of the resin are particularly good.

The graft polymerization method is not particularly limited, and a known method is used. For example, a polyolefin resin and an unsaturated carboxylic acid or an anhydride thereof may be combined with dibenzoyl peroxide, dibutyl peroxide, dicumyl peroxide, t-butyl peroxide. A method in which the reaction is performed under heating in the presence of an organic peroxide such as benzoate, t-butyl hydroperoxide, cumene hydroperoxide, and the like. Such reactions include benzene, toluene, xylene,
The reaction can be performed at a temperature of 100 to 240 ° C. in the presence or absence of a solvent such as t-butylbenzene and cumene.

The polyolefin-based resin obtained by graft-polymerizing the unsaturated carboxylic acid or its anhydride thus obtained is used as it is or after being reacted with a metal compound. By using a modified polyolefin resin obtained by reacting with a metal compound, the moldability of the obtained laminate may be particularly good. The reaction of a polyolefin resin obtained by graft polymerization of an unsaturated carboxylic acid or an anhydride thereof with a metal compound is carried out, for example, by blending the resin with a metal compound. As the metal compound, a compound of an alkali metal or an alkaline earth metal is suitably used. Examples of the alkali metal or alkaline earth metal compound include salts with alkali metal acids such as sodium carbonate, lithium carbonate, and sodium acetate;
Hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; oxides of alkali metals such as sodium oxide; salts with acids of alkaline earth metals such as magnesium carbonate; alkalis such as calcium hydroxide and magnesium hydroxide Hydroxides of earth metals; oxides of alkaline earth metals such as calcium oxide; and the like, among which, salts with alkali metal acids, hydroxides or oxides are preferable, and sodium hydroxide is particularly preferable. . Alkali metal or alkaline earth metal compounds are not necessarily limited thereto, but free carboxyl groups contained in a polyolefin-based resin obtained by graft polymerization of an unsaturated carboxylic acid or an anhydride thereof and a form of an anhydride form. 0.02-0.6 times equivalent to the total with carboxyl groups, especially 0.03
It is often desirable to incorporate up to 0.3 equivalents. That is, by adding 0.02 equivalents or more, it is easy to suppress morphological inconveniences that may occur in the obtained laminate, such as a wavy pattern and unevenness. In addition,
When the equivalent weight is 0.6 times or less, the coloring of the polyolefin resin is suppressed, and the flowability is improved, so that the laminate of the present invention tends to be advantageous in terms of appearance and production.

The above-mentioned modified polyolefin-based resin alone may constitute the layer (A) in the laminate of the present invention, but a thermoplastic resin such as an unmodified polyolefin-based resin; an antioxidant, an ultraviolet absorber, a plasticizer, Additives such as inhibitors, lubricants, fillers and the like may be additionally added to the layer (A). As the unmodified polyolefin-based resin, those described above as examples which can be used for producing the modified polyolefin-based resin can be used. The amount of the unmodified polyolefin resin used is usually
The total resin resin constituting the layer (A) combined with the modified polyolefin resin is 90% by weight or less, but within the range of 40 to 98% by weight, the production cost may be reduced and the moldability may be improved. is there. The above additives include 2,5-
Di-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, 4,4'-thiobis (3-methyl-6
-T-butylphenol), 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), tetrakis [methylene 3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate] Antioxidant such as methane, octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate; ethyl 2-cyano-3,3-diphenyl acrylate, 2- (2-hydroxy -5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-t-butyl-5-
Methylphenyl) -5-chlorobenzotriazole, 2
UV absorbers such as -hydroxy-4-methoxybenzophenone; plasticizers such as dimethyl phthalate, diethyl phthalate, dioctyl phthalate, wax, liquid paraffin, and phosphate esters; pentaerythritol monostearate, sorbitan monopalmitate; Antistatic agents such as polyethylene oxide and carbowax; Lubricants such as ethylene bisstearamide and butyl stearate; carbon black, phthalocyanine, quinacridone, azo pigments,
Coloring agents such as titanium oxide and red iron; glass fiber;
Fillers such as asbestos, mica, wollastonite and aluminum silicate are exemplified.

Next, the layer (B) made of a polyester resin constituting the laminate of the present invention will be described below.

The above polyester resin is a condensation polymer of a dicarboxylic acid or an ester-forming derivative thereof and a diol. Examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid; and mixed dicarboxylic acids of the aromatic dicarboxylic acid and a small amount of saturated aliphatic dicarboxylic acids such as adipic acid and sebacic acid. Can be Representative examples of the ester-forming derivative of dicarboxylic acid include lower alkyl esters such as methyl ester and ethyl ester of dicarboxylic acid described above. Among them, it is preferable to use, as the dicarboxylic acid or the ester-forming derivative thereof, one containing at least 70 mol% of terephthalic acid or the ester-forming derivative thereof, since the mechanical performance and the like of the obtained laminate are particularly excellent. As the diol, one or more aliphatic saturated diols or alicyclic diols such as ethylene glycol, butane diol, hexane diol, and cyclohexane dimethanol can be used, and furthermore, diethylene glycol, polytetramethylene glycol, and the like. And a diol mixed with a small amount of an aromatic diol such as bisphenol A, or a trialkyl or higher alcohol such as pentaerythritol. As the polyester resin, the degree of polymerization is not particularly limited, but the intrinsic viscosity (η) measured at 30 ° C in a mixed solvent of phenol and tetrachloroethane at a weight ratio of 50 to 50 is 0.3 to 2.0 dl / g. Some are preferred.

A cured product obtained by reacting a polyester-based polyurethane polyol having a nitrogen atom content of 3% by weight or more and constituting a laminate of the present invention with an organic compound having an average of more than 2 isocyanato groups in a molecule The layer (C) formed will be described below.

The above-mentioned polyester-based polyurethane polyol contains a nitrogen atom derived from a urethane bond in a molecule, and the content of the nitrogen atom is 3% by weight or less based on the polyester-based polyurethane polyol. Nitrogen atom content is 3
If the content exceeds the weight percentage, the layer made of the cured product becomes too hard, and a disadvantage occurs that a sufficiently high peel adhesive strength cannot be obtained. The content of the nitrogen atom is preferably in the range of 0.8 to 3.0% by weight.

The above-mentioned polyester-based polyurethane polyol is obtained by reacting a polyester diol with an organic diisocyanate according to a conventional method. The polyester diol is reacted, for example, with an alkylene glycol and a dicarboxylic acid or an ester-forming derivative thereof under conditions employed in a usual polyester formation reaction, or by ring-opening polymerization of a lactone using an alkylene glycol as an initiator. It is manufactured by As the alkylene glycol, for example, ethylene glycol, 1,4-
Butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, a linear alkylene glycol having 2 to 10 carbon atoms which may have an oxygen atom interposed in an alkylene portion such as diethylene glycol; 2-methyl-1,3-propanediol, neopintyl glycol,
3-methyl-1,5-pentanediol, 2-methyl-1,8
A branched alkylene glycol having 4 to 10 carbon atoms such as octanediol is used alone or in a mixture of two or more, and among these, one or more of branched alkylene glycols having 4 to 10 carbon atoms or 30 It is preferable to use a mixed alkylene glycol with a linear alkylene glycol containing at least mol% in order to develop good adhesive strength to the polyester resin. Representative examples of dicarboxylic acids include saturated aliphatic dicarboxylic acids having 4 to 10 carbon atoms, such as succinic acid, glutaric acid, adipic acid, azelaic acid, and sebacic acid; terephthalic acid, isophthalic acid,
Examples thereof include aromatic dicarboxylic acids having 8 to 12 carbon atoms such as phthalic acid, 2,5-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid. Representative examples of the ester-forming derivative of dicarboxylic acid include lower alkyl esters such as methyl ester and ethyl ester of dicarboxylic acid described above. The above dicarboxylic acids or ester-forming derivatives thereof are used alone or in a mixture of two or more. Representative examples of lactones include ε-caprolactone, β-methyl-δ-valerolactone, and the like. The polyester diol preferably has a number average molecular weight in the range of 500 to 10,000, more preferably 700 to 5,000, based on the hydroxyl value. In a laminate containing a layer composed of a cured product of a polyester-based polyurethane polyol produced using a polyester diol having a number average molecular weight of less than 500, flexibility may be impaired. Further, a layer made of a cured product of a polyester-based polyurethane polyol produced using a polyester diol having a number average molecular weight of more than 10,000 may have insufficient adhesive strength with a layer made of a polyester resin. A commercially available product may be used as the polyester diol. Representative examples of commercially available polyester diols include:
Nipporan 4070 manufactured by Nippon Polyurethane Industry (adipic acid,
Polyester diol having a number-average molecular weight of 2,000 using neopentyl glycol and 1,6-hexanediol as monomers) and 155 (a number-average molecular weight 1500 using adipic acid, ethylene glycol and diethylene glycol as monomers)
Polyester diol), Praxel 220 (a poly (ε-caprolactone) diol having a number average molecular weight of 2,000) manufactured by Daicel Chemical Industries, and the like.

The type of the organic diisocyanate used for producing the polyester-based polyurethane polyol is not particularly limited, but when it is required to obtain a laminate having a good color tone, it is less likely to adversely affect the color tone. It is preferred to use aliphatic or alicyclic diisocyanates which are excellent in yellowing. Examples of the aliphatic diisocyanate include hexamethylene diisocyanate, and examples of the alicyclic diisocyanate include isophorone diisocyanate and 4,4'-dicyclohexylmethane diisocyanate. When coloring of the upper layer (C) is not a problem, xylylene diisocyanate as an organic diisocyanate, 4,4'-
Aromatic diisocyanates such as diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 1,5-naphthylene diisocyanate may be used.

The weight average molecular weight in terms of polystyrene of the polyester-based polyurethane polyol determined by gel permeation chromatography is preferably in the range of 30,000 to 300,000. In a layer composed of a cured product of the polyester-based polyurethane polyol having a weight-average molecular weight of less than 30,000, a sufficient adhesive performance may not be exhibited. Since the viscosity in the state becomes high, there may be a problem in the production of the laminate.

Organic compounds having an isocyanate group in a molecule having an average value exceeding 2 and acting as a curing agent for a polyester-based polyurethane polyol (hereinafter, sometimes referred to as a polyisocyanate) in a molecule are particularly limited in their types. Used without. The number of isocyanato groups contained in the molecule of the polyisocyanate is an average of 2.5
It is desirable to be in the range of from 6.0 to obtain a layer (C) having excellent adhesive performance. When it is required to obtain a laminate having a good color tone, it is desirable to use a polyisocyanate which is excellent in yellowing resistance because it is unlikely to adversely affect the color tone. As the polyisocyanate that is preferably used from this viewpoint, tri- or tetrahydric alcohols such as 1,1,1-trimethylolpropane, pentaerythritol, and glycerin and isophorone diisocyanate and hexamethylene diisocyanate have the excellent yellowing resistance. And urethane compounds having an average of 2.5 to 6.0 isocyanato groups in one molecule obtained by reacting the compound with an aliphatic or alicyclic diisocyanate. Commercially available polyisocyanates having excellent yellowing resistance may be used, and typical examples thereof include Coronate HL (1,1,1) manufactured by Nippon Polyurethane Industry.
Addition products of 1-trimethylolpropane and hexamethylene diisocyanate in a molar ratio of 1: 3). When coloring of the upper layer (C) is not a problem, the above-mentioned tri- to tetrahydric alcohols and 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 1,5-naphthylene diisocyanate are used. A urethane-based compound having an average value of 2.5 to 6.0 isocyanato groups in one molecule obtained by reacting the compound with an aromatic diisocyanate may be used. Commercially available products may be used as such urethane-based compounds. Typical examples thereof include Coronate L (manufactured by Nippon Polyurethane Industry Co., Ltd.) (addition and production of 1,1,1-trimethylolpropane and tolylene diisocyanate at a molar ratio of 1: 3). Material). Polyisocyanate is a polyester-based polyurethane polyol 10
It is desirable to use 5 parts by weight or more based on 0 parts by weight. However, if the amount of the polyisocyanate is too large, the flexibility of the resulting laminate may be impaired, so the amount of the polyisocyanate used is 30 parts by weight or less based on 100 parts by weight of the polyester-based polyurethane polyol. It is desirable to keep it to a certain amount.

The layer (C) is formed, for example, by subjecting a mixture containing the above-mentioned polyester-based polyurethane polyol and polyisocyanate interposed between the above-mentioned layers (A) and (B) to a heat treatment. And exhibits an adhesive ability to the layer (A) and the layer (B). The temperature employed in the heat treatment is not necessarily uniform depending on the type of the polyester-based polyurethane polyol and the adherend to be used, the heat treatment time employed, and the like, but is usually in the range of about 60 to 200 ° C., for example, a polyester resin. Is a polyethylene terephthalate polyester resin,
Generally, a range of about 80-140 ° C is preferred.

The layer (C) is mainly composed of a cured product obtained by reacting a polyester-based polyurethane polyol with a polyisocyanate. If necessary, additives such as an antioxidant and an ultraviolet absorber may be added to the cured product. May be blended. Representative examples of such additives include those exemplified above as additives that may be blended in the layer (A).

The thickness of each layer constituting the laminate of the present invention is not particularly limited, and a suitable thickness can be adopted depending on the application and the like, but the layer (A) usually has a thickness in the range of 20 to 300 μm. Is sufficient for exhibiting good adhesion performance to metal. If the layer (C) has a thickness in the range of usually 10 to 80 μm, it is sufficient for the layer (A) and the layer (B) to come and go firmly.

The laminate of the present invention has a structure in which the layer (A), the layer (C) and the layer (B) are laminated in this order, and is not limited to the three-layer structure. On the surface other than the surface in contact with the layer (C) of (A) and / or on the surface other than the surface of the layer (B) in contact with the layer (C),
It also includes a structure composed of four or more layers having a structure laminated with another material. For example, a three-layer having a layer (A) exposed on the surface, such as a three-layer laminate comprising only a layer (A), a layer (C) and a layer (B), which is one embodiment of the laminate of the present invention. Ability to firmly adhere to metals such as iron, tin, zinc, nickel, stainless steel, and aluminum due to the excellent adhesion of the above-mentioned laminate and layer (A) to various metals possessed by the neutral polyolefin resin. Having. Further, only four layers having a structure in which a layer (D), a layer (A), a layer (C) and a layer (B) made of a metal, which is another embodiment of the laminate of the present invention, are laminated in this order. A laminate having four or more layers having a layer (B) and a layer (D) firmly bonded via a layer (A) and a layer (C), such as a laminate comprising Excellent mechanical performance, electrical insulation, printability, etc. derived from resin and excellent water permeation resistance, gas permeation resistance, oil permeation resistance, conductivity, etc. derived from the metal in layer (D) It has various performances. As another example of a laminate of four or more layers having the layer (B) and the layer (D) bonded via the layer (A) and the layer (C), a layer (D), a layer (A) ), A layer (C), a layer (B), a layer (A), and a layer (D) having a structure in which the layers (A) and (D) are stacked in this order. A) having a structure in which A), layer (D), layer (A), layer (C) and layer (B) are laminated in this order
And a layered product of the layers.

The shape of the laminate of the present invention is not particularly limited,
Suitable ones can be arbitrarily adopted depending on the use and the like, and typical examples thereof are sheets, films, rods,
Containers, hollow tubes and the like can be mentioned.

The laminate of the present invention is produced according to a known laminate production method. For example, the layer (B) is coated with a mixture preferably containing a polyester-based polyurethane polyol and a polyisocyanate, preferably in a solution state, by a known method such as gravure coating, knife coating, roll coating, or calendering. By performing a heat treatment in the stacked state to generate a cured product from the polyester-based polyurethane polyol and polyisocyanate, the layer (A),
A three-layer laminate having a structure in which the layer (C) and the layer (B) are laminated in this order is obtained. The layer (A) exposed on the surface of the three-layer laminate thus obtained is brought into contact with a metal under heating, whereby the modified polyolefin resin in the layer (A) is thermally fused to the metal. Thus, a four-layer laminate having a structure in which the layer (D), the layer (A), the layer (C) and the layer (B) made of the metal are laminated in this order is obtained. The temperature employed in such heating is not uniform depending on the components of the layer (A), but is usually from 130 to 180 ° C.
Is within the range.

Hereinafter, the present invention will be described with reference to the drawings, but the present invention is not limited to these drawings. FIG. 1 is a cross-sectional view schematically showing the structure of one example of the laminate of the present invention. One example of the laminate shown in FIG. 1 is a layer (A) 1 made of a modified polyolefin-based resin, a layer (B) 2 made of a polyester resin, and a cured product obtained by reacting a polyester-based polyurethane polyol with a polyisocyanate. It is a three-layer laminate composed of a layer (C) 3 made of an object. FIG. 2 is a sectional view schematically showing the structure of another example of the laminate of the present invention. 2 of the laminate shown in FIG.
Examples are a layer (D) 4 composed of a metal, a layer (A) 1 composed of a modified polyolefin-based resin, a layer (B) 2 composed of a polyester-based resin, and a cured material obtained by reacting a polyester-based polyurethane polyol with a polyisocyanate. This is a four-layer laminate composed of a layer (C) 3 made of a material.

(Examples) Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Reference Example 1 Production Example of Modified Polyolefin Resin and Film Thereof Acrylic acid ethyl ester content: 25% by weight, melt index MI (190 ° C., 2160 g) 6.3 g / 10 min, density
215 parts by weight of an ethylene-acrylic acid ethyl ester copolymer having a melting point of 0.936 g / cm ³ and a melting point of 70 ° C. and 1.8 parts by weight of maleic anhydride were dissolved in 648 parts by weight of purified toluene and kept at 180 ° C.
Under stirring, 100 parts by weight of a purified toluene solution in which 5 parts by weight of maleic anhydride was dissolved was continuously added to this solution over 2.0 hours. The reaction was continued for 30 minutes after the addition was completed. After cooling the obtained reaction mixture, it was poured into a large amount of methyl alcohol to precipitate a polymer. The obtained polymer was subjected to reprecipitation purification using purified toluene as a solvent and methyl alcohol as a non-solvent. The resulting purified product had a maleic anhydride component content of 1.5% by weight, MI
The grafted polyolefin resin was 4.3 g / 10 minutes.

To 1,000 parts by weight of the grafted polyolefin-based resin thus obtained, an aqueous solution containing 0.7 parts by weight of sodium hydroxide was uniformly added, and after partially drying, the mixture was dried under reduced pressure using a vented extruder. The polyolefin resin graft-modified with a partially hydrolyzed maleic anhydride component was obtained by melt-kneading the pellets while expelling the material. The modified polyolefin-based resin thus obtained was heated at a temperature of 150 ° C. and 0.5 kg / cm ²
The film was heat-pressed at a pressure of 1 minute for 1 minute to obtain a film (a) of the modified polyolefin resin having a thickness of about 100 μm.

Reference Example 2 Production example of polyester-based polyurethane polyol Polyester diol having a number average molecular weight of 1500 produced from 3-methyl-1,5-pentanediol and adipic acid
1000 parts by weight, 109.9 parts by weight of hexamethylene diisocyanate and 1110 parts by weight of toluene as a reaction solvent were charged into a three-necked flask equipped with a Dimroth condenser, and stirred at 108 ° C. for 12 hours under a nitrogen atmosphere to obtain a polyester-based polyurethane polyol. Was obtained.
The obtained polyester-based polyurethane polyol solution was further diluted with toluene to obtain a toluene diluted solution having a solid content of 30% by weight. The viscosity of the toluene dilution is
When measured with a B-type viscometer at 25 ° C, the viscosity was 70
It was 00cps. Furthermore, a part of the toluene dilution is collected, diluted to a 1000-fold volume with tetrahydrofuran, and then subjected to gel permeation chromatography (developing solvent: tetrahydrofuran; flow rate: 1.0 ml / min). As a result, the weight-average molecular weight (in terms of polystyrene) of the polyester-based polyurethane polyol was determined to be 100,800. In the gel permeation chromatography, Yanagimoto Pump L-4000W, Showa Denko Column Shiodex KF805 and KF803 (consolidated), and Showa Denko RI Detector SE51 were used as measuring devices. The nitrogen content of the obtained polyester-based polyurethane polyol was measured by elemental analysis and found to be 1.7% by weight.

Reference Example 3 Production example of polyester-based polyurethane polyol Polyester diol having a number average molecular weight of 1500 produced from 3-methyl-1,5-pentanediol and adipic acid
1000 parts by weight, hexamethylene diisocyanate 329.4 parts by weight, 3-methyl-1,5-pentanediol 157.4 parts by weight as a chain extender and toluene 149 as a reaction solvent
Using 0 parts by weight, a polyester-based polyurethane polyol was obtained in the same manner as in Reference Example 2. The viscosity in a 30% by weight diluted toluene solution was 10600 cps. The weight average molecular weight (in terms of polystyrene) determined by gel permeation chromatography was 117,000. The nitrogen atom content was 3.7% by weight.

Example 6 6 parts by weight of a polyisocyanate (Coronate HL, manufactured by Nippon Polyurethane Industry Co., Ltd.) was added to 100 parts by weight of a solid content of a toluene diluent containing 30% by weight of the polyester-based polyurethane polyol obtained in Reference Example 2. The resulting mixture was applied to a polyethylene terephthalate film (thickness: 65 μm; Lumilar, manufactured by Toray Industries Inc.) so as to have a solid content of about 30 g / m ^2, and the solvent was removed at 90 ° C. using a hot air drier. Evaporated. The film coated on one side with the mixture of the obtained polyester-based polyurethane polyol and polyisocyanate was heated at a temperature of 110 ° C. and 0.5 kg / c
An adhesive laminate was obtained by contacting the modified polyolefin resin film (a) obtained in Reference Example 1 with a pressure of m ² for 30 seconds.

The obtained adhesive laminate is placed on a surface of the layer composed of the film (a) at a temperature of 150 ° C. and a pressure of 0.56 kg / cm ² with a metal plate selected from tinplate, cold-rolled steel and aluminum. By contacting for two seconds, three kinds of metal layer-containing laminates were obtained.

Comparative Example 1 A polyethylene terephthalate film coated on one side with a mixture of a polyester polyurethane polyol and a polyisocyanate without laminating the modified polyolefin resin film (a) was heated at a temperature of 110 ° C. Three corresponding metal layer-containing laminates were obtained in the same manner as in the example except that the metal plate was directly contacted with the metal plate at a pressure of 0.5 kg / cm ² for 30 seconds.

Comparative Example 2 Polyethylene terephthalate film (thickness: 65μ)
m, manufactured by Toray Co., Ltd.) and a metal plate selected from tin, cold-rolled steel and aluminum via the modified polyolefin-based resin film (a) obtained in Reference Example 1.
By bonding at a temperature of 0 ° C. and a pressure of 0.5 kg / cm ² for 30 seconds, three types of corresponding metal layer-containing laminates were obtained.

Comparative Example 3 Three corresponding metal-containing laminates were obtained in the same manner as in the Example except that the toluene dilution containing the polyester-based polyurethane polyol obtained in Reference Example 3 was used.

Adhesion test The three kinds of metal layer-containing laminates obtained in the examples and the three kinds of metal layer-containing laminates obtained in Comparative Examples 1 to 3 were each tested with a tensile tester (Shimadzu Autograph DCS-100). And subjected to a 180 ° peel test at a tensile speed of 50 mm / min. The tensile test was performed on two or three layers selected from a modified polyolefin-based resin layer, a cured product layer and a polyester resin layer.
Separate the resin part composed of layers and the metal plate and attach them to each of several test pieces and pull them (hereinafter, this test method is referred to as method (a)), or a part including the modified polyolefin resin layer and the metal plate The polyester resin layer was separated from the polyester resin layer, and each was attached to several test pieces and pulled (hereinafter, this test method is referred to as method (b)).

The fracture surface in the peeling test of the method (a) was the interface between the resin portion and the metal plate in the metal layer-containing laminates obtained in Examples, Comparative Examples 1 and 3, and Comparative Example 2
In the metal-layer-containing laminate obtained in the above, there was an interface between the modified polyolefin-based resin layer and the polyester resin layer.

Table 1 shows the results of the peel test by the methods (a) and (b).

From the results of the above-mentioned adhesiveness test, in the metal layer-containing laminate obtained in the example, the modified polyolefin resin layer was used regardless of whether the metal constituting the metal layer was tin, cold-rolled steel or aluminum. It is clear that the cured product layer and the cured product layer each exhibit strong adhesive performance. On the other hand, in the metal layer-containing laminates obtained in Comparative Examples 1 to 3, it is apparent that the modified polyolefin-based resin layer or the cured product layer contained therein does not exhibit sufficient adhesive performance.

(Effects of the Invention) As is clear from the above examples, among the laminates provided by the present invention, the laminate having on its surface a layer made of a modified polyolefin-based resin has excellent adhesive ability to various metals. A laminate having a metal layer adjacent to a layer made of a modified polyolefin-based resin maintains high adhesive strength.

[Brief description of the drawings]

FIG. 1 and FIG. 2 are cross-sectional views each showing an example of the laminate of the present invention. 1: Layer composed of modified polyolefin resin (A) 2: Layer composed of polyester resin (B) 3: Layer composed of a cured product obtained by reacting polyester polyurethane polyol with polyisocyanate (C) 4: Metal layer Layer (D)

Claims (2)

(57) [Claims] 1. A layer (A) composed of a polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof, a layer (B) composed of a polyester resin, and a polyester series having a nitrogen atom content of 3% by weight or less. A layer (C) composed of a cured product obtained by reacting a polyurethane polyol with an organic compound having an isocyanato group in a molecule having more than 2 isocyanate groups on average, and wherein the layer (A) and the layer (B) are A laminate bonded through the layer (C). 2. A layer (A), a layer (B), a layer (C) and a layer (D) made of a metal, wherein the layer (C) and the layer (D) are adhered via the layer (A). The laminate according to claim 1, wherein