JPH045045A - Laminate - Google Patents

Abstract

PURPOSE:To obtain a laminate used for preparing a laminate strongly bonding a resin base material layer and a metal layer by bonding a specific thermoplastic resin layer and the resin base material layer through an intermediate layer. CONSTITUTION:A laminate consists of a thermoplastic resin layer 1 composed of tetramethylene terephthalate type copolymerized polyester, a resin base material layer 2 composed of polyester and an intermediate layer 3 composed of cured matter obtained by reacting polyester type polyurethane polyol with nitrogen atom content of 3wt.% or less with an org. compound having isocyanate groups in a number exceeding 2 on an average in its molecule. The thermoplastic resin layer 1 and the resin base material layer 2 are bonded through the intermediate layer 3. The laminate having the thermoplastic resin layer 1 composed of tetramethylene terephthalate type copolymerized polyester on the surface thereof has excellent bonding capacity to various metals and, in a laminate having the metal layer adjacent to the thermoplastic resin layer 1 composed of tetramethylene terephthalate type copolymerized polyester, high adhesive strength is held.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention provides a thermoplastic resin layer made of tetramethylene terephthalate copolyester, a resin base layer made of polyester, and a specific resin for bonding these layers. The present invention relates to a laminate comprising an intermediate layer.

Among the laminates of the present invention, those having a thermoplastic resin layer made of tetramethylene terephthalate copolyester polyester on the surface have excellent adhesion ability to adhere to various types of adhesives. Further, a laminate including a layer made of metal obtained by bonding both is also included in the laminate of the present invention. Therefore,
The uninvented laminate is a packaging material, an article with a laminate structure containing a metal layer such as a conductive film and a polyester resin base layer, and one liter of the article is useful as a material for manufacturing the article (conventionally). BACKGROUND OF THE INVENTION It has been known that laminates comprising a resin base layer made of polyester and a layer made of metal are useful as packaging materials, conductive films, and the like.

Furthermore, the adhesive force between the polyester constituting the base material and the metal is insufficient for the laminate.

A laminate has been proposed in which the adhesion strength between the resin base layer and the metal layer is increased by interposing an adhesive layer between the polyester resin base layer and the metal layer. ing. For example, JP-A-53-14498
In Publication No. 6, a conductive laminated film was proposed in which a thin film of gold, silver, palladium, aluminum, etc. was formed on a polyester film with an organopolysiloxane layer interposed therebetween, and a polymer layer of titanium oxide. ing.

1 Hole, Japanese Patent Application Laid-open No. 5353-1492l proposes a laminated film in which a -axis oriented polyester film and an aluminum layer are formed from a curable solvent-based polyurethane adhesive and are bonded together via a film layer. has been done.

(Problem to be Solved by the Invention) However, even in a laminate with an adhesive layer of the above-mentioned size interposed, the adhesive strength between the resin base layer made of the present polyester and the layer made of metal is not necessarily sufficient. Although it is expensive, depending on the purpose of use, the adhesive strength of both 1 and 1 is more popular, and the laminate is required.

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

(Means for Solving the Problems) According to the present invention, the above object is achieved by using a thermoplastic resin made of tetramethylene terephthalate copolyester +
11 (A), a resin base layer made of polyester (B
) and a polyester-based polyurethane polyol having a nitrogen atom content of 3 times or less are reacted with an organic compound having an average number of more than 2 isonic groups in the molecule, and is a constant cured product. It is constructed by providing a laminate consisting of an intermediate layer (C), in which a thermoplastic resin layer (A) and a resin base layer (B) are bonded together with the intermediate layer (C) as a valve.

The thermoplastic resin layer (A) made of the tetramethylene terephthalate copolyester constituting the laminate of the present invention will be explained below. ) is composed essentially of dicarboxylic acid units containing terephthalic acid units and glycol units containing 1,4-butanediol units, and dicarboxylic acid units other than terephthalic acid units and /1t
is a copolyester having glycol units other than 1,4-butanediol units. In addition, in this specification,
"Dicarboxylic acid unit such as terephthalic acid unit j" means a t-shaped structural unit obtained by removing two hydroxyl groups contained in two carboxyl groups from a corresponding dicarboxylic acid such as terephthalic acid.

"Glycol units" such as 1.4-butanediol unit 1 are 1.4-butanediol and other corresponding glycols that have a box-shaped structure by removing two hydrogen atoms that can be transferred into two hydroxyl groups. The terephthalic acid unit in the copolymerized polyester (1) contributes to raising the softening point of the polyester and improving its heat resistance. If the content of terephthalic acid base is too low, the peel adhesion strength of the copolymerized polyester (11) at high temperatures will be low, and if the content is too high, the copolymerized polyester (11) will be Peel adhesion strength at room temperature becomes low. Thermoplastic resin layer (A)
In order to exhibit particularly excellent adhesion to Reiyi at both room temperature and high temperature, a copolymerized polyester (the content of terephthalic acid units in 11 is in the range of 45 to 85 molti based on the total dicarboxylic acid units) is used. Preferably, it has the effect of imparting a range of 60 to 75 moles to develop hot melt adhesive properties, and the content is preferably in the range of 30 to 80 moles based on the total glycol units. Yes.

Dicarboxylic acid units other than terephthalic acid units and/or glycol units other than 1,4-butanediol units, which are carried in the copolymerized polyester (1), improve the cohesive force 2 and adhesive strength of the copolymerized polyester tt+, It has the effect of controlling the integrity of the casing, and any structural structure can be selected and adopted as appropriate depending on the purpose of use of the laminate of the present invention. Typical examples of dicarboxylic acid units other than terephthalic acid units include saturated aliphatic dicarboxylic acids having 6 to 36 carbon atoms such as 17-binic acid, azelaic acid, cepatic acid, decanecarboxylic acid, eicosandicarboxylic acid, and dimer acid. Zeta-derived units; phthalic acid, inophthalic acid, 2.5-
Examples include nine units derived from aromatic dicarboxylic acids having 8 to 12 carbon atoms such as naphthalene dicarboxylic acid and 2,6-naphthalene dicarboxylic acid.

Representative examples of glycol units other than 14-butanediol units include ethylene glycol, 20,000 benthyl IJ
Cole, 1,6-hexanedimeryl, 2-methyl-18
-Octanediol% 1,9-nonanediol, 1.
T units derived from alkylene glycols having 2 to 10 carbon atoms other than 1,4-butanediol such as 10-decanediol; polyethylene glycol, polyethylene glycol, polytetramethylene glycol, polyhebutamethylene glycol, polyoctamethylene glycol, ho1
Examples include nine-chain derivatives derived from polyalkylene glycols such as 1-nonamenalene glycol. Copolymer polyester Cl1ri1 can be used because it can impart particularly high adhesive strength to metals to copolyester +11.
．． 2-methyl-1,8-million-tanediol units and/or 1,9-nonanediol units are added as glycol monomers other than 4-butanediol units, and the total amount is 20 to 70 molti based on all glycol units. It is preferable to have it in the allocation. In addition, the above-mentioned exemplified workpiece 11
Alkylene glycol unit is copolymerized polyester (1)
The peel bonding strength of 711 at low room temperature machining is increased to the same level as that of
In some cases, it has the effect of completely suppressing the decline in adhesion strength over time, and for that purpose it is usually about 350 to 60 tJ.
Polyalkylene glycol units having a number average molecular weight of O, preferably about 600 to 4000 are used as at least a portion of the glycol units other than the 1.4-7 tanediyl units.

The copolymerized polyester (11) used in the present invention has a glass transition point of 140 as measured by differential scanning calorimetry.
It can be seen that peel adhesion strength at material temperature S- and high temperature is particularly good when the melting point is in the range of ~20°C and the melting point is in the range of 80~160°C.

The co-polyester (1) used in the present invention has a weight ratio of phenol and tetrachlorene of 5.
It was measured at 3 () ℃ with 0:50 mixture 'F & solvent instep.
Viscosity 05-1.5 dl/? Especially those in the range of f? L7 is moldy because it exhibits adhesive properties.

The method for producing the copolymerized polyester (1) used in the present invention is not particularly limited, and conventional methods can be employed. As a method for producing it, for example, dicarboxylic acids corresponding to the dicarboxylic acid units or lower alkyl esters thereof, ester-forming derivatives such as Can be adopted. It should be noted that any known catalysts, stabilizers, modifiers, additives, etc. may be used during the polymerization, direct esterification, and ester conversion reactions, and the copolymerized polyester (1) can be used alone in the lamination of the present invention. 2 on the body
The core layer (A) contains additives such as intensification inhibitors, ultraviolet absorbers, and fillers.
It may be additionally blended with.

The above additives include 2,5-di-t-butylnohydroquinone, 2,6-di-t-butyl-p-cresol, 2,2'-methylene-bis(4-methyl-6-t-butylphenol) ), tetrakis [methylene 3-(3,
5-di-t-butylene-4-hydroxyphenyl)globionate] methane, octadenyl 3-(3,5-di-
t-Butyl-4-hydroquinphenyl)probionate. Antioxidants such as 44'-thiobis(3-methyl-6-t-butylphenol); ethyl 2-cyano-3,3
-diphenylacrylate, 2-(2-hydroxy-5
-methylphenyl)-5-chlorobenzotriazole,
UV absorbers such as 2-(2-hydroxy-3-t-butyl-5-methylphenyl)-5-chlorobenzotriazole and 2-hydroxy-4-methquinbenzophenone;
Power, talc, mica.

Optical fillers such as titanium oxide are examples.
Regarding B), it is a condensation product of the above-mentioned polyester, dicarboxylic acid or its ester-forming derivative, and dimanyl. Dicarboxylic acids include, for example, one or more aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid; alone, the ratio of 1 is 1 with a small amount of saturated aliphatic dicarboxylic acids such as adibic acid and separochenic acid; It is conveniently used as an attachment. As the ester-forming derivatives of dicarboxylic acids, lower alkyl esters such as methyl esters and ethyl esters; aryl esters of dicarboxylic acids as exemplified above are used. Among them, as a dicarboxylic acid or its ester-forming derivative, 70 moh% of terephthalic acid or its ester-forming derivative is used.
The use of materials containing the above is preferred because the resulting laminate has particularly good mechanical properties.

Examples of diols include ethylene glycol, phthanediol, hexanediol, and chlorohexanedimethanol. By using one or two or more alicyclic diols with saturated glycols, Hata et al.
5-Flurulene glycol such as Nokol; Bentae 7 Nothritol la: Trihydric or higher alcohol;
Mixtures of bispheno-AA with small amounts of aromatic diols and the like can also be used. As polyester, I
! Although there are no restrictions on the preparation, the intrinsic viscosity measured at 30°C in a mixed solvent of Funinol and tetrachloroethane in a weight ratio of 50:50 is 0.43 to 2.0 dl/f. preferable.

A laminate obtained by reacting a polyester-based polyurethane polyol having a nitrogen atom content of 3% by weight or less, which constitutes the laminate of the present invention, with an organic adduct having an average number of isocyanato groups in the molecule exceeding 2. The middle class consisting of treasures (
C) will be explained below.

The above-mentioned polyester-based polyurethane polyol contains nitrogen atoms derived from urethane bonds in the molecule, but the content of primary nitrogen atoms is 3 weight or less based on the difference between the polyester-based polyurethane polyol groups. Nitrogen S atom content is 3
If the weight exceeds 1, the intermediate layer made of silica becomes hard and gaps occur, resulting in a failure in which a high peel adhesion of 5:1 degree cannot be obtained in the era name. The nitrogen atom content is 08
A range of 3.0% to 3.0% is preferred.

The above-mentioned polyester-based poly-11 urethane polyol is obtained by reacting poly-11 esterneol and an organic diincyanate according to a conventional method. The polynisderdiol is reacted with, for example, an alkylene glycol and a dicarboxylic acid or an ester-forming derivative thereof under conditions employed in a normal polyester insect repellent reaction, or
Alternatively, it is produced by one-way polymerization of lactone using alkylene glycol as an initiator. As the alkylene glycol, 1, for example, ethylene glycol, 1
, 4-butanedio-A, L6-hexanediol, 1,
9-nonanediol, 1,10-decanediol, dichloromethane, 2-methyl-1, 2-methyl-1, 2-methyl-1, 2-methyl-1, 3-propane 7'
All, pentyl glycol, 3-methyl-1,5
-Bentanediol 2-Methyl-1,8-octanediol and other branched alkylene groups having 4 to 10 carbon atoms 11
Cole, etc. appeared in Arashi Germany and was used as a mixture of two or more types.
7 mi. It is important that at least 30 mo/I-1 of the alkylene glycol reacted with the ester-forming derivative of the dicarboxylic acid is a branched alkylene glycol having carbon v4 to 10, which is suitable for the resin base material made of polyester. Desirable for developing adhesive strength. Typical examples of dicarboxylic acids are succinic acid and glutaric acid.

4 carbon atoms such as ambic acid, azelaic acid, and cepatic acid
~10 saturated aliphatic dicarboxylic acids; terephthalan powder, inphthalic acid, phthalic acid, 2,5-naphthalene dicarboxylic acid 9
, 8-1 carbon atoms such as 2.6-naphthalenedicarboxylic acid
2 aromatic dicarboxylic acids and the like. Typical examples of ester-forming derivatives of dicarboxylic acids include lower dicarboxylic esters, ethyl esters and the like; aryl varnishes and esters; The above dicarboxylic acid or its ester-forming derivative may be used alone or in a mixture of two or more. Representative examples of lactones include ε-caprolactone and β-methyl-δ-valerolactone. The polyester diol preferably has a number average molecular weight of 500 to 10,000 based on the hydroxyl value, and more preferably 700 to 5,000. In the case of a laminate manufactured using a polyester diol having a number average molecular weight of less than 500 and containing an intermediate layer made of a cured product from a polyester-based polyurethane polyol, the flexibility may be impaired.
Ru. However, if the intermediate layer is manufactured using a polyester diol with a number average molecular weight exceeding 10 (+00) and is made of a cured product from a polyester-based polyurethane polyol, the adhesive strength with the resin base layer made of polyester will be insufficient. There are cases.

Note that a commercially available product may be used as the polyester diol. A representative example of a commercially available polyester diol is Ninoboran 40 manufactured by Nippon Polyurethane Industries.
7 (J (adipic acid, neopentyl glycol and 1
．． Number average molecular weight of 6-hexanediol as monomer: 2
000 polyester diol), 1ss (polyester diol with a number average molecular weight of 1,500, consisting of adipic acid, ethylene glycol and diethylene glycol as monomers), Daicel Chemical Industries Plaxel 220 [poly(ε-caprolactone) diol with a number average molecular weight of 2,000 ] etc.

The type of organic diinocyanate conveniently used for producing polyester-based polyurethane polyols is not particularly limited, but if it is required to obtain a laminate with a bright color tone, there is a possibility that the color tone will be adversely affected. It is preferable to use alicyclic diiso/anate because of its low yellowing resistance and its excellent yellowing resistance. Examples of such aliphatic diisocyanates include hexamethylene diisocyanate and the like. Examples of the alicyclic diiso/anate include isophorone diinopronate, 4,4'-dinochlorofluoromethane diiso/anate, and the like.

For purposes of use, if there is no problem with the coloring of the intermediate layer, organic diiso/anates such as xylylene diisonate, 4,4'-diphenylmethane diisonate 62 ,4-tolylene diiso/anate.

Aromatic diisones such as 1.5-naphnalene diisones may also be used. For the polyester-based polyurethane polyol used in the present invention, the polyester diol and organic diiso/anate are mixed according to conventional methods.

It is obtained by weight addition in the presence or absence of an organic solvent.

What is the weight average molecular weight of the polyurethane polyol based on IJ ester in terms of polystyrene for gel permeation chromatography?

It is preferable that the weight average molecular weight is in the range of 30,000 to 30,000 (J). An intermediate layer made of a cured product from a polyester polyurethane polyol with a weight average molecular weight of 30 fJOO may not exhibit sufficient adhesion performance. A polyester yarn having an average molecular weight of Xt exceeding 30 (JOOU) may have a high viscosity in a solution state and a molten state, which may cause problems in the production of a laminate.

Organic compounds having an average number of isocyanate groups exceeding 2 in their molecules (hereinafter sometimes referred to as polyisocyanates) that act as curing agents for polyester polyurethane polyols must be particularly limited in type. Used without exception. The average number of isocyanate groups contained in the polyisocyanate molecule is 2.5.
It is desirable that the value is within the range of 6.0 to 6.0 from the viewpoint of obtaining an excellent interlayer layer (Q). It is desirable to use a polyisocyanate which has excellent yellowing resistance and has a low risk of adversely affecting the surface of the skin.From this point of view, examples of polyisocyanates that are desirable to use include limethylolpropane, pentaerythritol, glycerin, etc. An average of Urethane compounds having 2.5 to 6.0 isocyanato groups are exemplified. Commercial products may be used as such polyisocyanates with excellent yellowing resistance, and representative examples include Nippon Polyurethane Kogyo Chikorofutto) iL (1,1,1-trimenalolpropane and hexamethylene). Molar ratio with diisocyanate 1:3
addition products). In addition, if coloring of the intermediate layer (C) is not a problem for the purpose of use, the above-mentioned trivalent or tetravalent alcohol and 4,4'-diphenylmethane diisocyanate (4-), 2,4-) lylenediyne Cyanate.

A urethane compound having an average of 25 to 6.0 isocyanato groups in the molecule obtained by reacting it with an aromatic diisocyanate such as 1.5-naphthylene diisocyanate may be used. Commercially available products may be used as such urethane compounds.

A representative example thereof is Coronate L (addition product of 1,1,1-trimethylolfuropane and tolylene diisocyanide at a molar ratio of 1n3) manufactured by 1 Nippon Polyurethane Industries. It is desirable to use 5 parts by weight or more per 11JO Higashi tS of polyester-based polyurethane polyester polyurethane. However, if too much polyisocyanate is used in a 4-hour warehouse, the flexibility of the resulting laminate may be impaired, so the amount of polyisocyanate used is 30 parts by weight per 100 parts by weight of Bo-11 ester polyurethane polyol. It is desirable to keep the amount to less than 30%.

The intermediate layer (C) is 1, for example, the above thermoplastic resin layer (A, 1
and the resin base layer CB) are formed by heat-treating the mixture containing the above polyester-based polyurethane polyol and polyisocyanate. Demonstrates adhesion ability against. The temperature adopted in the heat treatment depends on the polyester polyurethane polyol used, the type of adherend,
Although it is not necessarily uniform depending on the heat treatment time employed, etc.1, it is usually within the range of about 6υ to 200°C. In general, the temperature range of about 80 to 140° C. is preferably 1 to 70° C. The temperature of each layer constituting the laminate of the present invention is not particularly limited, and a suitable value is adopted depending on the application. However, the thermoplastic resin layer (A) usually has a thickness in the range of 20 to 300 pm, which is sufficient to exhibit excellent adhesion performance with the 7' Ld metal. If the layer (C) usually has a thickness in the range of 11J-1 layer 0μm, it is a thermoplastic resin layer (A
) and the resin base layer (H) are strongly bonded together.

The laminate 11 of the present invention has a structure in which the above thermoplastic resin layer (A), intermediate layer (C) and resin base layer (11) are laminated in this order, and is a three-layer structure. Without limitation, the non-chamfered surface of layer (A) that is in contact with layer (shi) and /1 is the non-chamfered surface that is in contact with layer (shi) of layer (13). It also includes a structure consisting of four or more layers that is laminated with other materials. For example, in one embodiment of the laminate of the present invention, the thin layer (A
) A core layer (A) of tetramethylene terephthalate of clF is added to a laminate of three or more layers having a layer (A) on the surface, such as a three-layer laminate consisting of only one layer (C) and a layer (B). Derived from the excellent adhesion properties of co-polyester to various metals, it is suitable for iron, tin, zinc, nickel,
It has the ability to firmly adhere to pot metals such as stainless steel and aluminum. In addition, another embodiment of the uninvented laminate is a metal F'J layer (D) 1 layer (A) 1 layer (,C)
One layer (A) and one layer (CB) are laminated in this order.
C) layer (f3) and layer (1) firmly bonded via
A laminate of four or more layers has excellent mechanical performance, electrical insulation, printability, and other properties derived from the polyester in layer (B), and excellent water resistance derived from the metal in layer CD). It has various properties such as permeability, gas permeability, oil permeability, and electrical conductivity. Above layer (A): J? and layer <C)
Another example of a laminate of four or more layers is a t-layer CB) and a skin (D) that are bonded together via a t-layer CB).

Layer (D) 1 layer (A) 1 layer (C), layer (B-1 layer (C)
, 4 (A) and layer (i)) are laminated in this order, with one layer (B) and one layer (A) of seven layers.

Examples include a seven-layer laminate having a structure in which layer (D) 1 layer (A) 1 layer (C) 2 and layer (B) are laminated in this ridge order. The shape of the uninvented laminate is not particularly limited, and any suitable shape can be adopted depending on the purpose. Examples include a sheet, a film, a rod-shaped body, a container, and a hollow tube. Examples include.

The laminate of the present invention) is manufactured according to the published method for manufacturing a laminate. The mixture is coated by a publicly available method such as gravure coating, knife coating, roll coating, etc., and the thermoplastic resin layer (A) is further heat-treated in a heavy T:i state.1. One layer (A) is created by producing a cured product from polyol and polyisocyanate.

A three-layer laminate having a structure in which the intermediate layer [C) and the layer CB) are laminated in this order is obtained. Layer (A) where the product of the three layers that can be served in this way is expressed as N1 salary.
The tetramethylene terephthalate copolyester in the layer (A) is heated and brought into contact with the copolymerized polyester under heating.
A 4-layer laminate having a structure in which , 2 layers and 3 layers are laminated in this order is obtained. The temperature employed in such heating varies depending on the structure and components of the layer (8), but is usually within the range of 11 (J to 190°C). However, the present invention is not limited by these drawings.
ff. FIG. 1 is a side view schematically showing the structure of an example of an inventive laminate. An example of the laminate shown in FIG. 1 is a thermoplastic resin layer (A) 1 made of tetramethylene terephthalate copolyester.

Resin base layer (B) 2 made of polyester and polyester yarn 11 urethane;) All'r;t'I
This is a three-layer laminate consisting of an intermediate layer (C) 3 made of a cured product obtained by reacting with + incyanate.

′! FIG. 2 is a Wr side view showing the structure of an example of the uninvented laminate. In one direction of the laminate shown in FIG. 2, a layer (0) 4. A thermoplastic resin layer (A) made of a tetramethylene terephthalate copolymer polyester, a resin base layer (r3) 2sr made of a polyester, and a polyester polyurethane polyol are obtained by reacting with a polyinone atom. -(C)3〃・4
It is a laminate of layers.

(Practice)) Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the Examples.

A mixture of 65 moles of terephthal rR,/methyl, 35 moles of 7-divic acid, 115 moles of 14-butanediol, 22.5 moles of 1,9-nonanediol, and 22.5 moles of 2-methyl-1°8-octanediol. 0.02 mol of tetraisogropoxy titanate as a catalyst was added to the mixture, and an ester conversion reaction was carried out at 200°C for 3 minutes in a nitrogen atmosphere.
Next, the tetramethylene terephthalate copolyester (
Intrinsic viscosity: 0.7 bdl/p; melting point = 102°C) was obtained. 1 of the copolymerized polyester thus obtained
50℃? ! A film (IL) made of the copolyester having a thickness of about 1 μm and a Ll of 0 μm was obtained by applying heat for 1 minute at a pressure of 0.5 h/lit.

Reference Example 2 Production Example of Polyester Polyurethane Polyol 3 -Methyl-1,5-bentanediol ζ Polyester diol 10001i1. produced from zeta adipic acid and having an average molecular weight of t15oO. 109.9 parts by weight of hexamethylene diisocyanate and 1 part of toluene as the reaction solvent.
A solution of polyester polyurethane polyol was obtained by charging 1101ti into a nine-way flask equipped with a Dimroth condenser and stirring at 108° C. for 12 hours under a nitrogen atmosphere. 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 diluted solution was measured at 25°C using a B-ya viscometer, and it was found that the viscosity was 7000% (! p. After diluting to 1000 times the volume, it was subjected to gel permeation chromatography (developing solvent: tetrahydrofuran: flow rate: 1.QWLl/min) to obtain the weight average molecular weight (in terms of polystyrene) of the polyester polyurethane polyol. As a result of measuring #
, the weight average molecular weight is 100,800, which is the 6th order. In addition, as measurement devices for Kel permeation chromatography, we used Yanagimoto Pump L-4000W, Showa Denko Moxibustion Column Showdex KFsos and Showa Denko KF803 (connected), and Showa Denko RI Detector 5E51.

Further, the nitrogen atom content of the nine polyester-based polyurethane polyols obtained was measured using an organic elemental analyzer (PerkinElmer Nilemental Analyzer Model 240C) and found to be 17% by weight.

Reference Example 3 Surface Structure Example 3 of Polyester Polyurethane Polyol - Number average molecule t15 produced from nonal-1.5-pentanediol and phosphoric acid (1000 parts by weight of polyester diol of JO, hexamethylene cyinone anate) 329.4 parts by weight, 3-methyl-1,5-pene as a chain extender, 157.4 parts by weight of tandiol2, and 1490 parts by weight of toluene as a reaction solvent. A polyurethane polyol was obtained (30% by weight) with a viscosity of 10,600 cps when diluted with toluene. The following weight average molecular weight (
Polystyrene equivalent) is 117,000, which is 9 times. Box, f
The fl elementary atom content is 3.7% by weight.

Example: Add polyisocyanate 6 (Nippon Poly9 Rethane Kogyo Korofu-1-HL) to 100 weight equivalent solids of the toluene diluted solution containing 30% by weight of the polyester polyurethane polyol obtained in Reference Example 2 at a solid content of 6 weight. Part equivalent amount addition ratio. the resulting mixture.

After applying a polyethylene terephthalate film (thickness = 65 μm: Toshiko Lumirano) to a solid content of approximately 30 f//m', dry it at 90°C using a hot air dryer.
The solvent was evaporated. One side of the film was coated with 4 tla of the resulting polyester-based polyester polyester and polyino/anate mixture.

On the coated surface, a temperature of 110°C, 0.5Kf/c
! A film made of the tetramethylene terephthalate copolyester obtained in Reference Example 1 under pressure A (a
) to obtain an adhesive laminate by contacting for 30 seconds.

The obtained adhesive laminate was heated at a temperature of 150° C. and 0.5 Kf/d on the surface of the layer made of film (a).
by contacting for 30 seconds with a plate of metal selected from tinplate, cold-rolled steel and aluminium, under pressure of
Three types of metal layer-containing laminates were obtained.

Comparative Example 1 A polyethylene terephthalate film was coated on one side with a mixture of polyurethane polyol and polyisocyanate without laminating the film (&).
2 on the coated surface, a temperature of 110°C, 0.5Kf/cr
Three types of corresponding metal layer-containing laminates were obtained in the same manner as in Example except that they were brought into direct contact with the metal plate for 30 seconds under pressure A.

Comparative Example 2 Polyethylene terephthalate film (thickness: 65μ
A plate selected from tinplate, cold-rolled steel and aluminum was heated through a film (a) at a temperature of 150°C, o, and 5Kf.
3 corresponding metal layer-containing laminates were obtained by pasting and stirring for 30 seconds under a pressure of /-.

Comparative Example 3 A corresponding metal layer-containing laminate 3811 was obtained in the same manner as in Example, except that the toluene diluted solution containing the polyester-based polyurethane polyol was used as that obtained in Reference Example 3.

The test pieces of the three metal layer-containing laminates obtained in the adhesion test example and the three metal layer-containing laminates obtained in Comparative Examples 1 to 3 were tested using a tensile tester (DC8 made by Drawho Co., Ltd.). Attached to the 1800 peel N test using -10 (J) at a tensile rate of 50 points/min.

The tensile test was performed using a tetramethylene terephthalate copolyester resin layer.

Peel the resin part consisting of two or three layers selected from the cured product I and a polyethylene terephthalate film layer and the metal plate at one end of the test piece, attach each to the grip of a testing machine and pull it [below] This test method is referred to as method (a)], and the part containing the tetramethylene terephthalate copolyester resin layer and the metal plate and the polyethylene terephthalate film layer are peeled off at one end of the test piece, and each is placed in a testing machine. This test method is hereinafter referred to as method (b).

In the metal layer-containing laminates obtained in Examples, Comparative Examples 12 and 3, the fracture surface in the peel test of method (a) was the interface between the resin portion and the metal plate.

In the metal layer-containing laminate obtained in Comparative Example 2, the tetramethylene terephthalate copolyester ma layer,!
: Lost at the interface with the polyethylene terephthalate film layer.

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

Table 1 Example 7.4 (4,5) 10.1J (4,3)
10.0 (4,3) ratio 4 layers 2 examples 1 3.4
4.3 1.6 Comparative Example 2 1.5
1.4 1.5 (Note 1) The numbers outside () indicate the peel strength using method (a).

The numbers in parentheses indicate the peel strength according to method (b).

From the results of the above adhesion test, it was found that in the metal layer-containing laminates obtained in Examples, tetramethylene terephthalate copolymerization was possible regardless of whether the metal constituting the metal layer was tinplate, cold-rolled steel, or aluminum. It is clear that the polyester resin layer and the cured material layer each exhibit n] strong adhesive performance. On the other hand, in the composite layer-containing laminates obtained in Comparative Examples 1 to 3, the tetramenalene terephthalate-based TL polyester II resin I' contained in Seven et al.
It is clear that ll' or the cured product 1 did not exhibit sufficient adhesion performance.

(Effects of the Invention) As is clear from the above examples, among the products provided by the invention, the laminate having a thermoplastic resin layer on the surface made of tetramethylene terephthalate copolyester is effective against various spirits. It has excellent adhesion ability, and also maintains high bonding strength in a laminate having a layer made of metal in instant contact with a thermoplastic resin layer made of tetramethylene terephthalate-based co-N-polyester.

[Brief explanation of the drawing]

FIG. 1 and FIG. 2 are -f: lfr plane views showing an example of the laminate of the present invention, respectively. 1: Thermoplastic resin consisting of tetramethylene terephthalate-h system and xe boss ester/11 (A) 2: Tiger resin base layer consisting of polyester (B) 3: Polyester base 11
Intermediate layer 111 (C) consisting of a cured product obtained by reacting urethane IJol with poly(1/A) 4: Layer made of metal (D) Patent applicant Rira Shi Co., Ltd.

Claims (1)

[Claims] 1. A thermoplastic resin layer (A) made of tetramethylene terephthalate copolyester, a resin base layer (B) made of polyester, and a nitrogen atom content of 3% by weight.
An intermediate layer (
C), in which a thermoplastic resin layer (A) and a resin base layer (B) are bonded together via an intermediate layer (C). 2. Consisting of a thermoplastic resin layer (A), a resin base layer (B), an intermediate layer (C), and a metal layer (D), the intermediate layer (
The laminate according to claim 1, wherein C) and layer (D) are bonded to each other via a thermoplastic resin layer (A).