JP2000178416A - Polyester resin composition and laminate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyester resin composition having good adhesion to a metal plate and a PET film (or a PET sheet) without using a technique such as addition of a curing agent or formation of a bonding layer into a multilayer. SOLUTION: This composition comprises (a) 35-85 pts.wt. of a crystalline copolyester resin containing terephthalic acid, isophthalic acid and an aliphatic dicarboxylic acid as main acid components and butanediol as a main alcohol component and (b) 65-15 pts.wt. of an amorphous copolyester resin having >=35 deg.C glass transition temperature and a carboxyl value within the range of 5-60 mg KOH/g.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polyester resin composition and a laminate using the same. More specifically, it comprises a crystalline copolyester resin having a specific structure having good adhesion to metal and PET, and an amorphous copolyester resin (b) having a specific glass transition temperature and a carboxyl number. Polyester resin composition, and metal sheet and PET film (or PET film)
A sheet) used as an adhesive layer.

[0002]

2. Description of the Related Art PET film (or PET sheet)
It is difficult to obtain good adhesion to a metal plate as compared with a film (or sheet) made of another material, and usually, a method of improving adhesion by a method such as corona treatment or anchor coating is used. However, there is a problem that the cost of the product is increased.

On the other hand, it is known that an amorphous copolyester resin having a low glass transition temperature (for example, lower than room temperature) has good adhesiveness to a PET film (or a PET sheet). However, when these are used as an adhesive layer, they do not pose a problem when they are directly applied on a PET film (or a PET sheet) and are used as they are. When it is removed, it has tackiness, so that there is a problem that it adheres to the back surface of the PET film (or PET sheet). Therefore, usually, a non-crystalline copolymerized polyester resin, isocyanate, melamine, phenolic resin, a curing agent such as epoxy is blended, a means is employed to cure the adhesive layer by heat treatment, the number of manufacturing steps increases This has led to a problem of increased product cost.

In order to obtain good adhesion to different adherends, a technique of forming two or more kinds of adhesive layers into a multilayer is employed. The problem was that the cost of the product increased due to the increase in the number.

[0005]

SUMMARY OF THE INVENTION The present invention solves the problems of the prior art and provides a polyester resin composition having good adhesion to a metal plate and a PET film (or a PET sheet); A laminate using the same is provided.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that terephthalic acid, isophthalic acid, aliphatic dicarboxylic acid and 1,4-butanediol are the main components. This purpose can be achieved by forming a polyester resin composition in which a prescribed ratio of a crystalline copolymerized polyester resin and an amorphous copolymerized polyester resin having a specific glass transition temperature and a carboxyl number are blended. And arrived at the present invention.

That is, the gist of the present invention is as follows. (1) terephthalic acid, isophthalic acid and aliphatic dicarboxylic acid as a main acid component, and a crystalline copolyester resin containing 1,4-butanediol as a main alcohol component (a)
35 to 85 parts by weight and an amorphous copolyester resin (b) having a glass transition temperature of 35 ° C. or higher and a carboxyl number in the range of 5 to 60 mgKOH / g (b) characterized by comprising 65 to 15 parts by weight. Polyester resin composition. (2) At least a metal plate layer (A) selected from copper, iron, aluminum, and tin, an adhesive layer (B) made of the polyester resin composition described in (1), and a PET film (or PET sheet) layer A laminate characterized by being present in this order.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

It is necessary that the crystalline copolymerized polyester resin (a) in the present invention contains terephthalic acid, isophthalic acid and aliphatic dicarboxylic acid as a main acid component and 1,4-butanediol as a main alcohol component. And those soluble in general-purpose organic solvents such as toluene, methyl ethyl ketone and cyclohexanone.

Here, the crystalline resin is a resin having a heat of fusion of 1 cal / g or more corresponding to the melting point when measured at a heating rate of 20 ° C./min in a nitrogen atmosphere using a differential scanning calorimeter.
It has a distinct melting point. The heat of fusion is 1 cal /
If it is less than g and does not have a clear melting point, when it is mixed with amorphous copolyester resin (b) and used as an adhesive layer, its solubility in general-purpose organic solvents and PET film (or PET sheet) Is good, but tackiness makes it difficult to handle in the above-described winding step, which is not preferable.

The main acid components in the crystalline copolymerized polyester resin (a) are terephthalic acid, isophthalic acid and aliphatic dicarboxylic acid. Of these, the combined ratio of terephthalic acid and isophthalic acid is preferably at least 50 mol%, more preferably at least 60 mol%, of the entire acid component. If this ratio is less than 50 mol%, it is difficult to obtain a crystalline copolyester resin.

Further, the ratio of terephthalic acid and isophthalic acid is represented by the following formula: Is preferably satisfied, and more preferably in the range of 0.50 to 0.65. If the proportion of terephthalic acid is less than 0.30, the solubility in general-purpose organic solvents such as toluene, methyl ethyl ketone and cyclohexanone is good,
Since the crystallization speed becomes extremely slow, or in some cases, crystallization does not occur, tackiness remains and causes trouble in manufacturing. On the other hand, if the proportion of terephthalic acid exceeds 0.65, the crystallinity of the resin increases, so that the solubility in general-purpose organic solvents decreases, and not only becomes difficult to use as an adhesive layer, but also, for example, hexafluoroisopropanol. Even if the adhesive layer is formed by dissolving in a special organic solvent such as the above, the PET film (or PET sheet) is damaged, and good adhesion to the PET film (or PET sheet) cannot be obtained.

The aliphatic dicarboxylic acid, which is one of the main acid components, has 2 to 36 carbon atoms and may have any structure as long as it has no aromatic ring. Specific examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, itaconic acid, fumaric acid, maleic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, and icoic acid dicarboxylic acid. Acids, dimer acids and the like.

The proportion of the aliphatic dicarboxylic acid is preferably at least 20 mol% and less than 50 mol% of the whole acid component.
It is more preferable that the content be at least mol% and less than 40 mol%. If this ratio is less than 20 mol%, the copolymerized polyester resin
Since the crystallinity of (a) increases, the solubility in general-purpose organic solvents such as toluene, methyl ethyl ketone, and cyclohexanone decreases, and not only is it difficult to use as an adhesive, but also special adhesives such as hexafluoroisopropanol are used. Even if the adhesive layer is formed by dissolving in an organic solvent, the PET film (or PET sheet) is damaged, and good adhesion to the PET film (or PET sheet) cannot be obtained. On the other hand, when the proportion is 50 mol% or more, there is no problem in solubility in general-purpose organic solvents, but the crystallization rate becomes extremely slow, and in some cases, crystallization does not occur. It causes the occurrence.

The main alcohol component in the crystalline polyester resin (a) is 1,4-butanediol. The proportion of 1,4-butanediol is preferably at least 80 mol%, more preferably at least 90 mol%, of the whole alcohol component. If this ratio is less than 80 mol%, a crystalline copolymerized polyester cannot be obtained.

The crystalline copolyester (a) includes, in addition to the above-mentioned main components, aromatic dicarboxylic acids such as (phthalic anhydride), naphthalenedicarboxylic acid and diphenic acid, and alkyl ester derivatives thereof, Aromatic polycarboxylic acids such as trimellitic anhydride and pyromellitic anhydride) and their alkyl ester derivatives; alicyclic dicarboxylic acids such as cyclobutane dicarboxylic acid and cyclohexane dicarboxylic acid; and their alkyl ester derivatives; Pentyl glycol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5 -Aliphatic groups such as pentanediol and polytetramethylene glycol Aromatic glycols such as alcohol, ethylene oxide adduct of bisphenol A, and ethylene oxide adduct of bisphenol S;
Alicyclic glycols such as cyclohexanedimethanol, 1,4-cyclohexanediethanol and spiroglycol, aliphatic polyhydric alcohols such as trimethylolpropane, pentaerythritol and glycerin, ε-caprolactone, γ-butyrolactone, p-hydroxybenzoic acid And the like may be copolymerized as long as the properties of the present invention are not impaired.

Although the molecular weight of the copolymerized polyester resin (a) is not particularly limited, it is preferable that the number average molecular weight is 10,000 or more in order to satisfy the adhesiveness to an adherend.

The amorphous copolymerized polyester resin (b) in the present invention must have a glass transition temperature of 35 ° C. or higher, a carboxyl number in the range of 5 to 60 mgKOH / g, and a glass transition temperature of 45 mgKOH / g. ℃ or more, carboxyl number 10 ~ 30 mgK
It is preferably in the range of OH / g.

Here, the non-crystalline resin is a resin having a heat of fusion corresponding to a melting point of less than 1 cal / g when measured at a heating rate of 20 ° C./min in a nitrogen atmosphere using a differential scanning calorimeter. , Which do not have a definite melting point. When the heat of fusion is 1 cal / g or more and has a clear melting point, when it is mixed with a crystalline polyester resin (a) and used as an adhesive layer, the adhesiveness to the PET film (or PET sheet) Is undesirably reduced.

If the glass transition temperature of the amorphous copolymerized polyester resin (b) is less than 35 ° C., when the crystalline copolymerized polyester resin (a) is blended with the glass transition temperature and used as an adhesive layer, there is tackiness. Therefore, handling in the above-described winding step becomes difficult, which is not preferable. When the amorphous copolymer polyester resin (b) has a carboxyl value of more than 60 mgKOH / g, when the crystalline copolymer polyester resin (a) is blended with the carboxyl value and used as an adhesive layer, the adhesion to the metal is reduced. Although the properties are satisfactory, the adhesive strength to the PET film (or PET sheet) is undesirably reduced. On the other hand, if the carboxyl number is less than 5 mgKOH / g,
When used as an adhesive layer, the adhesive strength to metal is undesirably reduced.

The amorphous copolymerized polyester resin (b)
Although the molecular weight of is not particularly limited, in order to satisfy the adhesion to the adherend, the number average molecular weight is from 2,000 to 10,000
And more preferably 5,000 to 10,000.

The above amorphous copolymerized polyester resin (b)
Has a glass transition temperature of 35 ° C. or higher and a carboxyl number of 5 to 5.
If it satisfies the range of 60 mgKOH / g, the constituent components are not particularly limited as long as it is composed of one or more dicarboxylic acid components and one or more glycol components.

As the dicarboxylic acid component, terephthalic acid, isophthalic acid,
Adipic acid and sebacic acid are used. Further, if necessary, oxalic acid, malonic acid, succinic acid, azelaic acid, carboxylic dicarboxylic acid, saturated aliphatic dicarboxylic acid such as dodecanedicarboxylic acid, fumaric acid, maleic acid, unsaturated aliphatic dicarboxylic acid such as itaconic acid , (Anhydride) phthalic acid, naphthalenedicarboxylic acid diphenic acid, etc., aromatic dicarboxylic acid, cyclobutanedicarboxylic acid, cyclohexanedicarboxylic acid, etc., alicyclic dicarboxylic acid, etc. may be used in combination. As these dicarboxylic acid components, dialkyl ester derivatives of the above-mentioned dicarboxylic acids may be used, and it is not necessary to use one kind alone, and it is also possible to use a mixture of two or more kinds.

As the glycol component, neopentyl glycol and ethylene glycol are mainly used from the viewpoint of adhesive properties and cost. Also, if necessary, diethylene glycol, triethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5 -Pentanediol, aliphatic glycols such as polytetramethylene glycol, aromatic glycols such as ethylene oxide adduct of bisphenol A, ethylene oxide adduct of bisphenol S, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, An alicyclic glycol such as spiro glycol may be used in combination. These glycol components are not necessarily 1
It is not necessary to use a plurality of types, and it is possible to use a mixture of a plurality of types.

Furthermore, an amorphous copolymerized polyester resin
(b), in addition to the above-described components, within a range that does not impair the characteristics of the present invention, trivalent or higher polycarboxylic acids such as trimellitic acid and pyromellitic acid, or anhydrides thereof, dialkyl esters, Polyhydric carboxylic acid derivatives such as diphenyl ester, polyhydric alcohols such as trimethylolpropane, pentaerythritol and glycerin, ε-caprolactone, γ-butyrolactone, p-hydroxybenzoic acid hydroxycarboxylic acid and the like may be copolymerized.

The crystalline copolymerized polyester resin (a) and the amorphous copolymerized polyester resin (b) in the present invention can be produced by basically the same method. Specifically, using the required components, under normal pressure, temperature 200
After performing a direct esterification or transesterification reaction at ~ 280 ° C, a melt polycondensation reaction can be carried out at a temperature of 200-280 ° C under a reduced pressure of 5 hPa or less in the presence of a conventionally known catalyst. .

At this time, the crystalline copolymerized polyester resin
As a method of adjusting the molecular weight of the (a) and the amorphous copolymerized polyester resin (b), a method of stopping the polymerization when the viscosity of the polyester melt at the time of polymerization reaches a desired point, or a method of once having a high molecular weight A method in which a polyester is produced and then a depolymerizing agent (acid or alcohol) is added, and a method in which a monofunctional alcohol or carboxylic acid is added in advance is exemplified.

In the case of producing the crystalline copolymerized polyester resin (a), it is preferable to stop the polymerization when the viscosity of the polyester melt at the time of polymerization reaches a desired value. It can be achieved by controlling with the torque of When it is desired to increase the number of specific functional groups, such as the amorphous copolymerized polyester resin (b), after increasing the molecular weight of the polyester to a certain viscosity, a low-molecular substance (depolymerization) having the functional groups to be increased is required. ) May be employed. In this case, as a depolymerizing agent, terephthalic acid, isophthalic acid, adipic acid, sebacic acid, oxalic acid, malonic acid, succinic acid, itaconic acid, azelaic acid, dicarboxylic acid iconate, naphthalenedicarboxylic acid, diphenic acid, dodecanedicarboxylic acid Examples thereof include acid, cyclohexanedicarboxylic acid, fumaric acid, maleic acid, trimellitic acid, trimellitic anhydride, and pyromellitic acid. These may be used alone or as a mixture of two or more.

The above-mentioned crystalline copolymerized polyester resin (a)
As a catalyst that can be used in producing the non-crystalline copolymerized polyester resin (b), a conventionally known metal compound can be used. Specifically, lithium oxide, lithium methylate, lithium ethylate, lithium glycolate, lithium acetate, sodium methylate, sodium ethylate, sodium glycolate,
Alkali metal compounds such as sodium formate, sodium acetate, potassium acetate, zinc oxide, zinc formate, zinc acetate, zinc propionate, zinc borate, zinc glycolate, zinc benzoate, zinc caproate, zinc butyrate, zinc valerate, Zinc compounds such as zinc antimonite, zinc germanate, zinc germanate, manganese compounds such as manganese acetate, manganese citrate, manganese borate, manganese glycolate, manganese antimonite, cobalt formate, cobalt chloride, cobalt acetate , Cobalt compounds such as cobalt propionate and cobalt hydroxybenzoate, calcium benzoate, calcium acetate, calcium malonate, calcium adipate, stringium acetate, barium acetate,
Alkaline earth metal compounds such as magnesium acetate, tetrabutyl titanate, tetraisopropyl titanate, titanyl ammonium oxalate, potassium titanyl oxalate, titanyl strontium oxalate, potassium titanyl tartrate, titanyl ammonium tartrate, titanium glycolate, titanium acetyl acetate, etc. Titanium compound,
Antimony trioxide, antimony pentoxide, antimony glycolate, antimony alcoholate, antimony acetate,
Antimony compounds such as antimony phenolate, germanium alcoholate, germanium phenolate, potassium germanate, sodium germanate, calcium germanate, potassium germanate, thallium germanate,
Examples include germanium compounds such as germanium dioxide, tin compounds such as dimethyltin maleate, dibutyltin oxide, hydroxybutyltin oxide, and monobutyltin tris (2-ethylhexanoate). These may be used alone or in combination of two or more. May be used.

The crystalline copolymerized polyester resin (a)
When producing the amorphous copolymerized polyester resin (b), a stabilizer such as triphenyl phosphate, triethyl phosphate, phosphoric acid, or a matting agent such as titanium dioxide does not impair the properties of the present invention. You may add in the range.

The weight ratio of the crystalline copolymerized polyester resin (a) and the amorphous copolymerized polyester resin (b) in the polyester resin composition of the present invention is as follows: It is necessary to satisfy If the ratio of the resin (a) is less than 35% by weight, the adhesion to a PET film (or a PET sheet) is impaired, which is not preferable.
On the other hand, if the ratio of the resin (a) exceeds 85% by weight, the adhesive strength to metal is undesirably deteriorated.

Next, the laminate of the present invention and a method for producing the same will be described. That is, the laminate of the present invention is made of copper,
Metal plate layer (A) selected from iron, aluminum, tinplate,
Adhesive layer (B) consisting of the polyester resin composition described above
And a PET film (or PET sheet) layer (C) at least in this order. Here, a PET film refers to a film having a thickness of 0.25 mm or less as described in JIS Z-0108, and a PET sheet refers to a film exceeding a thickness of 0.25 mm.

The method of forming the adhesive layer (B) in the laminate of the present invention may be performed by any method, but the polyester resin composition is dissolved in an organic solvent, and the solution is formed on a PET film (or PET sheet). A method of applying and then removing the solvent is preferred. Alternatively, the adhesive layer (B) can be formed by applying a solution of the polyester resin composition to the metal plate layer (A) and removing the solvent.

The organic solvent used for forming the adhesive layer (B) is not particularly limited as long as it dissolves the polyester resin composition of the present invention. Specifically, benzene, toluene, Aromatic solvents such as xylene, chlorinated solvents such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene, dichlorobenzene, ethyl acetate, isophorone , Ester solvents such as γ-butyrolactone, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketone solvents such as cyclohexone, diethyl ether, ethyl cellosolve, butyl cellosolve, tetrahydrofuran, ether solvents such as 1,4-dioxane, Methanol, ethanol, n-propanol, isopropanol, n-butanol, etc. Alcohol-based solvents, n-
Examples include aliphatic hydrocarbon solvents such as butane, isobutane, n-pentane, n-hexane, n-heptane, n-octane and nonane, and alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane. These can be used alone or in combination of two or more.

Next, a metal plate layer (A) selected from copper, iron, aluminum, and tinplate, an adhesive layer (B), and a PET film (or PET sheet) layer (C) are arranged so as to be heated. The laminate is formed by a conventionally known method such as sealing, roll bonding, and heat compression.

At this time, the preheating temperature of the adherend (usually a metal plate) when the adherends are bonded to each other via the adhesive layer (B) is:
Preferably in the range of 40-250 ° C, 100-200 ° C
It is more preferable to be within the range. If the preheating temperature is lower than 40 ° C., no matter how much the pressure is increased, a material having high adhesive strength cannot be obtained. On the other hand, if the preheating temperature exceeds 250 ° C., the PET film (or PET sheet) layer as the adherend is undesirably deformed or wrinkled. The pressure at the time of bonding is preferably set to 0.2 kg / cm ² or more, and more preferably set to 0.5 ~3kg / cm ^2. If the pressure at the time of bonding is less than 0.2 kg / cm ² , a material having high bonding strength cannot be obtained even if the preheating temperature is increased and the pressing time is increased. Furthermore, the crimping time for bonding is 0.2-30
Preferably, it is seconds. If the crimping time is less than 0.2 seconds,
Even if the preheating temperature is increased, a material having high adhesive strength cannot be obtained. On the other hand, when the pressing time exceeds 30 seconds, there is no problem in the adhesive strength of the obtained laminate, but it is not preferable because the productivity is poor.

[0037] The polyester resin composition of the present invention comprises a PE
It has particularly good adhesion to T film (or PET sheet) and metal plate (copper, iron, aluminum, tinplate),
The material used for the adherend is not limited to this, and can be used as an adhesive for various plastics. Specifically, chlorine resins such as polyvinyl chloride and polyvinylidene chloride, polycarbonate resins, polyarylate resins, polyester resins such as polybutylene terephthalate and polyethylene naphthalate, polyether sulfone resins, polysulfone resins, polystyrene resins, It is suitably used as an adhesive for (meth) acrylic resin and the like. The shape of the adherend is a film, a sheet,
The shape is not limited to a plate shape, and may be a fibrous shape, a cylindrical shape, or any other shape.

The polyester resin composition of the present invention can be used alone as an adhesive resin, but can also be used in combination with a curing agent such as an isocyanate resin, a phenol resin, a melamine resin, and an epoxy resin. . In addition, depending on the use, a halogen-based flame retardant, a phosphorus-based flame retardant, an antimony-based flame retardant, a melamine cyanurate-based flame retardant, or the like can be mixed to impart flame retardancy. Further, conventionally known additives such as a filler, a stabilizer, a lubricant, a matting agent, an antistatic agent, a foaming agent and the like can be blended as long as the characteristics of the present invention are not impaired.

[0039]

Next, the present invention will be described in detail with reference to examples and comparative examples. In Examples and Comparative Examples, the characteristic values of the copolymerized polyester resins (a) and (b) and the evaluation of the laminate were measured by the following methods. (i) Composition ^{1 of} Copolyester Resins (a) and (b) Using an NMR apparatus (Lamdba 300WB, manufactured by JEOL Ltd.), mol% of each component was determined. (ii) Glass transition temperature and melting point of copolymerized polyester resins (a) and (b) Differential scanning calorimeter (manufactured by Seiko Instruments Inc.
It was measured at a heating rate of 20 ° C./min using DSC-7). (iii) Carboxyl value of copolymerized polyester resin (b) 0.5 g of copolymerized polyester resin (b) was added to 1,4-dioxane 25
It was determined by titration with 0.1N KOH methanol solution using cresol red as an indicator. (iv) Adhesive strength of laminate The adhesive strength was measured using “Autograph AGS 100” manufactured by Shimadzu Corporation. The sample width of the laminate used for the measurement was 15 mm, the peeling rate was 50 mm / min, and the measurement temperature was 20 ° C.

The methods for producing the crystalline copolyester resin (a) were described in Reference Examples 1 to 10, and the amorphous copolyester resin was
The production method of (b) is shown in Reference Examples 11 to 17.

Reference Example 1 63.2 g of terephthalic acid, 63.1 g of isophthalic acid, sebacic acid
After charging 48.5 g and 121.7 g of 1,4-butanediol into a reactor and replacing the inside of the system with nitrogen, the reactor was heated to 240 ° C. and melted while stirring at 30 rpm.
The esterification reaction was performed for 4 hours after the temperature reached ° C. Next, as a catalyst, 10.2 g of a 2% by weight solution of tetrabutyl titanate in ethylene glycol was charged into the reactor, and the pressure in the system was reduced to 0.5 hpa while increasing the temperature in the system to 245 ° C.
For 6 hours. When the polycondensation reaction was completed, the system was returned to normal pressure while flowing nitrogen into the system, discharged in the form of a strand in a molten state, and cooled and solidified. The amount of the obtained copolyester resin was 229 g.

REFERENCE EXAMPLE 2 The raw materials were charged with 51.5 g of terephthalic acid and 5 parts of isophthalic acid.
1.5 g, 76.8 g of sebacic acid and 1,4-butanediol 121.
A copolymerized polyester resin was produced in the same manner as in Reference Example 1 except that the amount was changed to 7 g. The amount of the obtained copolyester resin was 234 g.

Reference Example 3 The raw materials were charged with 44.9 g of terephthalic acid and 4 parts of isophthalic acid.
4.9 g, 93.0 g of sebacic acid and 1,4-butanediol 121.
A copolymerized polyester resin was produced in the same manner as in Reference Example 1 except that the amount was changed to 7 g. The amount of the obtained copolyester resin was 237 g.

REFERENCE EXAMPLE 4 Raw materials were charged with terephthalic acid 56.5 g and isophthalic acid 4
6.5 g, sebacic acid 76.8 g and 1,4-butanediol 121.
A copolymerized polyester resin was produced in the same manner as in Reference Example 1 except that the amount was changed to 7 g. The amount of the obtained copolyester resin was 235 g.

REFERENCE EXAMPLE 5 Raw materials were charged with 63.1 g of terephthalic acid and 3 parts of isophthalic acid.
9.9 g, 76.8 g of sebacic acid and 1,4-butanediol 121.
A copolymerized polyester resin was produced in the same manner as in Reference Example 1 except that the amount was changed to 7 g. The amount of the obtained copolyester resin was 233 g.

REFERENCE EXAMPLE 6 Raw materials were charged with 44.9 g of terephthalic acid and 4% of isophthalic acid.
4.9 g, succinic acid 54.3 g and 1,4-butanediol 121.7
A copolymerized polyester resin was produced in the same manner as in Reference Example 1 except that the amount was changed to g. The weight of the obtained copolymerized polyester resin was 198 g.

Reference Example 7 The raw materials were charged with 63.1 g of terephthalic acid and 6 parts of isophthalic acid.
A copolymerized polyester resin was produced in the same manner as in Reference Example 1, except that the amounts were changed to 3.1 g, 55.2 g of dodecanedicarboxylic acid and 121.7 g of 1,4-butanediol. The obtained copolyester resin was 236 g.

Reference Example 8 The raw materials were charged with 69.8 g of terephthalic acid and 3 parts of isophthalic acid.
3.2 g, sebacic acid 76.8 g and 1,4-butanediol 121.
A copolymerized polyester resin was produced in the same manner as in Reference Example 1 except that the amount was changed to 7 g. The amount of the obtained copolyester resin was 234 g.

Reference Example 9 The raw materials were charged with 69.8 g of terephthalic acid and 6 parts of isophthalic acid.
9.8 g, 32.3 g sebacic acid and 1,4-butanediol 121.
A copolymerized polyester resin was produced in the same manner as in Reference Example 1 except that the amount was changed to 7 g. The amount of the obtained copolyester resin was 228 g.

Reference Example 10 The raw materials were charged with 38.2 g of terephthalic acid and 3 parts of isophthalic acid.
8.2 g, sebacic acid 109.2 g and 1,4-butanediol 12
A copolymerized polyester resin was produced in the same manner as in Reference Example 1 except that the amount was changed to 1.7 g. The amount of the obtained copolyester resin was 239 g.

Table 1 summarizes the physical properties of the crystalline copolymerized polyester resins (a) obtained in Reference Examples 1 to 10.

[0052]

[Table 1]

Reference Example 11 83.1 g of terephthalic acid, 83.1 g of isophthalic acid, 60.4 g of neopentyl glycol and 47.8 g of ethylene glycol were charged into a reactor, and the inside of the system was replaced with nitrogen. The mixture was heated to and melted, and the esterification reaction was performed for 4 hours after the temperature in the reactor reached 240 ° C. Next, 4.4 g of a 2 wt% ethylene glycol solution of zinc acetate as a catalyst was charged into the reactor, and the temperature in the system was lowered.
The pressure was reduced to 0.5 hpa while increasing to 280 ° C., and a polycondensation reaction was performed at 280 ° C. for 6 hours. Then, return to normal pressure while maintaining the temperature at 280 ° C while flowing nitrogen into the system.
1.7 g was added, and the depolymerization reaction was performed for 1 hour. When the depolymerization reaction was completed, the system was returned to normal pressure while flowing nitrogen into the system, and was discharged in a molten state into a sheet, cooled and solidified. The obtained copolyester resin was 213 g.

Reference Example 12 A copolymerized polyester resin was produced in the same manner as in Reference Example 11, except that the amount of isophthalic acid added during the depolymerization reaction was changed to 3.3 g. The amount of the obtained copolyester resin was 212 g.

Reference Example 13 A copolymerized polyester resin was produced in the same manner as in Reference Example 11, except that the amount of isophthalic acid added during the depolymerization reaction was changed to 6.6 g. The amount of the obtained copolyester resin was 214 g.

Reference Example 14 A copolymerized polyester resin was produced in the same manner as in Reference Example 11, except that the amount of isophthalic acid added during the depolymerization reaction was changed to 16.6 g. The amount of the obtained copolyester resin was 215 g.

Reference Example 15 A copolymerized polyester resin was produced in the same manner as in Reference Example 11, except that the amount of isophthalic acid added during the depolymerization reaction was changed to 19.9 g. The obtained copolyester resin was 213 g.

REFERENCE EXAMPLE 16 A polycondensation reaction was carried out in the same manner as in Reference Example 11, and the sheet was discharged as it was without depolymerization, cooled and solidified.
The amount of the obtained copolyester resin was 211 g.

Reference Example 17 Starting materials were charged with 83.1 g of terephthalic acid and 4 parts of isophthalic acid.
9.8 g, adipic acid 29.2 g, neopentyl glycol 60.
A copolymerized polyester resin was produced in the same manner as in Reference Example 11, except that 4 g of ethylene glycol and 47.8 g of ethylene glycol were used, and 3.32 g of isophthalic acid was used as a depolymerizing agent. The amount of the obtained copolyester resin was 210 g.

Table 2 summarizes the physical properties of the amorphous copolymerized polyester resins (b) obtained in Reference Examples 11 to 17.

[0061]

[Table 2]

Examples 1 to 14 and Comparative Examples 1 to 8 The crystalline copolymerized polyester resin (a) obtained in Reference Examples 1 to 10 and the amorphous copolymerized polyester resin obtained in Reference Examples 11 to 17 ( b) was dissolved in a mixed solvent of toluene and methyl ethyl ketone (weight ratio 1/1) so as to have a concentration of 30% by weight, and the mixture was dissolved on a 25 μm PET film. After applying the solution, the solvent was distilled off to form an adhesive layer having a thickness of 30 μm.
Next, the PET film on which the adhesive layer is formed is placed so that the metal plate preheated to 160 ° C. is in contact with the adhesive layer, and is pressed by a sealer under the conditions of a pressure of 1 kg / cm ² and a pressing time of 2 seconds. As a result, a laminate composed of a PET film / an adhesive layer composed of a polyester resin / a metal plate was obtained.

Table 3 summarizes the mixing ratio of the polyester resin composition, the solubility of the composition in the mixed solvent, the tackiness of the adhesive layer, the type of the metal plate as the adherend, and the adhesive strength of the laminate. .

[0064]

[Table 3]

[0065]

According to the present invention, a metal plate and a P plate can be formed without using a technique such as addition of a curing agent or multi-layering of an adhesive layer.
A polyester resin composition having good adhesion to an ET film (or a PET sheet) can be obtained. Accordingly, the polyester resin composition of the present invention can be used for adhesives in the fields of electricity, electronics, machinery, food, construction, and automobile, specifically, electric wire coatings, electric components such as flat cables, PCM paints, It can be suitably used as an adhesive resin for packaging materials such as building materials, bran, food and medicine.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F100 AB03 AB03A AB05 AB05A AB10 AB10A AB17 AB17A AK41G AK42B AL01G AL05G AT00 AT00A AT00B BA02 BA10A BA10B GB16 JA11G JA12G JK06 JL11 4J002 CF05W CF05X CF06W CF06X10 CF07 CF10 GG02 GH01 GL00 GM00 GN00 GQ00

Claims (2)

[Claims] 1. A crystalline copolyester resin (a) comprising terephthalic acid, isophthalic acid and aliphatic dicarboxylic acid as a main acid component and butanediol as a main alcohol component (a) 35 to 85 parts by weight; A polyester resin composition comprising: an amorphous copolymerized polyester resin (b) having a carboxyl number in the range of 5 to 60 mgKOH / g at 65 ° C. or higher and 65 to 15 parts by weight. 2. A metal plate layer (A) selected from copper, iron, aluminum and tinplate, an adhesive layer (B) comprising the polyester resin composition according to claim 1, and a PET film (or P).
(ET sheet) layer is present at least in this order.