JPH0632882A - Adhesive component and adherent polyester composition - Google Patents

Abstract

PURPOSE:To obtain an adhesive component having excellent heat resistance and retort resistance comprising a modified polyester prepared by uniformly grafting an ethylenic unsaturated carboxylic acid compound onto a specific unmodified aromatic polyester. CONSTITUTION:This adherent composition comprises a modified polyester having 20-150 deg.C glass transition temperature obtained by uniformly grafting 0.1-50wt.% (preferably 0.5-30wt.%) ethylenic unsaturated carboxylic acid compound (preferably maleic acid, etc.) onto an unmodified polyester comprising (10-80mol%) component unit derived from an aliphatic dialcohol (preferably 1,4- cyclohexanedimethanol) and/or (10-80mol%) component unit derived from an aliphatic dicarboxylic acid (preferably 1,4-cyclohexanedicarboxylic acid).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel adhesive component and an adhesive polyester composition containing the adhesive component. More specifically, the present invention relates to an adhesive component composed of a thermoplastic modified polyester modified with an ethylenically unsaturated carboxylic acid compound and adhesion to different plastics or metals containing the modified polyester,
The present invention relates to an adhesive polyester composition having excellent heat resistance and solvent resistance.

[0002]

BACKGROUND OF THE INVENTION Conventionally, various adhesives have been used for laminating a metal plate or metal foil and a plastic film, or laminating different kinds of plastic films. Particularly in recent years, a heat-adhesive adhesive has been used for applications such as retort packaging for foods where heating is performed after adhering, and polyester adhesives are drawing attention as such adhesives. In such polyester-based adhesives, it is difficult to obtain sufficient adhesion between the polyester-based adhesive and the substrate. Also,
Since the polyester itself has a problem of flexibility and its solubility in an organic solvent is not sufficient, it is difficult to apply the adhesive by dissolving it in a solvent. Therefore, copolyester is generally used as the polyester adhesive.

However, since the copolyester has a low crystallinity and a low glass transition temperature (Tg),
Properties such as heat resistance and solvent resistance of the adhesive layer are not sufficient. That is, since the crystallinity is low, the solubility in a solvent is improved, but the solvent resistance of the adhesive layer is decreased.
Further, since the glass transition temperature (Tg) is low, the adhesion heating temperature is low, but the heat resistance of the adhesive layer is low. Thus, in conventional polyester adhesives, the crystallinity and glass transition temperature (T
g) reduces its properties. For example, when it is used as an adhesive for food retort packaging film, retort treatment (treatment to heat the packaged object with hot water in a sealed state) causes film peeling. May cause problems.

In order to solve such problems of adhesion to substrates, heat resistance and solvent resistance, there has been proposed a method of mixing a curing agent such as an isocyanate compound or an epoxy compound with polyester ( JP 61-20
(See Japanese Patent No. 9,282).

However, in an adhesive using such an isocyanate compound or an epoxy compound, the isocyanate compound or the epoxy compound acts as a curing agent, and the adhesive strength varies depending on the dispersion state of these compounds. Must be evenly dispersed. When mixing the two components, two types of components which are essentially reactive with each other must be uniformly mixed under conditions such that the two do not substantially react,
The mixing work can be very complicated. In addition, many of these curing agents have toxicity, and when used in a large amount, it is necessary to maintain a working environment, which is disadvantageous in terms of equipment. In addition, an adhesive containing such a curing agent preliminarily undergoes a curing reaction during storage, but the adhesive performance is likely to change over time. Therefore,
The life spot of such an adhesive composition is generally short.

As described above, the conventional polyester-based adhesive has various problems in terms of workability during production, stability of the adhesive, and the like, and improvement is desired to solve these problems.

By the way, JP-A-48-68694 and 48-96900
No. 48-51179 and No. 52-70117, etc.
No. 1, No. 57-386, No. 53-19347, etc.
Graft modified aromatic polyesters are disclosed.

[0008] However, in these publications, after being formed into a certain shape such as fiber, non-woven fabric, synthetic paper or film, the surface properties such as hydrophilicity and dyeing are maintained in this shape. There is disclosed a method of graft-modifying the surface of the aromatic polyester in order to improve the property, or an aromatic polyester in a predetermined form thus graft-modified. Therefore, the graft modifying group is introduced on the surface of the fiber, for example, and the graft group is introduced nonuniformly when viewed from the whole fiber, that is, the whole aromatic polyester.

Further, for the purpose of the publication described in the above publication in which the graft-modifying group is introduced, naturally, the adhesive performance of the graft-modified aromatic polyester has not been studied.

As a result of the present inventor's study on such a graft-modified aromatic polyester, the adhesive strength of the graft-modified aromatic polyester was found to be the composition of the modified aromatic polyester, the modification rate, and the glass transition temperature of the modified aromatic polyester. It was found that it fluctuates significantly depending on the above.

Aromatic polyesters are resins having good heat resistance, and if such aromatic polyesters exhibit good adhesive performance, they are extremely useful as heat resistant adhesives.

[0012]

OBJECT OF THE INVENTION It is an object of the present invention to provide an adhesive component which is excellent in adhesiveness to metals, plastics and the like, and is also excellent in properties such as retort resistance.

Furthermore, the present invention contains the above-mentioned adhesive component and has excellent adhesiveness to a plastic film or a metal without using a curing agent and the like, and also has excellent heat-resistant adhesiveness and solvent resistance. The purpose of the present invention is to provide a hydrophilic aromatic polyester composition.

[0014]

SUMMARY OF THE INVENTION The adhesive component of the present invention comprises an unmodified aromatic polyester having a component unit derived from an alicyclic polyhydric alcohol and / or a component unit derived from an alicyclic polyhydric carboxylic acid, It consists of a modified polyester having a glass transition temperature of 20 to 150 ° C. in which an ethylenically unsaturated carboxylic acid compound is uniformly graft polymerized in an amount of 0.1 to 50 parts by weight.

The adhesive aromatic polyester composition of the present invention comprises an adhesive component composed of the above modified polyester and a thermoplastic polyester. The modified polyester, which is the adhesive component of the present invention, has excellent adhesiveness and, despite being a modified aromatic polyester, has good thermoplasticity. Moreover, this modified polyester has excellent heat resistance while being thermoplastic. Further, this modified polyester has a property of being dissolved in a solvent to some extent, but exhibits solvent resistance to a degree required for use as an adhesive.

The modified polyester can be used alone as an adhesive, or can be mixed with an unmodified thermoplastic polyester and used as an adhesive composition.

[0017]

DETAILED DESCRIPTION OF THE INVENTION Next, the adhesive component and the adhesive polyester composition of the present invention will be specifically described.

The modified polyester as the adhesive component of the present invention has at least one of a component unit derived from an alicyclic dialcohol and a component unit derived from an alicyclic dialcohol in its structure. It is a graft modified product in which a specific amount of an ethylenically unsaturated carboxylic acid compound is uniformly graft-polymerized to the aromatic polyester.

Aromatic Polyester [A] This aromatic polyester is basically composed of a repeating unit formed by an ester bond of a polyvalent carboxylic acid and a polyhydric alcohol. The component unit derived from a polyvalent carboxylic acid is mainly formed of a divalent carboxylic acid or its derivative, but a part thereof may be formed of a trivalent or higher polyvalent carboxylic acid or its derivative. The component unit derived from a polyhydric alcohol is mainly formed of a dihydric alcohol or a derivative thereof, but a part thereof may be formed of a polyhydric alcohol having a valence of 3 or more or a derivative thereof.

The polyvalent carboxylic acid includes aromatic polyvalent carboxylic acid, alicyclic polyvalent carboxylic acid, and aliphatic polyvalent carboxylic acid, and derivatives thereof include ester compounds and salts of carboxylic acid. And in this invention, a part of divalent carboxylic acid which forms aromatic polyester is aromatic dicarboxylic acid. The polyhydric alcohols include alicyclic polyhydric alcohols and aliphatic polyhydric alcohols, and the derivatives thereof include ester compounds of these alcohols.

Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid and p-phenylenedicarboxylic acid.

Further, examples of the alicyclic dicarboxylic acid include
1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, pinic acid, homopic acid, 1, 1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1 , 4-cyclohexanedicarboxylic acid,
1,1-cyclohexanediacetic acid, 1,2-cyclohexanediacetic acid, 2,3-bicyclo [2,2,2] octanedicarboxylic acid, 1,4-
Bicyclo [2,2,2] octanedicarboxylic acid, 2,5-dioxo-
1,4-bicyclo [2,2,2] octanedicarboxylic acid, 1,5-bicyclo [3,2,2] nonanedicarboxylic acid, 6,8-dioxo-1,5-bicyclononanedicarboxylic acid, 1,3 Mention may be made of -adamantanedicarboxylic acid, 4,8-dioxo-1,3-adamantanedicarboxylic acid and 2,6-spiro [3,3] heptanedicarboxylic acid.

Further, examples of the aliphatic dicarboxylic acid include succinic acid, glutaric acid, adipic acid, suberic acid,
Mention may be made of azelaic acid, sebacic acid and dodecanedioic acid. Examples of these dicarboxylic acid derivatives include ester compounds of the above dicarboxylic acids and lower alcohols such as methanol and ethanol, and alkali metal salts of the above dicarboxylic acids. These dicarboxylic acids or their derivatives can be used alone or in combination.

Examples of the aliphatic dialcohol include ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol,
Mention may be made of triethylene glycol, polyethylene glycol and polytetramethylene glycol.

Further, as an example of the alicyclic dialcohol,
1,1-cyclopropanedimethanol, 1,2-cyclopropanedimethanol, 1,1-cyclobutanedimethanol, 1,2-cyclobutanedimethanol, 1,3-cyclobutanedimethanol, 1,1-cyclopentanedimethanol , 1,2-cyclopentanedimethanol, 1,3-cyclopentanedimethanol,
1,1-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-
Cyclohexanedimethanol, 1,2-cyclohexanediethanol, 2,3-bicyclo [2,2,2] octanedimethanol, 1,4-bicyclo [2,2,2] octanedimethanol, 1,5-
Bicyclo [3,2,2] nonanedimethanol, 6,8-dioxo-1,
Mention may be made of 5-bicyclononane dimethanol, 1,3-adamantane dimethanol, 4,8-dioxo-1,3-adamantane dimethanol and 2,6- [3,3] heptaoxodimethanol.

The unmodified aromatic polyester used for preparing the adhesive component of the present invention comprises at least one of the above-mentioned alicyclic dialcohol-derived component unit and alicyclic dicarboxylic acid-derived component unit. It is a copolyester having one side. That is, in order to impart solvent resistance while securing solubility of the modified polyester [B], which is the adhesive component of the present invention, in an organic solvent, and further improve properties such as heat resistant adhesion and hot water resistance, It is necessary to control the crystallinity and glass transition temperature (Tg) of the modified aromatic polyester [A]. The glass transition temperature (Tg) of the unmodified aromatic polyester [A] can be controlled by the type of polyvalent carboxylic acid and / or polyhydric alcohol used. That is, this unmodified aromatic polyester [A] is a component derived from a compound in which at least one of a component unit derived from a polyvalent carboxylic acid and a component unit derived from a polyhydric alcohol has an alicyclic structure. It is a unit. Specifically, the unmodified aromatic polyester [A] has a component unit derived from an alicyclic dicarboxylic acid and / or a repeating unit derived from an alicyclic dialcohol.

Here, as preferable examples of the alicyclic dicarboxylic acid, among the alicyclic dicarboxylic acids exemplified above, 1,
4-Cyclohexanedicarboxylic acid, 1,4-bicyclo [2,2,2]
Octanedicarboxylic acid, 2,5-dioxo-1,4-bicyclo [2,
Examples thereof include 2,2] octanedicarboxylic acid, 1,5-bicyclo [3,2,2] nonanedicarboxylic acid, 2,6-spiro [3,3] heptanedicarboxylic acid and derivatives thereof. By using such an alicyclic dicarboxylic acid, the glass transition temperature of the unmodified aromatic polyester [A] can be easily adjusted and the obtained polyester molecule becomes linear. Among these, 1,4-cyclohexanedicarboxylic acid is particularly preferable.

The other dicarboxylic acid component unit forming the unmodified aromatic polyester [A] as described above is a component unit derived from an aromatic dicarboxylic acid. Thus, the unmodified aromatic polyester [A] having a component unit derived from an aromatic dicarboxylic acid shows excellent heat resistance.
Here, examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid and trimellitic acid, and among these, terephthalic acid is preferable. Further, it is preferable to use a small amount of an aliphatic dicarboxylic acid such as adipic acid in combination as the dicarboxylic acid.

Preferred examples of the alicyclic dialcohol which forms the unmodified polyester [A] with the above dicarboxylic acid include 1,3-cyclobutanedimethanol, 1,4-cyclohexanedimethanol and 1,4-bicyclo [alcohol]. 2,2,2] octanedimethanol, 2,5-dioxo-1,4-bicyclo [2,2,2] octanedimethanol, 1,5-bicyclo [3,2,2] nonanedimethanol and 2, Mention may be made of 6-spiro [3,3] heptanedimethanol. By using the alicyclic dialcohol as described above, the glass transition temperature of the unmodified aromatic polyester [A] can be easily adjusted, and
The resulting polyester molecule is linear. Of these, 1,4-cyclohexanedimethanol is particularly preferable. Polyhydric alcohols other than the alicyclic dialcohols that form the unmodified aromatic polyester [A] are usually aliphatic polyhydric alcohols, and in consideration of the linearity of the polyester molecule, ethylene glycol and propylene glycol are Among these, ethylene glycol is particularly preferable.

Further, unmodified aromatic polyester [A]
May have a component unit derived from a polycarboxylic acid having a valence of 3 or more and a derivative thereof in addition to the above-mentioned dicarboxylic acid. Examples of the trifunctional or higher polyvalent carboxylic acid and its derivative include trimellitic acid and pyromellitic acid, and ester compounds, acid anhydrides and salts thereof.

Similarly, as the polyhydric alcohol, a trifunctional or higher functional alcohol may be used in combination with the above dialcohol. Examples of the trifunctional or higher functional alcohol include trimethylolpropane and pentaerythritol. .

Among the unmodified aromatic polyesters [A] composed of the above component units, for example, aromatic aromatic polyesters composed of repeating units represented by the following formulas [I] to [IV] Polyester [A] is preferred.

[0033]

[Chemical 1]

[I] In the above formula [I], R ¹ is usually a hydrocarbon group having 1 to 6 carbon atoms, n is usually 0, 1 or 2, preferably 0, m is usually 1 to 10, preferably 2 to 6, and r has a relationship of 0 ≦ r ≦ n + 4.

[0035]

[Chemical 2]

[II] In the above formula [II], R ¹ is usually a hydrocarbon group having 1 to 6 carbon atoms, and R ² is independently a hydrogen atom or 1 to 4 carbon atoms. A hydrocarbon group of R ³ and R ⁴
Each independently represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 4 carbon atoms. Further, n is usually 0, 1 or 2, preferably 0, r has a relationship of 0 ≦ r ≦ n + 4, and p and q are each independently 0 to 0.
4, p and q are never 0, and s is usually 1-2. The alicyclic ring defined by s may form a spiro ring or a bicyclo ring.

[0037]

[Chemical 3]

[III] In the above formula [III], R ² and R ⁵ are each independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and R ³ , R ⁴ and R ⁶ And R ⁷ each independently represent a single bond or a divalent aliphatic hydrocarbon group having 1 to 4 carbon atoms. Further, p and q are each independently 0 to
4, p and q are never 0, and s and t are each independently 1 or 2 in general. The alicyclic ring defined by s may form a spiro ring or a bicyclo ring.

[0039]

[Chemical 4]

[IV] In the above formula [IV], R ⁵ is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and R ⁶ and R ⁷ are independently, Single bond or C1-4
Represents a divalent aliphatic hydrocarbon group. Also, p and q
Are, independently of each other, usually 0 to 4 and p and q
Both do not become 0, and t is usually 1 to 2. Further, the alicyclic ring defined by t may form a spiro ring or a bicyclo ring.

The unmodified aromatic polyester [A] contains the repeating unit represented by the above formula [I] in an amount of usually 20 to 90 mol%, preferably 30 to 87 mol%, particularly preferably 4
The content of the repeating unit represented by the above formula [II] is usually 10 to 80 mol%, preferably 15 to 70 mol%, particularly preferably 20 to 60 mol%. Contains in quantity. The repeating unit represented by the formula [III] is usually 0 to 80 mol%, preferably 0 to 6
0 mol%, particularly preferably 0 to 40 mol%, the amount of the component unit represented by the formula [IV] is usually 0 to 80 mol%, preferably 0 to 60 mol%, particularly preferably 0 to 40 mol%. Contained in.

Unmodified aromatic polyester [A]
Has a component unit derived from the alicyclic dicarboxylic acid, the content of the component unit in the component unit derived from the polyvalent carboxylic acid is usually 10 to 80 mol%, preferably 15 to It is in the range of 60 mol%. When the unmodified aromatic polyester [A] has a component unit derived from the alicyclic dialcohol, the content ratio of the component unit in the component unit derived from the polyhydric alcohol is usually 10 to 10. 80 mol%, preferably 1
It is in the range of 5 to 60 mol%. Furthermore, the total content of the alicyclic dicarboxylic acid component units and / or the alicyclic dialcohol component units in all the component units forming the unmodified aromatic polyester [A] is usually 10 to 8.
It is 0 mol%, preferably 15 to 60 mol%.

In this unreacted aromatic polyester [A], the content of component units derived from a trifunctional or higher polyvalent carboxylic acid and a trifunctional or higher polyhydric alcohol is usually 10 mol% or less. It is preferably 5 mol% or less.

By introducing an alicyclic structure which suppresses the rotational motion of the molecule into the polyester molecule in this way, the molecular motion of the polyester molecule is suppressed, so that the unmodified aromatic polyester [A] and modified polyester [ B]
It is considered that the glass transition temperature (Tg) of sucrose increases.
And as a result, the heat resistant adhesiveness of modified polyester [B] improves. Further, the polyester having the alicyclic structure introduced therein is crystallized from the unmodified aromatic polyester [A] and the modified polyester [B] even when a component that impairs the linearity of the polyester molecule is copolymerized. The modified polyester [B] exhibits excellent solvent resistance while ensuring the solubility in an organic solvent, and the hot water resistance is improved.

The glass transition temperature (Tg) of the unmodified aromatic polyester [A] having such a composition is usually from 20 to
Within the range of 150 ° C. In this way, for example, by adjusting the polymerization amount of the component to be copolymerized and making the glass transition temperature (Tg) within the above range, the graft modified product has characteristics such as good adhesiveness. Further, this glass transition temperature (Tg) is preferably in the range of 30 to 120 ° C, and particularly preferably in the range of 40 to 100 ° C.

The unmodified aromatic polyester [A] has crystallinity. Furthermore, when the number average molecular weight of this unmodified aromatic polyester [A] is determined using gel permeation chromatography (GPC), the number average molecular weight is usually 500 to 200,000, preferably 1,000 to 100,000, and more preferably Is 5,000-60,
It is in the range of 000. If the number average molecular weight deviates from the above range and is low, the adhesive strength may be lowered, and if it deviates from the above range and the workability may be lowered.

Further, the softening temperature (TMA) of this unmodified aromatic polyester [A] measured by a thermal mechanical analyzer is usually 40 ° C. or higher, preferably 60 ° C. or higher.

The unmodified aromatic polyester [A] is
For example, it can be synthesized by an esterification reaction or a transesterification reaction between a polyvalent carboxylic acid, a lower alkyl ester thereof or an anhydride of the polyvalent carboxylic acid, and a polyvalent alcohol. It can also be produced by reacting a halide corresponding to a polycarboxylic acid with an alkoxide of a polyhydric alcohol.

Ethylenically Unsaturated Carboxylic Acid Compound [C] In the adhesive component of the present invention, a predetermined amount of the ethylenically unsaturated carboxylic acid compound [C] is uniformly graft-polymerized on the above-mentioned unmodified aromatic polyester [A]. The modified polyester [B].

The ethylenically unsaturated carboxylic acid compound [C] used here includes ethylenically unsaturated carboxylic acids and derivatives of the ethylenically unsaturated carboxylic acids.
Examples of the ethylenically unsaturated carboxylic acid include acrylic acid, methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endocis-bicyclo [2, 2,1] Hept-5-ene-2,3-dicarboxylic acid (Nadic acid ^TM ) and methyl-endocis-bicyclo
Mention may be made of [2,2,1] hept-5-ene-2,3-dicarboxylic acid (methyl nadic acid ^™ ). Examples of the ethylenically unsaturated carboxylic acid derivative include acid halide compounds, amide compounds, imide compounds, acid anhydrides and ester compounds of the above ethylenically unsaturated carboxylic acids. Specific examples of the ethylenically unsaturated carboxylic acid derivative include maleenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate and dimethyl maleate.

Of these, ethylenically unsaturated dicarboxylic acids or acid anhydrides thereof are preferable, and maleic acid, nadic acid or acid anhydrides thereof are particularly preferable.
These compounds can be used alone or in combination. Further, the above-mentioned compound can be used in combination with another monomer which can undergo a graft reaction with the unmodified aromatic polyester [A] within a range not impairing the object of the present invention.

In the present invention, examples of other monomers which can be used in combination with the ethylenically unsaturated carboxylic acid compound [C] include dimethylaminoethyl acrylate, acrylamine, aminoethyl methacrylate, dimethylaminoethyl methacrylate. Amino group-containing ethylenically unsaturated compounds such as aminopropyl methacrylate, N, N-dimethylaminopropylacrylamide and aminostyrene; hydroxyl groups such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate and allyl alcohol Containing ethylenically unsaturated compound; styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, m-ethylstyrene, p-ethylstyrene, o-isopropylstyrene, m-isopropylstyrene Preliminary p- isopropyl styrene styrene series hydrocarbon compounds such as and the like. At this time, the ratio of the ethylenically unsaturated carboxylic acid compound [C] contained in all graft monomer components is
It is preferably 50 to 100% by weight. Therefore, the amount of the other monomer used is usually 0 to 50% by weight.

Ethylenically unsaturated carboxylic acid compound [C]
Is usually 0.1 to 60 parts by weight, preferably 0.5 to 4 parts by weight, relative to 100 parts by weight of the unmodified aromatic polyester [A].
Used in an amount of 5 parts by weight. By using the ethylenically unsaturated carboxylic acid compound [C] in such an amount,
The modified polyester [B] contains 0.1 to 5 component units derived from the ethylenically unsaturated carboxylic acid compound [C].
Graft polymerize in an amount of 0% by weight, preferably 0.5 to 35% by weight.

Ethylenically unsaturated carboxylic acid compound [C]
The modified polyester [B] obtained by graft-polymerizing the component units derived from the above in an amount within the above range exhibits good adhesiveness to the substrate. That is, if the graft amount is less than 0.1% by weight, the adhesiveness between the modified polyester, which is the adhesive component, and the substrate will not be sufficiently exhibited. Also, 50% by weight
If it is more than the above range, the internal cohesive force of the adhesive layer is lowered, the adhesive force itself is lowered, and it is disadvantageous from the economical aspect.

Modified polyester [B] The following method can be employed to uniformly graft-copolymerize the ethylenically unsaturated carboxylic acid compound [C] with the unmodified aromatic polyester [A].

For example, unmodified aromatic polyester [A]
A molten state, and a graft copolymerization by adding an ethylenically unsaturated carboxylic acid compound [C], and
A method of adding an ethylenically unsaturated carboxylic acid compound [C] to a solution in which the unmodified aromatic thermal polyester [A] is dissolved and performing graft copolymerization can be adopted.

When the unmodified aromatic polyester [A] in a molten state is graft-copolymerized with the ethylenically unsaturated carboxylic acid compound [C], the reaction temperature is usually the glass transition temperature of the unmodified aromatic polyester [A]. The temperature is set to (Tg) or higher, preferably a temperature higher than the glass transition temperature (Tg) by 150 ° C. higher than the glass transition temperature (Tg), specifically, a temperature generally in the range of 50 to 200 ° C.
The reaction time under such temperature conditions is usually 0.1.
It is 5 to 10 minutes, preferably 1 to 5 minutes.

When the unmodified aromatic polyester [A] is dissolved in a solvent to graft-copolymerize the ethylenically unsaturated carboxylic acid compound [C], the reaction temperature is
Usually, it is set to a temperature not higher than the boiling point of the solvent used, preferably 30 ° C. lower than the boiling point to the boiling point. The reaction time under such temperature conditions is usually 0.5-
It is 15 hours, preferably 1 to 10 hours. The solvent used in this reaction has no reactivity with the unmodified aromatic polyester [A] and the ethylenically unsaturated carboxylic acid compound [C] and is stable, and at least the unmodified aromatic polyester [A], preferably A solvent that can dissolve both the unmodified aromatic polyester [A] and the ethylenically unsaturated carboxylic acid compound [C] is used. Generally, an aromatic solvent, a halogenated hydrocarbon solvent, or the like has such characteristics, and when a graft copolymerization is carried out using the above method, an unmodified aromatic solvent is selected from these solvents. The solvent can be appropriately selected in consideration of the reactivity with respect to the component unit constituting the group polyester [A] and the solubility of the resin and the like.

Examples of aromatic solvents that can be used here include anisole, orthochlorophenol and dichlorobenzene. In addition, examples of the solvent other than the aromatic solvent, particularly the halogenated hydrocarbon solvent, include carbon tetrachloride and chloroform. These solvents can be used alone or in combination.

Thus, when the ethylenically unsaturated carboxylic acid compound [C] is graft-copolymerized with the unmodified aromatic polyester [A], a radical initiator can be used for efficient reaction. . As the radical initiator, for example, organic peroxides, organic peresters and azo compounds can be used.

Examples of organic peroxides used herein are benzoyl peroxide, dicumyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis- (tert- Butylperoxy) hexane, 2,5-dimethyl-2,5-bis- (tert-butylperoxy) hexyne-3,1,3-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-
4,4-bis (tert-butylperoxy) valerate, dibenzoyl peroxide, tert-butyl peroxybenzoate acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, uranoyl peroxide, 3,5,5-trimethyl hexa Mention may be made of noyl peroxide, 2,4-dichlorobenzoyl peroxide and m-toluoyl peroxide.

As an example of the organic perester, te
rt-butyl peracetate, tert-butyl perphenyl acetate, tert-butyl peroxyisobutyrate, ter
Mention may be made of t-butyl per-sec-octaate, tert-butyl perpivalate, cumyl perpivalate and tert-butyl perdiethyl acetate. Furthermore, examples of the azo compound include azobisisobutyronitrile and dimethylazoisobutyrate.

Such radical initiators can be used alone or in combination. Among such radical initiators, dicumyl peroxide, di-tert-
Butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (tert-
Dialkyl peroxides such as butylperoxy) hexane, 1,4-bis (tert-butylperoxyisopropyl) benzene and dibenzoyl peroxide are preferred. Such a radical initiator is usually used in an amount of 0.1 to 1 relative to 100 parts by weight of the unmodified aromatic polyester [A].
Used in an amount of 5 parts by weight.

Further, with or without using these organic peroxides, organic peresters or azo compounds, energy rays such as ionizing radiation or ultraviolet rays can be separately used as a radical generating source.

In the present invention, among the above methods, a method in which the unmodified aromatic polyester [A] is dissolved or dispersed in an organic solvent and graft-polymerized is preferable, and particularly unmodified in an aromatic organic solvent such as anisole. Aromatic polyester [A] and ethylenically unsaturated carboxylic acid [C]
The method of dissolving and graft polymerizing is particularly preferable.
By adopting this method, the graft polymerization reaction proceeds more uniformly and the graft group is uniformly introduced into the entire modified polyester. That is, for example, when polyester fibers or the like are dispersed as they are in a solvent and graft-modified, a non-uniform graft-modified fiber in which graft groups are present at a high density on the surface of the fiber is produced. For example, by dissolving the unreacted aromatic polyester [A] in an organic solvent such as anisole and performing graft modification, the modification reaction uniformly proceeds over the entire aromatic polyester, and a modified polyester having excellent adhesiveness can be obtained. it can. Further, since the heating during the modification is suppressed by the modification in this way, the unmodified aromatic polyester [A] is not thermally decomposed by the reaction heat, and thus the unmodified aromatic polyester [A] used can be obtained. The molecular weight of the modified polyester [B] hardly changes.

Modified polyester [B] as an adhesive component
Has a main skeleton similar to that of the unmodified aromatic polyester [A] composed of repeating units represented by the above formulas [I] to [IV], and the main skeleton has an ethylenically unsaturated carboxylic acid [ The component unit derived from C] has a form of graft polymerization. The graft amount of the component unit derived from the ethylenically unsaturated carboxylic acid [C] in the modified polyester [B] is 0.1 to 5 as described above.
It is in the range of 0% by weight, preferably 0.3 to 30% by weight, particularly preferably 0.5 to 25% by weight.

The modified polyester in which the component unit derived from the ethylenically unsaturated carboxylic acid [C] within the above range is graft-polymerized is a different plastic or metal without using a curing agent such as isocyanate or epoxy compound. Etc. and has good adhesiveness. Furthermore, the adhesive layer containing this modified polyester [B] as an adhesive component has good heat resistance, and for example, even when the adhesive layer is in contact with boiling water, the adhesive layer softens. Does not peel off.

The modified polyester [B] which is the adhesive component of the present invention has a glass transition temperature in the range of 20 to 150 ° C.
It is necessary to have (Tg). The modified polyester [B] having such a glass transition temperature (Tg) exhibits good adhesiveness. Furthermore, this glass transition temperature (Tg)
Is preferably in the range of 30 to 120 ° C., and particularly preferably in the range of 40 to 100 ° C.

The modified polyester [B] has crystallinity, like the above-mentioned unmodified aromatic polyester [A]. Furthermore, gel permeation chromatography (GPC) was performed on this modified polyester [B].
When the number average molecular weight is determined using, the number average molecular weight is usually in the range of 500 to 200,000, preferably 1,000 to 100,000, and more preferably 5,000 to 60,000. When the number average molecular weight is less than 500, the cohesive force of the adhesive layer becomes small, so that sufficient adhesive force may not be obtained.
When the number average molecular weight is larger than 100,000,
Since the viscosity in a solution state or a molten state becomes high, the workability of bonding work may deteriorate when used as an adhesive. Furthermore, the molecular weight distribution (Mw /
Mn) is usually in the range of 1-8, preferably 1.2-5.

The softening temperature (TMA) of this modified polyester [B] measured by a thermal mechanical analyzer is usually 40 ° C. or higher, preferably 60 ° C.
That is all. That is, this modified polyester [B]
Has thermoplasticity.

The modified polyester [B] of the present invention having the above-mentioned properties shows excellent thermal adhesiveness to various materials such as different kinds of plastics, metals or metal foils. Further, the modified polyester [B] dissolves in a solvent having a relatively high solubility such as anisole, but does not show any solubility in a solvent having a solubility to some extent lower than these solvents. That is, the modified polyester [B] can be used in a solution state in which it is dissolved in a highly soluble solvent such as anisole, but once adhered, the adhesive layer has excellent solvent resistance. As shown. In addition, this modified polyester [B]
Shows very excellent resistance to water, the modified polyester [B] is not attacked even if it is contacted with water at room temperature for a long time, and when used as an adhesive,
The contact with boiling water does not destroy the adhesive layer due to decomposition, softening, etc. of the modified polyester [B]. Adhesive Polyester Composition The modified polyester [B] can be used alone as an adhesive, but the modified polyester [B] and a thermoplastic polyester may be mixed and used as an adhesive resin composition. it can.

The thermoplastic polyester used here is not particularly limited and may be a thermoplastic polyester such as polyethylene terephthalate. However, considering the affinity with the modified polyester, the modified polyester [B] is formed. It is preferable to use the same polyester as the aromatic polyester.

In this adhesive polyester composition, the modified polyester [B] and the thermoplastic polyester (preferably unmodified aromatic polyester [A]) are 100: 0.
It is compounded in the weight ratio ([B]: [A]) of about 2:98. Further, in the case of the composition, the weight ratio of [B]: [A] is 99: 1.
It is preferable to be within the range of 5:95 to 99: 1 to 1
It is particularly preferable to set it within the range of 0:90.

This adhesive polyester composition can be produced by mixing the thermoplastic polyester and the modified polyester [B]. As the mixing method, various methods such as a method of heating and kneading the both until they are in a molten state, a method of dissolving both in a solvent and mixing, can be adopted. And this adhesive composition has very good adhesive performance by itself, and therefore, the adhesive polyester composition shows good adhesiveness without using a curing agent such as isocyanate. .

The adhesive polyester composition of the present invention can be used for adhering plastics of the same kind or different kinds, or metal. The following polymers can be mentioned as examples of the plastics that can be bonded by the adhesive component and the adhesive polyester composition of the present invention.

(I) A polymer derived from a hydrocarbon having one or two unsaturated bonds. Specific examples include polyethylene, polypropylene,
Synthesized from hydrocarbon compounds having one or two unsaturated bonds in the molecule such as polyisobutylene, polymethylbutene-1, poly4-methylpentene-1, polybutene-1, polyisoprene, polybutadiene and polystyrene Polymers and copolymers of monomers constituting the polymer [Examples: ethylene / propylene copolymer, propylene / butene-1 copolymer, propylene / isobutylene copolymer, styrene / butadiene copolymer, ethylene A terpolymer such as propylene / diene (eg, hexadiene, cyclopentadiene, ethylidene norbornene)] and the like. A crosslinked structure may be formed in these polymers or copolymers.

(Ii) A halogen-containing vinyl polymer. Specific examples include polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polychloroprene and chlorinated rubber.

(Iii) Polymers derived from α, β-unsaturated carboxylic acids and their derivatives. Specific examples thereof include polyacrylate, polymethacrylate, polyacrylamide and polyacrylonitrile, and further, a copolymer of a monomer forming these polymers and another monomer may be used. Examples of such copolymers include acrylonitrile-butadiene-styrene copolymer, acrylonitrile-
Examples thereof include styrene copolymers and acrylonitrile / styrene / acrylic acid ester copolymers.

(Iv) Polymers derived from unsaturated alcohols and amines or acyl derivatives thereof, or acetals. Specific examples include polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, vinyl polybenzoate, vinyl polymaleate, polyvinyl butyral, polyallyl phthalate and polyallyl melamine, and further, for example, ethylene acetic acid. Examples thereof include a copolymer of a monomer constituting the above polymer such as a vinyl copolymer and a monomer copolymerizable with this monomer.

Specific examples of such copolymers include ethylene / vinyl acetate copolymers and ethylene / vinyl alcohol copolymers. (v) Polymers derived from epoxides.

Specific examples include polymers derived from polyethylene oxide or bisglycidyl ether. (vi) Polyacetal.

Specific examples include polyoxymethylene, polyoxyethylene, and polyoxymethylene containing ethylene oxide as a comonomer.

(Vii) Polyphenylene oxide. (iix) Polycarbonate. (ix) Polysulfone.

(X) Polyurethane and urea resins. (xi) Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or the corresponding lactams.

Specific examples include nylon 6, nylon 66, nylon 11 and nylon 12. (xii) A polymer having a crosslinked structure derived from an aldehyde and phenol, urea or melamine.

Specific examples include phenol / formaldehyde resins, urea / formaldehyde resins, and melamine / formaldehyde resins. (xiiv) Alkyd resin.

Specific examples include glycerin / phthalic acid resins. (xiv) Saturated and unsaturated polyesters obtained by polycondensation of polyhydric carboxylic acids and polyhydric alcohols.

Specific examples include polyethylene terephthalate and polybutylene terephthalate. (xv) Natural resin.

As specific examples, cellulose, rubber,
Examples thereof include proteins or their derivatives (eg, cellulose acetate, cellulose propionate, cellulose ether).

Examples of metals that can be bonded by the adhesive component and the adhesive polyester composition of the present invention include:
Examples thereof include aluminum, iron, iron-plated products, copper, lead, nickel, zinc, and alloys composed of these elements.

The adhesive component and the adhesive polyester composition of the present invention include a melt type adhesive, a solution type adhesive, water and a poor solvent for the adhesive polyester composition.
Any form of a dispersion type adhesive dispersed in (eg alcohol, ketone, ether, etc.) can be used. For example, in order to bond the adhesive component or the adhesive polyester composition by using it as a melt type adhesive, the adhesive component or the adhesive polyester composition is heated to a molten state, and then the adherends are joined. Can be glued by.

When the adherend is not thermoplastic, a method of laminating the molten adhesive polyester composition on the adherend, preliminarily laminating the adherend, the adhesive layer and both layers of the adherend. After that, a method of heating, melting and pressing, a method of adhering an adhesive polyester composition or an adhesive component to an adherend by static electricity or the like to form an adhesive layer and then melting the adhesive layer to form an adhesive layer, Examples include a method of preheating above the melting point of the adhesive component or the adhesive polyester composition, and then adhering the adhesive component or the adhesive polyester composition on the adhesive component to bring it into a molten state to laminate and adhere the adherend. be able to.

When the adherend is thermoplastic, a method of melting and laminating both the adhesive component or the adhesive polyester composition and the adherend, the adhesive component or adhesive polyester melted on the adherend The method of laminating a composition can be illustrated.

Further, as a method for carrying out the adhesion processing using the adhesive component or the adhesive polyester composition of the present invention as a solution type or dispersion type adhesive, the adhesive is applied to one side of one substrate by a dry laminator. After volatilizing the solvent, a method of laminating with the other substrate can be exemplified.

At the time of the above-mentioned adhesion, sufficient adhesion strength is exhibited even if the adherend is not surface-treated, but if necessary, a pretreatment method conventionally used, for example, flame treatment of the adhesion surface is performed. Alternatively, a treatment such as corona discharge and / or a treatment such as application of a primer may be performed.

Since the adhesive component and the adhesive polyester composition of the present invention have good adhesive properties themselves unlike the conventional polyester adhesives, the composition further contains an isocyanate or the like. It is not necessary to add a curing agent. However, it is possible to add a curing agent to the adhesive polyester composition of the present invention to enhance the adhesive performance of the adhesive polyester composition in a reinforcing manner. Particularly when used as a dry laminate adhesive, it is often useful to use a curing agent together. Specific examples of the curing agent used in this case include hexamethylene diisocyanate,
Examples thereof include phenylene diisocyanate, polyisocyanate compounds such as 2,4- or 2,6-tolylene diisocyanate, and melamine compounds such as dimethylol melamine and trimethylol melamine. The mixing ratio of these curing agents is such that the equivalent ratio of the hydroxyl group in the polyester composition to the isocyanate group in the polyisocyanate compound or the methylol group in the melamine compound is 0.5 to 5, preferably 0.8 to 4.5. Is determined to be.

The hardener is usually mixed just before using the adhesive. When such a curing agent is blended, the curing reaction after bonding the base materials sufficiently proceeds at room temperature, that is, near room temperature (0 to 40 ° C.), but may be heated if necessary.

The adhesive polyester composition or modified polyester [A] of the present invention can be used alone as an adhesive as described above, but various known additives are added to the extent that the characteristics are not impaired. You can also do it. The additives used here include heat stabilizers and pigments.

The heat resistance stabilizer used in the present invention includes
Examples thereof include phenolic antioxidants, sulfur antioxidants and phosphorus antioxidants. Examples of phenolic antioxidants used here include 2,6-di-tert-
Butyl-p-cresol, stearyl (3,3-dimethyl-4-hydroxybenzyl) thioglycolate, stearyl-β-
(4-Hydroxy-3,5-di-tert-butylphenol) propionate, distearyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphate, 2,4,6-tris (3'5'- Di-t
ert-Butyl-4'-hydroxybenzylthio) -1,3,5-triazine, distearyl (4-hydroxy-3-methyl-5-tert-butylbenzyl) malonate, 2,2'-methylenebis [6- ( 1-methylcyclohexyl) p-cresol], bis [3,5-bis (4-
Hydroxy-3-tert-butylphenyl) butyric acid acid] glycol ester, 4,4'-butylidene bis (6-tert-
Butyl-m-cresol), 1,1,3-tris (2-methyl-4- (5-t
ert-Butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2 , 6-Dimethyl-3-hydroxy-4-tert-butyl) benzyl isocyanurate, 1,3,5-tris (3,5, -di-tert-butyl-4-hydroxybenzyl) -2,4,6- Trimethylbenzene, tetrakis
[Methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 1,3,5-tris (3,5-di-tert
-Butyl-4-hydroxybenzyl) isocyanurate, 1,
3,5-Tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 2-octylthio-4,6-di (4-hydroxy-3,5-di-tert -Butyl)
Phenoxy-1,3,5-triazine and 4,4'-thiobis (6-t
ert-butyl-m-cresol) and the like; and
Carbonic acid oligoesters such as carbonic acid oligoesters such as 4,4′-butylidene bis (2-tert-butyl-5-methylphenol) (eg, degree of polymerization: about 2 to 10) can be mentioned.

Examples of sulfur type antioxidants include dialkylpropionate (eg, dilaurylpropionate, distearylpropionate), alkylthiopropionic acid.
(Example: butylthiopropionic acid, octylthiopropionic acid, laurylthiopropionic acid, stearylthiopropionic acid) and polyhydric alcohols (e.g. glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyisocyanurate) Mention may be made of esters (eg pentaerythritol tetralauryl thiopropionate).

Examples of phosphorus antioxidants include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl-diphenyl phosphite, tris (2,4, -di-tert-butylphenyl). Phosphite, triphenyl phosphite, tris (butoxyethyl) phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol phosphite, tetra (tridecyl) -1,1,3-
Tris (2-methyl -5-tert-butyl-4-hydroxyphenyl) butane diphosphite, tetra (C ₁₂ -C ₁₃ mixed alkyl) -4,4'-isopropylidene phenyl phosphite, tetra (tridecyl) -4 4,4'-butylidene bis (3-methyl-6-tert-butylphenol) diphosphite, tris (3,5-di-tert-butyl-4-hydroxyphenyl phosphite, tris (mono / di mixed nonylphenyl) phosphite , Hydrogenated-4,4'-isopropylidene diphenyl polyphosphite, bis (octylphenyl) -bis [4,4'-
Butylidene bis (3-methyl-6-tert-butylphenol)] ・
1,6-hexanediol diphosphite, phenyl-4,
4'-isopropylidene diphenol pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-
Di-tert-butyl-4-methylphenyl) pentaerythritol diphenylphosphite, tris [4,4'-isopropylidenebis (2-tert-butylphenol)] phosphite, phenyl diisodecylphosphite, di (nonylphenyl) penta Erythritol diphosphite, tris (1,3-di-stearoyloxyisopropyl) phosphite, 4,4'-isopropylidenebis (2-tert-butylphenol) / di (nonylphenyl) phosphite, 9,10
-Dihydro-9-oxa-10-phosphaphenanthrene-10-
Mention may be made of oxides and tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite.

Further, for example, various tocopherols of α, β, γ or δ or a mixture thereof; 2,5-dimethyl substitution product of 2- (4-methyl-pent-3-enyl) -6-hydroxychroman, 2 2,5,8-Trimethyl substitution, 2,5,7,8-Tetramethyl substitution; 2,2,7-Trimethyl-5-tert-butyl-6-
Hydroxychroman, 2,2,5-trimethyl-7-tert-butyl
-6-hydroxychroman, 2,2,5-trimethyl-6-tert-butyl-6-hydroxychroman and 2,2-dimethyl-5-tert
It is also possible to use 6-hydroxychroman derivatives such as -butyl-6-hydroxychroman.

Examples of pigments include carbon black, silica, diatomaceous earth, zinc oxide and magnesia. Since the adhesive component and the adhesive polyester composition of the present invention have good heat resistance, they are suitable as an adhesive for use after heating after adhesion such as packaging of retort foods. Especially for the adhesive component and adhesive polyester composition of the present invention JIS-
In accordance with the method of peeling adhesive strength test of adhesive described in K-6854, width 1 from the adherend / adhesive / adherent laminate
When a 5 mm test piece is peeled in the direction of 180 ° at 80 ° C, the peel strength is usually 2.3 kg / cm or more, and in most cases 3.0 kg / cm or more, showing excellent heat-resistant adhesion. Also,
Test pieces prepared in the same manner at 135 ° C. for 20 minutes, 3.
Peel strength treated under pressure of 3kg / cm ² is usually 1.8k
g / cm or more, and usually 2.8k in the case of a composition
Greater than g / cm and shows excellent retort resistance.

As described above, the adhesive component and the adhesive polyester composition of the present invention are adhesives for adhering adherends to each other, such as a laminated film, a laminated sheet, a laminated bottle and a hot melt adhesive. Besides, it can be used as a film-forming agent by utilizing its good adhesive performance. That is, it can be applied to many uses such as a film forming element such as a rust preventive coating for a metal plate or a metal tube or an inner surface coating for a metal can for food.

[0105]

According to the present invention, by graft-copolymerizing a specific unreacted aromatic polyester [A] with an ethylenically unsaturated carboxylic acid compound [C], adhesion with different kinds of plastics or metals, An adhesive component having excellent heat resistance and solvent resistance can be provided. The adhesive component thus obtained has good heat-resistant adhesive strength without using a curing agent such as a polyisocyanate compound, and when used for adhesion of a laminated film for food, etc. Good adhesive strength can be maintained even after the retort treatment.

Moreover, since the graft group is uniformly introduced into the aromatic polyester, the adhesive strength is uniform.

[0107]

The present invention will now be described in more detail with reference to the examples of the present invention, but the present invention should not be construed in a limited manner by these examples.

The properties of the modified polyester and the adhesive polyester composition in the present invention were evaluated by the methods described below. Peeling test According to the method of peeling adhesion strength test of adhesive described in JIS-K-6854, a test piece with a width of 15 mm is prepared from a laminate of adherend / adhesive / adherent and 180 ° The peel strength was measured by peeling in the direction. Also, the measurement of the peel strength at 80 ° C is 80 ° C.
The test piece was attached to the crosshead installed in the oven kept at 10 ° C., and after leaving it for 10 minutes, the peel strength was measured. A test piece was prepared in the same manner as the retort resistance peeling test, and this test piece was
After treating at 20 ° C. for 20 minutes under a pressure of 3.3 kg / cm ² , it was cooled to room temperature, and the peel strength was measured and the appearance was inspected. Solvent resistance According to the method of adhesive chemical resistance test described in JIS-K-6858, the test piece was immersed in acetic ester at 20 ° C. for 7 days, and then the peel strength was measured and the appearance was inspected. .

[0109]

Example 1 Terephthalic acid (sometimes abbreviated as “TA”) / ethylene glycol (sometimes abbreviated as “EG”) / 1,4-cyclohexanedimethanol (“CHD”)
Abbreviated as "M") Copolymer (TA / EG / C
HDM = 100/68/32 mol) was prepared. This T
The A / EG / CHDM copolymer was produced as follows.

In a stainless steel reactor, 76.8k
g of terephthalic acid, 19.5 kg of ethylene glycol and 21.3 kg of cyclohexanedimethanol were charged. This mixture was heated to a temperature of 180 to 240 ° C. for 2.5 hours under a nitrogen gas atmosphere, and water generated as a by-product during this time was removed from the reaction system.

Then, the reaction mixture was transferred to a stainless steel polymerization tank, and a solution of 16.0 g of germanium dioxide dissolved in 61.3 g of 20% ethylammonium hydroxide aqueous solution and 23.1 g of monomethylphosphite were added. Then, the reaction temperature was raised to 220 to 250 ° C. over 2 hours. Further, the pressure is gradually decreased to 0.5 Torr over 1 hour, and the temperature is increased to 265
It was raised to ℃.

During the following hour, the temperature rose to 275 ° C. After maintaining the reaction solution for 3 hours under these conditions to continue the reaction, nitrogen gas was introduced into the reactor to return the internal pressure to atmospheric pressure, the polymer was extruded from the reactor, pelletized while cooling, and TA * EG / CHDM copolymer pellets were obtained. In addition, in the present invention, the unmodified polyester used in the following Examples and the like was produced according to the above method.

125 g of the TA / EG / CHDM copolymer thus obtained was dissolved in 840 ml of anisole.
Next, this solution is put into a reactor and maleic anhydride (M
Anisole solution (sometimes abbreviated as AH) (12.
3g / 80ml) and dicumyl peroxide (DCP)
Of anisole solution (6.8 g / 80 ml) was slowly fed to the reactor through a separate conduit over 4 hours.

After the completion of dropping, the reaction was further continued at 145 ° C. for 2 hours, and then the temperature of the reaction solution was cooled to room temperature. Then, the reaction solution was poured into a large amount of acetone to precipitate a polymer. The precipitated polymer was filtered, washed repeatedly with acetone, and dried under reduced pressure at 80 ° C. for 24 hours to obtain the target modified polyester.

This composition was dissolved in chloroform and KO
The amount of graft polymerization of MAH was measured by titrating with H ethanol solution (0.1 N), and it was found that 1.0 g of MAH was graft-polymerized per 100 g of modified polyester. The number average molecular weight of this modified polyester determined by gel permeation chromatography was 31,000. Furthermore, this modified polyester is manufactured by DuPont Dynam.
The glass transition temperature (Tg) measured by ic Mechanical Analyzer (DMA) was 80 ° C, and the softening temperature was 90 ° C.

[0116]

[Examples 2 to 16] The grafting conditions and graft monomers of Example 1 are as shown in the table, and TA / E used in Example 1 is used.
A modified polyester was obtained in the same manner except that the unmodified aromatic polyester shown in the table was used instead of the G.CHDM copolymer.

The properties of this modified polyester were measured in the same manner as in Example 1. The results are shown in the table.

[0118]

Example 17 The modified polyester obtained in Example 1 was used as 2
The sheet was sandwiched between aluminum foils having a thickness of 0.6 mm, and a laminate of aluminum foil / modified polyester / aluminum foil was produced by a press molding machine. From this stack, width 1
A test piece having a length of 5 mm and a length of 150 mm was cut out and the adhesive strength between the modified polyester and the aluminum foil was measured. As a result, the peel strength was 3.5 kg / cm.

Further, a test piece similar to the above was cut out from this laminate, and the adhesive strength between the modified polyester and the aluminum foil was measured at an ambient temperature of 80 ° C. as a result,
The peel strength was 3.7 kg / cm.

[0120]

Examples 18 to 24 Example 17 is repeated except that the adhesive polyester composition or modified polyester shown in the table is used in place of the modified polyester used in Example 17.
The adhesive strength was measured in the same manner as in.

The results are shown in the table.

[0122]

Example 25 The modified polyester obtained in Example 1 was melted with one extruder and fed to a two-layer composite T-die sheet forming die. Separately, an ethylene / vinyl alcohol copolymer (Kuraray Co., Ltd., Eval EP-F, sometimes abbreviated as "EVOH") is melted with another extruder to give a thickness of 1 mm.
A +1 mm two-layer sheet was created.

Cut a 10 mm test piece from this sheet,
An attempt was made to measure the interlaminar adhesive strength between the ethylene / vinyl alcohol copolymer and the modified polyester, but the resins were compatible with each other at the two-layer interface and could not be peeled off.

[0124]

Examples 26 to 37 Instead of the modified polyester and ethylene / vinyl alcohol copolymer used in Example 25, the adhesive polyester composition (or modified polyester) shown in the table and the adherend were used. The peel strength was measured in the same manner.

The results are shown in the table.

[0126]

Comparative Examples 1 to 6 The peel strength was measured in the same manner except that the unmodified thermoplastic polyester shown in the table was used instead of the modified polyester used in the above examples.

[0127]

Comparative Example 7 In Example 37, TA / adipic acid / EG = 50: 50: 10 instead of the modified polyester.
A modified polyester of 0 was used. The amount of graft polymerization in this modified polyester was 1.0% by weight, and the glass transition temperature (Tg) was -28 ° C.

Aluminum foil was adhered using this modified polyester, and the adhesive strength was measured. The results are shown in the table.

[0129]

[Table 1]

[0130]

[Table 2]

[0131]

[Table 3]

[0132]

[Table 4]

[0133]

[Table 5]

[0134]

[Table 6]

[0135]

[Table 7]

[0136]

[Table 8]

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Claims (5)

[Claims] 1. An ethylenically unsaturated carboxylic acid compound is added to an unmodified aromatic polyester having a constituent unit derived from an alicyclic dialcohol and / or a constituent unit derived from an alicyclic dicarboxylic acid. Glass transition temperature 20 to 1 in which uniform graft polymerization is carried out in an amount of 50 to 50% by weight
An adhesive component made of modified polyester at 50 ° C. 2. The amount of component units derived from an alicyclic dialcohol in the total polyhydric alcohol component units forming the unmodified aromatic polyester is in the range of 10 to 80 mol%, The amount of the component unit derived from the alicyclic dicarboxylic acid in the carboxylic acid component unit is 10 to
It is in the range of 80 mol% and is characterized in that
The adhesive component according to the item. 3. The adhesive according to claim 1, wherein the alicyclic dialcohol is 1,4-cyclohexanedimethanol and the alicyclic dicarboxylic acid is 1,4-cyclohexanedicarboxylic acid. component. 4. An adhesive polyester composition comprising the adhesive component according to any one of claims 1 to 3 and a thermoplastic polyester. 5. The adhesive polyester composition according to claim 4, wherein the adhesive component and the thermoplastic polyester are contained in a weight ratio of 100: 0 to 2:98.