TWI585174B - Polyester resin aqueous dispersion composition and the use of this dispersion composition of the access Agent composition - Google Patents

Description

Aqueous dispersion composition of polyester resin and use of the composition of the dispersion Primer composition

The present invention relates to an aqueous dispersion of a polyester resin and an adhesive composition using the same.

Conventionally, in the field of various treatment agents such as paints, inks, coating agents, adhesives, fiber products, and papers, a large amount of organic solvents have been used, and in recent years, problems such as environmental pollution caused by such organic solvents and deterioration of the working environment have begun. It appears, so both domestic and international, the regulations on the emission of organic solvents are being strengthened every year. Because of this trend, as a strategy to reduce the use of organic solvents, there has been a shift to water-based shifts in many applications.

As a method of dispersing or dissolving a polyester resin in water, a method of copolymerizing a hydrophilic raw material and introducing it into a molecular skeleton, for example, a raw material containing a metal sulfonate group and a polyalkylene glycol A method such as copolymerization alone or together is known (for example, Patent Document 1). However, in either case, in order to impart excellent solubility or dispersibility to water, it is necessary to use a large amount of the above-mentioned hydrophilic raw material, and the obtained film also has a hydrophilic group remaining, so that the film has a problem in water resistance. .

In order to solve this problem, a carboxylic acid is added to a polyester resin to make it a high acid value copolymerized polyester resin, and it is neutralized with ammonia (Ammonia) and a low boiling amine. Thus, a method of making a hydrophilic group, that is, a carboxylic acid neutralizing salt, to disperse or dissolve the polyester resin in water is known (for example, Patent Document 2). According to the film obtained by the method, since the ammonia and the low-boiling amine which neutralize the carboxylic acid are volatilized when the film is formed, there is no residual hydrophilic group in the film, that is, the carboxylic acid neutralizing salt, so that the obtained film can be improved. Water resistance.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Publication No. Sho 47-40873

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-223039

However, the film obtained by copolymerizing the polyester resin prepared by the method disclosed in Patent Documents 1 and 2 is not smooth compared to the film obtained by the copolymerized polyester resin dissolved in a solvent, and thus it is not yet available. Adequate water resistance and solvent resistance.

Furthermore, in the case of the interlayer adhesive resin to be used for the two substrates, the general method is to carry out long-term storage in the state where the substrate 1 is coated with an adhesive, and to adhere it to the substrate 2 at the time of use. Since it is used, a non-hardening resin is generally used. However, the use of a non-curable resin in the adhesive layer has a problem of adhesion strength, solvent resistance, and water resistance.

Although it also has a two-liquid hardening type adhesive formed by mixing an isocyanate-based crosslinking agent into a hydroxyl group-containing resin, after the hardening agent is blended into the resin and applied to the substrate (substrate 1), it must be cured and hardened. Before the completion of the reaction of the agent, the next substrate (substrate 2) is bonded to each other, and the substrate 1 cannot be stored for a long period of time in the state in which the substrate 1 has been applied. Therefore, there is a problem that the method of use is limited.

Further, in the case of such an adhesive, the blended isocyanate reacts with water over time, so that it has a problem of poor stability in the state of the blended liquid.

Further, in order to solve the above problems, an adhesive agent formed by blending a blocked isocyanate system is also provided. However, after a curing agent is blended into a resin and applied to a substrate (substrate 1), the next substrate is bonded. In the case of the material 2), if the long-term treatment is not carried out at a high temperature, the blocking component of the isocyanate-based curing agent cannot be dissociated, which has a problem of poor productivity.

An object of the present invention is to provide an adhesive which, when applied to a substrate 1, reacts a polyester resin with a small amount of a curing agent, thereby improving the molecular weight without performing a complete curing reaction, and further improving the molecular weight. (1) Long-term storage is carried out in the state where the adhesive is applied, and the lamination property after the substrate 2, the adhesion after lamination, the solvent resistance, and the water resistance are good.

An object of the present invention is to provide an adhesive which is excellent in adhesion to various substrates such as cloth, paper, or plastic film even when a polyester resin is copolymerized using an aqueous dispersion, and has solvent resistance to various solvents. Excellent water resistance and soap resistance.

In order to achieve the above problems, the inventors of the present invention conducted intensive studies and further proposed the following invention. That is, the present invention is a polyester resin aqueous dispersion composition, an adhesive composition, and a laminate shown below.

The present invention relates to a polyester resin aqueous dispersion composition comprising a polyester resin (A), a polyester resin (B) and a hardener (C), and satisfies any of the following [1] to [3] And meet the following [4].

[1] Polyester resin (A) is a polyester resin having an acid value of 10 to 400 eq/t and a glass transition temperature of 5 to 50 ° C; and a polyester resin (B) is amorphous having a glass transition temperature of 25 ° C or less. The polyester resin; the glass transition temperature of the polyester resin (A) is higher than the glass transition temperature of the polyester resin (B).

[2] Polyester Resin (A) is a mixture of an amorphous polyester resin (A1) having a glass transition temperature of 50 ° C or higher and a crystalline polyester resin (A2) having a glass transition temperature of 0 ° C or less, (A1) The weighted average of the glass transition temperature with (A2) is 5 to 50 ° C, the weighted average of the acid value is 10 to 400 eq/t, and the polyester resin (B) is an amorphous polymer having a glass transition temperature of 25 ° C or less. The weighted average of the glass transition temperature of the ester resin, the polyester resin (A1) and the polyester resin (A2) is higher than the glass transition temperature of the polyester resin (B).

[3] A film having a thickness of 8 μm is formed from a polyester resin aqueous dispersion composition, and after the film is absolutely dried, at least one of the glass transition temperature of the polyester resin (A) or the polyester resin (B) contained therein is at least one It is 5~50 °C.

[4] When a film having a film thickness of 8 μm is formed from a polyester resin aqueous dispersion composition, the film has an elastic modulus at 120 ° C of 1 MPa to 1 kPa.

Further, the curing agent (C) is preferably a carbodiimide-based curing agent.

It is preferable to contain 10 to 100 parts by mass of the polyester resin (B) and 0.5 to 40 parts by mass of the curing agent (C), based on 100 parts by mass of the polyester resin (A).

The invention is further an adhesive composition comprising the aqueous dispersion of the polyester resin.

The above-mentioned adhesive composition is used to bond a film to a film or paper.

The present invention is further a laminate obtained by laminating the composition of the adhesive.

The present invention is a method for producing a laminate, which comprises applying a polyester resin aqueous dispersion composition containing the polyester resin and the curing agent (C) according to any one of the following [1] to [3]. The material 1 was bonded to the substrate 2 by forming a film having a film thickness of 8 μm and an elastic modulus at 120 ° C of 1 MPa to 1 kPa.

[1] Polyester resin (A) is a polyester resin having an acid value of 10 to 400 eq/t and a glass transition temperature of 5 to 50 ° C; and a polyester resin (B) is amorphous having a glass transition temperature of 25 ° C or less. The polyester resin; the glass transition temperature of the polyester resin (A) is higher than the glass transition temperature of the polyester resin (B).

[2] Polyester Resin (A) is a mixture of an amorphous polyester resin (A1) having a glass transition temperature of 50 ° C or higher and a crystalline polyester resin (A2) having a glass transition temperature of 0 ° C or less, (A1) The weighted average of the glass transition temperature with (A2) is 5 to 50 ° C, the weighted average of the acid value is 10 to 400 eq/t, and the polyester resin (B) is an amorphous polymer having a glass transition temperature of 25 ° C or less. The weighted average of the glass transition temperature of the ester resin, the polyester resin (A1) and the polyester resin (A2) is higher than the glass transition temperature of the polyester resin (B).

[3] After the film is absolutely dried, at least one of the glass transition temperature of the polyester resin (A) or the polyester resin (B) contained therein is 5 to 50 °C.

The polyester resin aqueous dispersion composition of the present invention contains a plurality of polyester resins having a specific glass transition temperature and an acid value, and a curing agent, so that it is easy to form water resistance, solvent resistance, soap water resistance, and adhesion. A resin composition is used.

Hereinafter, embodiments of the present invention will be described in detail.

<Polyester Resin (A)>

The polyester resin (A) used in the present invention is preferably a chemical obtained by polycondensing a carboxylic acid component formed of a divalent or higher polyvalent carboxylic acid compound and an alcohol component formed of a divalent or higher polyvalent alcohol compound. The polyester, hydroxycarboxylic acid and lactone of the structure are copolymerized. When a carboxylic acid component formed of a divalent or higher polyvalent carboxylic acid compound and a polyester component obtained by polycondensation of an alcohol component formed of a divalent or higher polyvalent alcohol compound, a polyvalent carboxylic acid compound and a polyhydric alcohol At least one of the compounds is preferably a copolymerized polyester resin formed of two or more kinds of components. Further, the polyvalent carboxylic acid compound and the polyol compound are preferably a copolymerized polyester resin formed of a dicarboxylic acid component and a diol component. Here, "mainly" means that the total amount of the dicarboxylic acid component and the diol component is based on the total amount of all the acid components and all the alcohol components constituting the polyester resin (A) used in the present invention. The lower accounted for more than 50%. The total amount of the dicarboxylic acid component and the diol component is preferably 70 mol% or more, more preferably 85 mol% or more, more preferably 95 mol% or more, and may be 100 mol%.

The dicarboxylic acid is preferably an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid, and among them, an aromatic dicarboxylic acid is preferred. When the total amount of the carboxylic acid component is 100 mol%, the copolymerization amount of the aromatic dicarboxylic acid component is 40 mol% or more, preferably 45 mol% or more, and more preferably 50 mol% or more. More preferably 55% or more. In the case of less than 40% by mole, the mechanical strength of the obtained coating film may become low, and in such a case, the coating film is not practical.

Specific examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, and naphthalene dicarboxylic acid, but are not limited thereto. Specific examples of the aliphatic dicarboxylic acid include succinic acid, adipic acid, sebacic acid, sebacic acid, and dodecanedicarboxylic acid, but are not limited thereto. These dicarboxylic acid components may be used alone or in combination of two or more. Further, an aromatic hydroxycarboxylic acid such as p-hydroxybenzoic acid or p-hydroxyacetic acid benzoic acid; fumaric acid, maleic acid, itaconic acid, hexahydrofurfuric acid or tetrahydrofurfuric acid may be used. a saturated alicyclic group; an alicyclic dicarboxylic acid such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid or 1,4-cyclohexanedicarboxylic acid; Carboxylic acid component. Further, depending on the demand, tri- and tetracarboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid, and anhydrides thereof may be contained.

It is preferred to use an aliphatic diol as a diol component. When the total amount of the diol component is 100 mol%, the amount of the copolymerization of the aliphatic diol component is 40 mol% or more, preferably 50 mol% or more, more preferably 60 mol% or more, and more preferably 70% or more. In the case of less than 40% by mole, the glass transition temperature (hereinafter also referred to as Tg) of the obtained coating film may become high, and it is not suitable as an adhesive.

Specific examples of the aliphatic diol include ethylene glycol, propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, and 2-methyl-1,3-propanediol (hereinafter also referred to as 2MG). ), 1,4-butanediol, 1,5-pentane Alcohol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene Alcohol or the like, but is not limited thereto. These diol components may be used singly or in combination of two or more. Further, ethylene oxide addition of 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecanediol, and bisphenol A can also be used. As the other diol, the propylene oxide adduct, the ethylene oxide adduct of hydrogenated bisphenol A, and the propylene oxide adduct are used. In addition, a small amount of a trihydric alcohol and a tetrahydric alcohol such as trimethylolethane, trimethylolpropane, glycerin or pentaerythritol may be contained depending on the demand.

The acid value of the polyester resin (A) is preferably in the range of 10 to 400 eq/t. It is preferably 11~360eq/t, more preferably 12~320eq/t, and most preferably 13~280eq/t. When the acid value exceeds 400 eq/t, hydrolysis of the aqueous dispersion of the polyester resin is promoted and the long-term storage stability is deteriorated. When the acid value is less than 10 eq/t, the solvent layer and the water resistance of the adhesive layer obtained by using the polyester resin aqueous dispersion composition of the present invention may be deteriorated due to the inability to sufficiently react with the curing agent.

In order to disperse the polyester resin (A) in water, it is preferred to introduce a hydrophilic polar group into the resin skeleton. Examples of the polar group include a sulfonic acid metal salt group, a carboxyl group, a phosphoric acid group, and the like, and are preferably a sulfonic acid metal salt group or a carboxyl group; further, from the viewpoint of dispersibility and excellent long-term stability of the obtained aqueous dispersion, Most preferred is a metal sulfonate group. Further, the polar groups may be used alone or in combination depending on the requirements.

The method of introducing the sulfonic acid metal salt group is not particularly limited, and for example, when the polyester resin (A) is polymerized, a dicarboxylic acid or a diol containing a sulfonic acid metal salt group is copolymerized. The dicarboxylic acid containing a sulfonic acid metal salt group means a dicarboxylic acid containing an alkali metal salt or an alkaline earth metal salt of a sulfonic acid, and specific examples thereof include sodium 5-sulfonate isophthalate and 5-sulfonate isophthalate. Potassium formate, sodium 4-sulfonate-2,7-dicarboxylate, 5-(4 - sulfonic acid phenoxy) sodium isophthalate or the like, but is not limited thereto. The diol containing a sulfonic acid metal salt group means an ethylene glycol containing an alkali metal salt of an sulfonic acid or an alkaline earth metal salt, and specific examples thereof include a sodium salt of 2-sulfo-1,4-butanediol, and 2 The sodium salt of 5-dimethyl-3-sulfo-2,5-hexanediol, etc. is not limited to this. These dicarboxylic acids or diols containing a sulfonic acid metal salt group may be used singly or in combination of two or more.

In the case where the sulfonic acid metal salt group is introduced as the hydrophilic group, the functional group concentration derived from the sulfonic acid in the polyester resin (A) is preferably from 70 to 400 eq/t in order to satisfy both water dispersibility and water resistance. It is preferably from 90 to 320 eq/t, particularly preferably from 110 to 290 eq/t. When the concentration of the functional group derived from the sulfonic acid is less than 70 eq/t, sufficient dispersion stability cannot be ensured, and if it exceeds 400 eq/t, the water resistance of the film may be lowered.

A carboxyl group may also be introduced as a hydrophilic group other than the metal sulfonate. The method of introducing a carboxyl group is a method of adding a polycarboxylic acid anhydride under normal pressure and a nitrogen atmosphere to give an acid value after polymerization of a polyester resin; and introducing a polyvalent acid anhydride into an oligomer state before high molecular weighting of the polyester. Then, a method of imparting a molecular weight by a polycondensation reaction under reduced pressure to give an acid value or the like is carried out. The former should be used as a method of easily obtaining the target acid value. Specific examples of the polycarboxylic acid anhydride include trimellitic anhydride, phthalic anhydride, pyromellitic anhydride, succinic anhydride, maleic anhydride, 1,8-naphthalic anhydride, and 1,2-cyclohexanedicarboxylate. Anhydride, cyclohexane-1,2,3,4-tetracarboxylic acid-3,4-anhydride, ethylene glycol trimellitic anhydride, 5-(2,5-di-oxytetrahydro-3-furanyl)- 3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, naphthalene-1,4,5,8-tetracarboxylic acid dianhydride, etc., but is not limited thereto. These polycarboxylic acid anhydrides may be used alone or in combination of two or more.

In the case where a carboxyl group is introduced as a hydrophilic group, the functional group concentration derived from the carboxylic acid in the polyester resin (A) (acid value) should be 10~400eq/t. It is preferably 100~320eq/t, more preferably 120~320eq/t, especially 150~280eq/t. When the concentration of the functional group derived from the carboxylic acid is less than 10 eq/t, sufficient dispersion stability cannot be ensured, and if it exceeds 400 eq/t, not only the water resistance of the film is lowered, but also the molecular chain hydrolysis is more likely to be promoted. In particular, in the case where the metal sulfonate is not introduced, it is preferably 100 eq/t or more in order to secure water dispersibility and water resistance.

A conventional method can be used as a method for producing the polyester resin (A). For example, the dicarboxylic acid and the diol component can be esterified at 150 to 250 ° C, and then decompressed at 230 to 300. Polycondensation was carried out at ° C to obtain a target polyester resin. Further, in the case of introducing a hydrophilic polar group, a monovalent inorganic salt such as sodium acetate or potassium acetate is preferably added as a polymerization stabilizer. Further, a compound such as a hindered phenol or a hindered amine may be added as a heat stabilizer.

<Polyester Resin (B)>

In the same manner as the polyester resin (A), the polyester resin (B) used in the present invention is preferably a carboxylic acid component formed of a divalent or higher polyvalent carboxylic acid compound and a polyvalent alcohol compound having a divalent or higher value. The polyester, the hydroxycarboxylic acid, and the lactone having a chemical structure obtained by polycondensation of the formed alcohol component are copolymerized. When a carboxylic acid component formed of a divalent or higher polyvalent carboxylic acid compound and a polyester component obtained by polycondensation of an alcohol component formed of a divalent or higher polyvalent alcohol compound, a polyvalent carboxylic acid compound and a polyhydric alcohol At least one of the compounds is preferably a copolymerized polyester resin formed of two or more kinds of components. Further, the polyvalent carboxylic acid compound and the polyol compound are preferably a copolymerized polyester resin formed of a dicarboxylic acid component and a diol component. Here, "mainly" means a dicarboxylic acid component and a total amount of all the acid components and all the alcohol components constituting the polyester resin (B) used in the present invention, under the molar reference. The total amount of the diol component accounts for 50 mol% or more. The total amount of the dicarboxylic acid component and the diol component is preferably 70 mol% or more, more preferably 85 mol% or more, more preferably 95 mol% or more, and may be 100 mol%.

As in the case of the polyester resin (A), a conventional method can be used as a method for producing the polyester resin (B). For example, the above dicarboxylic acid and diol component can be esterified at 150 to 250 ° C, and then polycondensed at 230 to 300 ° C under reduced pressure to obtain a target polyester resin. Further, in the case of introducing a hydrophilic polar group, a monovalent inorganic salt such as sodium acetate or potassium acetate is preferably added as a polymerization stabilizer. Further, a compound such as a hindered phenol or a hindered amine may be added as a heat stabilizer.

In the same manner as the polyester resin (A), the polyester resin (B) is preferably introduced with a hydrophilic polar group into the resin skeleton in order to be dispersed in water. Examples of the polar group include a sulfonic acid metal salt group, a carboxyl group, a phosphoric acid group, and the like, and are preferably a sulfonic acid metal salt group or a carboxyl group; further, from the viewpoint of dispersibility and excellent long-term stability of the obtained aqueous dispersion, Most preferred is a metal sulfonate group. Further, the polar groups may be used alone or in combination depending on the requirements. The preferred amount of introduction of the functional group is the same as that of the polyester resin (A).

And the composition ratio of the composition used in the present invention, the polyester resin (A) and the polyester resin (B) may be ¹ H-NMR integral ratio obtained by calculation, the ¹ H-NMR-based polyester resin (A) was dissolved The solvent was measured by deuterated chloroform or the like.

The aqueous polyester resin dispersion composition used in the present invention must satisfy any of the following [1] to [3] and satisfy the following [4].

<Aqueous dispersion composition of polyester resin satisfying [1]>

Polyester resin (A) is a polyester resin having an acid value of 10 to 400 eq/t and a glass transition temperature of 5 to 50 ° C, and a polyester resin (B) is an amorphous polyester resin having a glass transition temperature of 25 ° C or lower. The glass transition temperature of the polyester resin (A) is preferably higher than the glass transition temperature of the polyester resin (B).

The acid value of the polyester resin (A) used in the present invention is preferably in the range of 10 to 400 eq/t. It is preferably 11~360eq/t, more preferably 12~320eq/t, and most preferably 13~280eq/t. When the acid value exceeds 400 eq/t, hydrolysis of the aqueous dispersion of the polyester resin is promoted and the long-term storage stability is deteriorated. When the acid value is less than 10 eq/t, the solvent layer and the water resistance of the adhesive layer obtained from the aqueous polyester resin composition of the present invention may be deteriorated due to the inability to sufficiently react with the curing agent.

The glass transition temperature of the polyester resin (A) used in the present invention is preferably in the range of 5 to 50 °C. It is preferably 7 to 45 ° C, more preferably 10 to 43 ° C, and particularly preferably 15 to 40 ° C. When the glass transition temperature is less than 5 ° C, the adhesive layer obtained from the aqueous polyester resin composition of the present invention tends to have good adhesion and the like, but tends to have a large viscosity. On the other hand, when the glass transition temperature exceeds 50° C., when it is bonded to the base material 2, the lamination property may be lowered and it may not be possible to continue. Further, it has a tendency to have water resistance, solvent resistance, and soap water resistance.

The polyester resin (B) used in the present invention is preferably an amorphous polyester resin. Further, the glass transition temperature is preferably 25 ° C or lower. It is preferably 15 ° C or less, more preferably 10 ° C, and most preferably 5 ° C or less. The lower limit is not particularly limited and is usually -30 ° C or higher, preferably -25 ° C. When the glass transition temperature exceeds 25° C., when the substrate 2 is bonded to the substrate 2, the laminate property may be lowered and the film may not be able to be bonded. Further, it has a tendency to have water resistance, solvent resistance, and soap water resistance. The acid value should be in the range of 0~20eq/t, preferably 0~15eq/t, more It should be 0~10eq/t, and most preferably 0~5eq/t. When the acid value exceeds 20 eq/t, the polyester resin (B) reacts with the curing agent, and the elastic modulus of the adhesive layer increases, and the lamination property may deteriorate.

The glass transition temperature of the polyester resin (A) is preferably higher than the glass transition temperature of the polyester resin (B). The effect of improving the lamination property can be expected by making the glass transition temperature of the polyester resin (A) higher than the glass transition temperature of the polyester resin (B).

The blending ratio (mass ratio) of the polyester resin (A) to the polyester resin (B) is preferably 10 to 100 parts by mass based on 100 parts by mass of the polyester resin (A). It should be 15 to 70 parts by mass, more preferably 18 to 50 parts by mass. When the blending amount of the polyester resin (B) is too large, the adhesiveness of the obtained aqueous polyester resin dispersion is good, but the viscosity tends to be large. If it is in this range, viscosity is also good, and it is preferable. On the other hand, when the blending amount of the polyester resin (B) is too small, when it is bonded to the base material 2, the lamination property may be lowered and it may not be possible to continue. Further, it has a tendency to have water resistance, solvent resistance, and soap water resistance.

The polyester resin (A) and the polyester resin (B) can be blended, and the aqueous polyester resin dispersion prepared by using the polyester resin (A) and the polyester resin produced by using the polyester resin (B) can be aqueous. The dispersion may be mixed, and water dispersion may be carried out in a state where the polyester resin (A) and the polyester resin (B) are mixed. It is also possible to mix other polyester resins or aqueous dispersions within a range that does not impair the performance of the present invention.

<Aqueous dispersion composition of polyester resin satisfying [2]>

The polyester resin (A) is a mixture of an amorphous polyester resin (A1) having a glass transition temperature of 50 ° C or higher and a crystalline polyester resin (A2) having a glass transition temperature of 0 ° C or lower, (A1) and (A2). Glass transition temperature The weighted average is 5~50°C, the weighted average value of acid value is 10~400eq/t; the polyester resin (B) is amorphous polyester resin with glass transition temperature below 25°C, polyester resin (A1) The weighted average of the glass transition temperature with the polyester resin (A2) is preferably higher than the glass transition temperature of the polyester resin (B).

The polyester resin (A) used in the present invention may not be a single polyester resin, but may be a mixture of two or more kinds of polyester resins. In the case of a mixture of two or more kinds of polyester resins, it is preferred to contain a polyester resin (A1) and a polyester resin (A2) described below, and a glass transition temperature of the polyester resin (A1) and the polyester resin (A2). The weighted average is in the range of 5 to 50 °C.

<Polyester Resin (A1)>

The polyester resin (A1) is preferably an amorphous polyester resin. The glass transition temperature is preferably 50 ° C or more, more preferably 55 ° C or more; preferably 100 ° C or less, preferably 90 ° C or less. When the glass transition temperature is less than 50 ° C, the adhesive layer obtained from the aqueous polyester resin dispersion composition of the present invention has a large viscosity, which may cause problems in use. The acid value should be in the range of 5 to 400 eq/t, preferably 10 to 360 eq/t, more preferably 11 to 320 eq/t, and most preferably 12 to 280 eq/t. When the acid value exceeds 400 eq/t, hydrolysis of the obtained aqueous dispersion of the polyester resin may be promoted, and the long-term storage stability may be deteriorated. When the acid value is less than 10 eq/t, the solvent layer and the water resistance of the adhesive layer obtained from the aqueous polyester resin composition of the present invention may be poorly affected by the sufficient reaction with the curing agent. .

<Polyester Resin (A2)>

The polyester resin (A2) is preferably a crystalline polyester resin. In the case of amorphous, the adhesive layer obtained from the aqueous polyester resin dispersion composition of the present invention has a large viscosity and is problematic in use. The glass transition temperature should be below 0 ° C, preferably below -5 ° C; preferably above -30 ° C, preferably -20 ° C the above. When the glass transition temperature exceeds 0 ° C, the melting point becomes high, and good lamination property cannot be exhibited at the time of bonding. The acid value should be in the range of 5 to 400 eq/t, preferably 10 to 360 eq/t, more preferably 11 to 320 eq/t, and most preferably 12 to 280 eq/t. When the acid value exceeds 400 eq/t, hydrolysis of the obtained aqueous dispersion of the polyester resin may be promoted, and the long-term storage stability may be deteriorated. When the acid value is less than 10 eq/t, the adhesive layer obtained by using the aqueous polyester resin composition of the present invention may have poor solvent resistance and water resistance due to insufficient reaction with the curing agent.

The crystalline polyester resin of the present invention refers to a temperature rise of 20 ° C / min at -100 ° C to 250 ° C using a differential scanning calorimeter (DSC), and shows a clear melting during the heating process. Peak person. The amorphous polyester resin is a temperature which is heated at a rate of 20 ° C /min at -100 ° C to 250 ° C using a differential scanning calorimeter (DSC), and does not show a clear melting peak during the temperature rise.

In the case of using the polyester resin (A1) and the polyester resin (A2), the weighted average of the glass transition temperature of the polyester resin (A) is preferably in the range of 5 to 50 °C. It is preferably 7 to 45 ° C, more preferably 10 to 43 ° C, and particularly preferably 15 to 40 ° C. When the glass transition temperature is less than 5 ° C, the adhesiveness of the adhesive layer obtained from the aqueous polyester resin dispersion composition is good, but the viscosity tends to be large. On the other hand, when the glass transition temperature exceeds 50° C., when the substrate 2 is bonded to the substrate 2, the laminate property may be lowered and the film may not be able to be bonded. Further, there is a tendency that water resistance, solvent resistance, and soap water resistance are lowered.

The weighted average of the glass transition temperatures can be calculated as follows.

Weighted average value of glass transition temperature of polyester resin (A) = [(glass transition temperature of polyester resin (A1) × mass part of polyester resin (A1)) + (glass transition temperature of polyester resin (A2)) × parts by mass of the polyester resin (A2)] / [parts by mass of the polyester resin (A1) + parts by mass of the polyester resin (A2)]

Further, in the case where three or more kinds of polyester resins are used in combination, the glass transition temperature of the polyester resin (A) can also be determined from the weighted average of the respective polyester resins.

In the case of using the polyester resin (A1) and the polyester resin (A2), the weighted average value of the acid value of the polyester resin (A) is preferably in the range of 10 to 400 eq/t. It is preferably 11~360eq/t, more preferably 12~320eq/t, and most preferably 13~280eq/t. When the acid value exceeds 400 eq/t, hydrolysis of the aqueous dispersion of the polyester resin is promoted and the long-term storage stability is deteriorated. When the acid value is less than 10 eq/t, the solvent layer and the water resistance of the adhesive layer obtained from the aqueous polyester resin composition of the present invention may be deteriorated due to the inability to sufficiently react with the curing agent.

The weighted average of the acid value can be calculated by the following formula.

The weighted average value of the acid value of the polyester resin (A) = [(acid value of polyester resin (A1) × mass part of polyester resin (A1)) + (acid value of polyester resin (A2) × polyester Parts by mass of the resin (A2)] / [parts by mass of the polyester resin (A1) + parts by mass of the polyester resin (A2)]

Further, in the case where three or more kinds of polyester resins are used in combination, the acid value of the polyester resin (A) can also be determined from the weighted average of the respective polyester resins.

The preferred blending ratio (mass ratio) of polyester resin (A1) and polyester resin (A2) is preferably polyester resin (A1) / polyester resin (A2) = 90/10~10/90, preferably It is 80/20~20/80, more preferably 70/30~30/70, especially 60/40~40/60.

The polyester resin (A1) and the polyester resin (A2) may be blended, and the aqueous polyester resin dispersion prepared by using the polyester resin (A1) and the polyester resin produced by using the polyester resin (A2) may be aqueous. Dispersion Further, water may be dispersed in a state in which the polyester resin (A1) and the polyester resin (A2) are mixed. Other polyester resins or aqueous dispersions may also be blended insofar as they do not affect the performance of the present invention.

The polyester resin (B) used in the present invention is preferably an amorphous polyester resin. Further, the glass transition temperature is preferably 25 ° C or lower. It is preferably 15 ° C or less, more preferably 10 ° C, and most preferably 5 ° C or less. The lower limit is not particularly limited and is usually -30 ° C or higher, preferably -25 ° C. When the glass transition temperature exceeds 25° C., when the substrate 2 is bonded to the substrate 2, the laminate property may be lowered and the film may not be able to be bonded. Further, it has a tendency to have water resistance, solvent resistance, and soap water resistance. The acid value is preferably in the range of 0 to 20 eq/t, more preferably 0 to 15 eq/t, more preferably 0 to 10 eq/t, and most preferably 0 to 5 eq/t. When the acid value exceeds 20 eq/t, the polyester resin (B) reacts with the curing agent, and the elastic modulus of the coating layer increases, and the lamination property may deteriorate.

The weighted average of the glass transition temperatures of the polyester resin (A1) and the polyester resin (A2) is preferably higher than the glass transition temperature of the polyester resin (B). The effect of improving the lamination property can be expected by making the weighted average value of the glass transition temperature of the polyester resin (A1) and the polyester resin (A2) higher than the glass transition temperature of the polyester resin (B).

<Aqueous dispersion composition of polyester resin satisfying [3]>

A film (film thickness: 8 μm) produced by using the aqueous polyester resin composition of the present invention is heat-treated at 200 ° C for 5 minutes (hereinafter also referred to as absolute drying), and the polyester resin contained in the film after absolute drying is used. The glass transition temperature of (A) or the polyester resin (B) is preferably in the range of 5 to 50 °C. It is preferably 7 to 45 ° C, more preferably 10 to 43 ° C, and particularly preferably 15 to 40 ° C. When the glass transition temperature is less than 5 ° C, the adhesiveness of the adhesive layer obtained from the aqueous polyester resin dispersion composition is good, but the viscosity tends to be large. On the other hand, when the glass transition temperature exceeds 50 ° C, when it is bonded to the substrate 2, There is a case where the lamination property is lowered and it is impossible to continue. Further, it has a tendency to have water resistance, solvent resistance, and soap water resistance.

In the case of using two or more kinds of compatible polyester resins, the average glass transition temperature after the compatibility is defined as the glass transition temperature of the polyester resin.

<Aqueous dispersion composition of polyester resin satisfying [4]>

When a film having a film thickness of 8 μm is produced by using the aqueous polyester resin composition of the present invention, the film has an elastic modulus at 120 ° C of preferably 1 MPa to 1 kPa.

The film of the aqueous polyester composition dispersion of the present invention is applied to a non-coroscopic surface of a polypropylene film (P2161, manufactured by Toyobo Co., Ltd., thickness: 50 μm) by a hand coater. After drying at about 120 ° C for about 1 minute to obtain a laminate having a film having a film thickness of 8 μm, the film was peeled off from the polypropylene film.

Next, using the dynamic viscoelasticity measuring apparatus DVA-220 manufactured by IT Measurement and Control Co., Ltd., the elastic modulus (Er) of the film was measured at 10 Hz and a temperature increase rate of 4 ° C/min. The value of the modulus of elasticity at 120 ° C is preferably in the range of 1 MPa to 1 kPa, more preferably in the range of 0.9 MPa to 10 kPa, and more preferably in the range of 0.8 MPa to 100 kPa. When the modulus of elasticity exceeds 1 MPa, the layering property of the film is lowered and it is impossible to continue. When the modulus of elasticity is less than 1 kPa, the amount of outflow of the film becomes large, and good adhesion cannot be obtained.

The drying method of the polyester resin aqueous dispersion composition is not particularly limited, and a conventional method such as a hot air dryer, induction heating, near infrared heating, far infrared heating, or indirect heating can be used.

<hardener (C)>

The curing agent (C) used in the present invention is not particularly limited, and is preferably a carbodiimide-based curing agent. It is considered that by using a carbodiimide-based curing agent, when applied to the substrate 1, it does not cause a complete hardening reaction with the polyester resin (A) and/or the polyester resin (B), but A small amount of hardening reaction to the extent that the molecular weight of the polyester resin (A) and/or the polyester resin (B) is increased. Thereby, the base material 1 can be stored for a long period of time after application, and the lamination property at the time of the base material 2, the adhesiveness after the following, the solvent resistance, and the water resistance become favorable. Further, a melamine-based compound, a blocked isocyanate, a water-dispersed isocyanate curing agent, an epoxy compound, an aziridine compound, an oxazoline compound, a metal ion or the like may be used in combination within a range that does not impair the effects of the present invention. The amount of the hardener (C) to be blended is preferably 0.5 to 40 parts by mass, more preferably 1 to 30 parts by mass, and more preferably 3 to 25 parts by mass, based on 100 parts by mass of the polyester resin (A). It is particularly preferably 5 to 20 parts by mass. When it is less than 0.5 part by mass, the solvent resistance and the soap-resistant water property tend to be lowered. When the amount is more than 40 parts by mass, a large amount of unreacted curing agent is present in the coating film, which causes a decrease in viscosity and adhesion. Case.

<Polyester Resin Aqueous Dispersion Composition>

The aqueous polyester resin dispersion composition of the present invention comprises an aqueous dispersion of a polyester resin (A), a polyester resin (B), and a curing agent (C). When the aqueous dispersion of the polyester resin of the present invention is produced, an organic solvent (hereinafter also referred to as a good solvent) capable of dissolving or swelling the polyester resin (A) and the polyester resin (B) can be used to untie the polyester molecular chains from each other. After entanglement, an aqueous dispersion is produced by adding water. An organic solvent (hereinafter also referred to as a poor solvent) which does not dissolve or swell the polyester resin (A) and the polyester resin (B) may be added as needed.

The heating temperature for dissolving or swelling the polyester resin (A) and the polyester resin (B) can be appropriately set according to the type and amount of the good solvent, and is preferably 40 to 160 ° C, preferably 50 to 140 ° C. More preferably, it is 60~120 °C, and most preferably 70~100 °C. If the temperature is less than 40 ° C, the polyester resin (A) and the polyester resin (B) are insufficiently dissolved or swollen, and the molecular chains are not sufficiently entangled, and if it exceeds 160 ° C, the polyester is caused. The possibility of molecular degradation is increased.

The good solvent of the polyester resin (A) and the polyester resin (B) is not particularly limited, and examples thereof include butanone, dimethylacetamide, dimethylformamide, N-methylpyrrolidone, and tetrahydrofuran. 1,4-dioxane, 1,3-dioxe, 1,3-dioxolane, 1,2-hexanediol, methyl stilbene, n-butyl 赛路苏, third Butyl sarbuta, Ethyl carbitol, Butyl Carbitol, propylene glycol monoacetone, propylene glycol monobutyl ether, triethylene glycol monobutyl ether, and the like. Among them, it is preferably butanone, butyl siroli, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like.

Examples of the poor solvent of the polyester resin (A) and the polyester resin (B) include methanol, ethanol, 1-propanol, isopropanol, and hexane. Among them, ethanol and isopropyl alcohol are particularly preferable. Here, the weight ratio of the poor solvent to the good solvent is preferably in the range of 0 to 70%. It is preferably 5~50%. If 70% or more of a poor solvent is used, the resin may aggregate and precipitate.

After the aqueous dispersion is obtained, the good solvent and/or poor solvent can be removed as needed. Among the cases where the removal is carried out, it is preferred to use a solvent having a boiling point of less than 100 ° C among the organic solvents.

When the aqueous dispersion of the carboxyl group-introduced polyester resin is produced, it is preferred to neutralize some or all of the polar groups such as carboxyl groups on the surface of the particles with a basic substance in order to stabilize the dispersed resin particles.

Examples of the alkaline substance which can be used for the neutralization include amines represented by triethylamine or the like, ammonia, sodium hydroxide, potassium hydroxide and the like. In order to eliminate the residual of the polyester resin composition after drying, and the resulting reduction in water resistance, ammonia and volatile amines are preferably used.

Examples of the volatile amines include monomethylamine, dimethylamine, trimethylamine, monoethylamine, mono-n-propylamine, dimethyl-n-propylamine, monoethanolamine, diethanolamine, and trisity. Ethanolamine, N-methylethanolamine, N-aminoethylethanolamine, N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N,N-dimethylethanolamine, And various amines such as N,N-dimethylpropanolamine. Particularly preferred is triethylamine and the like. These volatile amines may be used singly or in combination of two or more.

The particle diameter of the polyester resin phase contained in the aqueous polyester composition dispersion of the present invention has a great influence on the appearance and storage stability of the coating film, and is therefore very important, and it is preferably 30 to 250 nm. It is preferably 40 to 200 nm, more preferably 45 to 150 nm, and particularly preferably 50 to 100 nm. When the particle diameter exceeds 250 nm, not only the dispersion stability is greatly lowered, but also the film formability is lowered, so that the appearance and performance of the obtained film are deteriorated. In addition, when the thickness is less than 30 nm, the film forming property tends to be remarkably improved. However, fusion and aggregation between the dispersed particles are likely to occur, and as a result, the possibility of sticking and dispersing is high, which is not preferable. When the two kinds of polyester resins of the polyester resin (A) and the polyester resin (B) are used herein, the average particle diameters of the polyester resin (A) and the polyester resin (B) are further increased. When the three polyester resins of the polyester resin (A1), the polyester resin (A2), and the polyester resin (B) are used together, the polyester resin (A1), the polyester resin (A2), and the polyester resin (B) are used. The average particle size. Further, when four or more kinds of polyester resins are used, the average particle diameter of all the polyester resins used is used.

In the aqueous dispersion of the polyester resin of the present invention, the coarse particles of 1 μm or more are preferably 1% by mass or less, preferably 0.5% by mass or less, more preferably 0.2% by mass or less, and still more preferably 0.01% by mass or less. When it is more than 1% by mass, precipitates may be formed as time passes (long-term storage), and storage stability may be deteriorated, which may cause streaks or the like during coating drying.

The solid content concentration of the polyester resin of the aqueous dispersion of the polyester resin of the present invention is preferably 5 to 45% by mass, more preferably 10 to 40% by mass, more preferably 15 to 35% by mass, most preferably 20 to 33% by mass. The range of %. When the solid content of the resin exceeds 45% by mass, the viscosity of the solution becomes high, and since the aggregation of the resin particles is likely to occur, the dispersion stability is largely lowered. Moreover, when it is less than 5 mass%, it is not practical from the point of a manufacturing surface and a use surface.

<Anti-caking agent (D)>

The aqueous dispersion composition of the polyester resin of the present invention is preferably blended with an anti-caking agent. The blending amount is not particularly limited, and is preferably from 0 to 20 parts by mass, more preferably from 1 to 16 parts by mass, per 100 parts by mass of the polyester resin (A), in a range which does not adversely affect the subsequent properties. It is 3 to 14 parts by mass, and particularly preferably 5 to 12 parts by mass. The anti-caking agent (D) may be used alone or in combination of two or more.

The polyester resin aqueous dispersion composition of the present invention, in addition to the polyester resin (A), the polyester resin (B), the hardener (C), and the anti-caking agent (D), does not affect the performance. The amount of the emulsifier may be blended in an appropriate amount, or the additive used in a general aqueous binder such as a plasticizer, a dispersant, a tackifier, a solvent, a defoaming agent, a preservative, an anti-caking agent, etc. may be blended as required. .

<coating liquid>

The coating liquid is an aqueous dispersion composition of the polyester resin of the present invention and an anti-caking agent (D), an emulsifier, a plasticizer, a dispersing agent, a tackifier, a solvent, an antifoaming agent, a preservative, etc., which are required according to the requirements. A suitable amount of additives such as additives used in general aqueous adhesives are blended.

<Binder layer>

The adhesive layer can be produced using the aqueous polyester resin dispersion composition of the present invention. After the coating liquid is applied onto the substrate 1, the coating layer is obtained by drying. The coating amount of the aqueous dispersion of the polyester resin is preferably adjusted so as to have a thickness of 3 to 30 μm. The thickness of the film is preferably 3 to 30 μm, more preferably 5 to 20 μm, more preferably 6 to 15 μm, and most preferably 7 to 10 μm. If it is less than 3 μm, it is difficult to obtain a uniform adhesive layer, and if it exceeds 30 μm, the drying time becomes long, and it is difficult to efficiently produce.

Further, the elastic modulus of the adhesive layer at 120 ° C is preferably in the range of 1 MPa to 1 kPa, more preferably in the range of 0.9 MPa to 10 kPa, and still more preferably in the range of 0.8 MPa to 100 kPa. When the modulus of elasticity exceeds 1 MPa, when the substrate 1 and the substrate 2 are bonded together, the laminate property may be lowered and the film may not be able to be bonded. When the elastic modulus is less than 1 kPa, when the base material 1 and the base material 2 are bonded together, the amount of the flow of the adhesive layer becomes large, and good adhesion cannot be obtained.

The drying conditions of the coating liquid are not particularly limited, but are preferably 40 to 250 ° C, preferably 60 to 200 ° C, and more preferably 80 to 150 ° C. If it is less than 40 ° C, the drying time is long and industrial production is not reasonable. Moreover, there is a possibility that the drying of the coating liquid is incomplete. Further, if it exceeds 250 ° C, a drying furnace having a high capacity is required, which is not preferable. The method of drying is not limited, and a conventional method such as a hot air dryer, induction heating, near infrared heating, far infrared heating, and indirect heating can be used.

After the coating liquid is applied onto the substrate 1 and dried and cured to form an adhesive layer, the substrate 2 is bonded to the adhesive layer to obtain good solvent resistance, adhesion, and water resistance. A layered body that is resistant to soap and water. The base material 1 and the base material 2 are not particularly limited, and examples thereof include a plastic film, a processed paper or unprocessed paper, or a base fabric processed to a constant thickness. The plastic film is not particularly limited, and examples thereof include a polyvinyl alcohol (PVA) film, a polyethylene terephthalate (PET) film, a polyolefin film, a polyester film, a polyvinyl chloride film, and a polyurethane. The base fabric is not particularly limited, and examples thereof include cotton, synthetic fibers, and glass fibers.

Further, the substrate 1 and the substrate 2 may be of the same type or different types. One of the substrate 1 and the substrate 2 is preferably a porous body such as paper.

Next, the present invention will be specifically described by the following examples and comparative examples, but the present invention is not limited thereto. In the examples and the comparative examples, only the parts "parts" indicate the parts by mass. The characteristics of the polyester resin (A), the polyester resin (B), the aqueous polyester resin dispersion, and the adhesive composition were evaluated as follows.

1. Composition of polyester resin (A) and polyester resin (B)

The polyester resin was dissolved in chloroform D and determined by ¹ H-NMR analysis using a nuclear magnetic resonance spectrometer (NMR) GEMINI 200 manufactured by VARIAN.

2. Reduction viscosity ηsp / c (unit: dl / g)

0.10 g of the polyester resin was dissolved in a mixed solvent of 25 ml of phenol/tetrachloroethane (mass ratio: 6/4), and measured at 30 ° C using a Ubbelohde viscometer.

3. Number average molecular weight

A gel permeation chromatograph 150c manufactured by WATERS Co., Ltd. using tetrahydrofuran as a dissolving solution, and a differential refractometer as a detector, at a column temperature of 35 ° C, a flow rate of 1 ml/min, using gel permeation chromatography (GPC) The polyester resin (A) was analyzed to obtain a polystyrene-converted number average molecular weight. The pipe string is connected in series using Shodex KF-802, KF-804, and KF-806 of Showa Denko Co., Ltd.

4. Crystal melting point and glass transition temperature

Using a differential scanning calorimeter (DSC) DSC-220 manufactured by Seiko Instruments, Inc., 5 mg of the sample (polyester resin or absolutely dried film) was sealed in an aluminum cap type container at -100 ° C to 250 ° C. The temperature rise rate of 20 ° C / min was raised and measured to determine the maximum peak temperature of the heat of fusion as the crystal melting point. Further, the glass transition temperature was determined by using the measuring device, and the temperature at the intersection of the extension line of the baseline below the glass transition temperature and the line indicating the maximum slope between the peak rising portion and the peak apex was obtained under the same conditions. The absolute drying in the present invention means a film produced by using a polyester resin aqueous dispersion composition, and heat-treated at 200 ° C for 5 minutes.

5. Ionic base concentration

5-1. Carboxyl concentration

A 0.2 g sample (polyester resin) was weighed and dissolved in 20 ml of chloroform. Subsequently, titration was carried out with 0.01 N potassium hydroxide (ethanol solution), and potassium hydroxide equivalent was determined with respect to the polyester resin, and eq/ton units were obtained in terms of conversion. In addition, phenolphthalein was used as an indicator.

5-2. Sodium sulfonate concentration

The sodium concentration was measured by atomic absorption method, and this was converted into a sulfonic acid sodium salt base concentration, and eq/t unit was obtained.

6. Particle size and dispersion coefficient

The particle size and dispersion coefficient of the aqueous dispersion of the polyester resin were measured. The measurement was carried out using a laser diffraction, scattering particle size distribution measuring apparatus (Coulter counter LS13 320, manufactured by Beckman Co., Ltd.). Next, the particle distribution was prepared on a volume basis by the apparatus, and the average particle diameter and the dispersion coefficient were determined, and the numerical value of the average particle diameter was made into the particle diameter.

7. Viscosity

The aqueous dispersion of the polyester resin was placed in a 140 cc glass bottle, and a No. 1 or No. 2 rotor of a viscometer model BL (TOKIMEC INC.) was used in a 25 ° C thermostatic chamber. The measurement was carried out for 1 minute at a number of revolutions of 60 rpm, and the viscosity of the aqueous dispersion of the polyester resin was further measured.

8.120 °C elastic modulus

The coating liquid was applied to a non-corona surface of a polypropylene film (P2161, thickness: 50 μm, manufactured by Toyobo Co., Ltd.) by a hand coater, and dried at 120 ° C for 1 minute to obtain a laminate having a film having a thickness of about 8 μm. The film was peeled off from the polypropylene film, and measured using a dynamic viscoelasticity measuring apparatus DVA-220 manufactured by ITK Co., Ltd. at 10 Hz and a temperature increase rate of 4 ° C/min. The obtained Er value of 120 ° C in the range of 1 MPa to 1 kPa was ○, and the others were ×. In the cases of Examples 2 to 11 and Comparative Examples 1 to 4, the coating amount and the drying time were changed and measured so that the film thicknesses thereof were the values shown in Table 3.

9. Storage stability test of polyester resin aqueous dispersion composition

The aqueous polyester resin dispersion composition was placed in a 140 cc glass bottle, and placed in an incubator at 40 ° C for 30 days. After a predetermined number of days, the solution was taken out from the incubator, and the viscosity of the solution was measured by the method described above, and compared with the value immediately after the preparation of the coating liquid. The change is ○, and the system solidification is ×.

10. Coating film stability test

The coating liquid was applied to the substrate 1 by a hand coater, and dried at 120 ° C for 1 minute to obtain a laminate having a film having a thickness of about 8 μm. Two identical laminates were produced, and one laminate was laminated on the substrate 2 at a roll temperature of 120 ° C, a push pressure of 4 N/cm, and a speed of 1 m/min, and cut into a size of 1 × 1 cm. Sample 1 was prepared; and the adhesion of the sample 1, solvent resistance (butanthone resistance, ethyl acetate resistance, toluene resistance), soap water resistance, and water resistance were evaluated. On the other laminate, a non-corona surface of a polyester film (manufactured by Toyobo Co., Ltd., 5107, thickness: 25 μm) was coated on the laminate, and stored at a humidity of 60% at 25 ° C for four weeks. . After the storage, the laminate was processed on the substrate 2 at a roll temperature of 120 ° C, a pressing force of 4 N/cm, and a distance of 1 m/min, and cut into a size of 1 × 1 cm to obtain a sample 2. . The adhesion of the sample 2, solvent resistance (butanthone resistance, ethyl acetate resistance, toluene resistance), soap water resistance, and water resistance were evaluated and compared with the performance before storage (sample 1). Those who did not change the evaluation were ○, and those who had poor evaluation of the sample 2 were ×. A polyester film (E5107, manufactured by Toyobo Co., Ltd., thickness: 25 μm) was used as the substrate 1, and the coating liquid was applied to a non-corona surface. A loose-leaf notebook (manufactured by KOKUYO, NO-A836AH) of a thick paper of 100 g/m ² made of high-quality paper was used as the substrate 2. In the cases of Examples 2 to 11 and Comparative Examples 1 to 4, the coating amount and the drying time were changed and measured so that the film thicknesses thereof were the values shown in Table 3.

11. Viscosity

The coating liquid was applied to a non-corona surface of a substrate 1 (polyester film (E5107, manufactured by Toyobo Co., Ltd., thickness: 25 μm)) by a hand coater, and a layer having a film having a thickness of about 8 μm was obtained by drying at 120 ° C for 1 minute. Integral. The film faces were rubbed against each other by hand in an environment of 25 ° C, and the viscosity of the film was completely ◎, and it was slightly viscous, but the range in which there was no problem in use was ○, which was sticky but composed of a polyester resin. The ones which do not adhere to each other are Δ, which are viscous and the polyester resin composition adheres to each other as ×. In the cases of Examples 2 to 11 and Comparative Examples 1 to 4, the coating amount and the drying time were changed and measured so that the film thicknesses thereof were the values shown in Table 3.

12. Adhesion

The coating liquid was applied to a non-corona surface of a substrate 1 (polyester film (E5107, manufactured by Toyobo Co., Ltd., thickness: 25 μm)) by a hand coater, and dried at 120 ° C for 1 minute, thereby obtaining a film having a thickness of about 8 μm. The layered body. The laminate and the substrate 2 (a thick-sheet 100 g/m ² thick-leaf notebook made of high-quality paper (manufactured by KOKUYO, NO-A836AH) at a roller temperature of 120 ° C and a pushing force of 4 N/cm and 1 m/min. )) The laminate was processed and cut into a size of 1 × 1 cm to prepare a sample. The sample was peeled off by hand, and the damage of the substrate was ○, and it was ×.

13. Butanone resistance

A sample was prepared in the same manner as in the above (12. Adhesive item), and immersed in methyl ethyl ketone at room temperature (about 25 ° C) for 1 hour, and then taken out from the solution and dried, and then peeled off by hand, and the substrate was broken. ○, in addition to ×.

14. Acetone resistance

A sample was prepared in the same manner as in the above (12. Adjunct item), and immersed in acetone at room temperature (about 25 ° C) for 1 hour, and then taken out from the solution and dried, and then peeled off by hand, and the substrate was broken. In addition, it is ×.

15. Ethyl acetate resistance

A sample was prepared in the same manner as in the above (12. Adjunct item), and immersed in ethyl acetate at room temperature (about 25 ° C) for 1 hour, and then taken out from the solution and dried, and then peeled off by hand, and the substrate was broken. ○, in addition to ×.

16. Toluene resistance

A sample was prepared in the same manner as in the above (12. Adhesive item), and immersed in toluene at room temperature (about 25 ° C) for 1 hour, and then taken out from the solution and dried, and then peeled off by hand, and the substrate was broken. In addition, it is ×.

17. Resistance to soapy water

A sample was prepared in the same manner as in the above (12. Adhesive item), and immersed in soapy water at 70 ° C and 20% by mass for 1 hour, and then taken out from the solution, and the laminate was rinsed with water, dried, and then peeled off by hand. The damage of the substrate is ○, and it is ×.

18. Water resistance

A sample was prepared in the same manner as in the above (12. Adhesive item), and immersed in water at 25° C. for 30 minutes, and then taken out from the solution and dried, and then peeled off by hand. The damage of the substrate was ○, and it was ×.

Example of Polyester Resin (A)

Synthesis of polyester resin (a-1)

138 parts by mass of dimethyl terephthalate, 136 parts by mass of dimethyl isophthalate, 5-sulfonate in a reaction tank equipped with a stirrer, a thermometer, a heater, a cooling device, and a cooler for distillation 11 parts by mass of sodium isophthalate, 108 parts by mass of ethylene glycol, 120 parts by mass of 2,2-dimethyl1,3-propanediol, and 1 part by mass of tetrabutyl titanate, and the temperature was raised to 230 ° C for 4 hours. A transesterification reaction is carried out. After completion of the transesterification reaction, the temperature was raised to 240 ° C in the system, and the pressure was reduced to 10 torr over 60 minutes, and further reduced to a vacuum of 1 torr or less, and a polycondensation reaction was carried out at 240 ° C for 60 minutes. Thereafter, nitrogen gas was flowed through the system, and the polycondensation reaction was terminated by vacuum destruction. After completion of the reaction, the polyester resin was taken out, and the polyester resin a-1 was obtained by cooling. The NMR analysis results of the obtained polyester resin showed that the molar ratio of the carboxylic acid component was: terephthalic acid/isophthalic acid/5-sulfonate isophthalate = 50/47.5/2.5; The ear ratio is: ethylene glycol/2,2-dimethyl1,3-propanediol = 50/50. The measurement results are shown in Table 1 together with other resin physical properties.

Synthesis of polyester resin (a-10)

388 parts by mass of dimethyl terephthalate, 388 parts by mass of dimethyl isophthalate, and 554 parts by mass of 2-methyl-1,3-propanediol were placed in a reaction vessel equipped with a stirrer, a condenser, and a thermometer. 275 parts by mass of 1,5-pentanediol and 0.41 parts by mass of tetrabutyl titanate were heated from 160 ° C to 230 ° C over 4 hours to carry out a transesterification reaction. Subsequently, the pressure was gradually reduced in the system, and the pressure was reduced to 5 mmHg over 20 minutes, and further, under a vacuum of 0.3 mmHg or less, a polycondensation reaction was carried out at 260 ° C for 40 minutes. Under a nitrogen stream, it was cooled to 220 ° C, and 27 parts by mass of trimellitic anhydride was charged, and the reaction was carried out for 30 minutes. In the NMR composition analysis result of the obtained copolymerized polyester (a-1), the molar ratio of the acid component was: terephthalic acid / isophthalic acid / trimellitic acid = 50 / 50 / 3, diol component The molar ratio is: 2-methyl-1,3-propanediol/1,5-pentanediol = 65/35. The measurement results are shown in Table 1 together with other resin physical properties.

Synthesis of polyester resin (a-2)~(a-9)

In the same manner as in the synthesis example of the polyester resin (a-1), the compositions described in Table 1 were changed to synthesize the polyester resins (a-2) to (a-9). The measurement results of the physical properties of the resin are shown in Table 1.

Synthesis of polyester resin (a-11)

In the same manner as in the synthesis example of the polyester resin (a-10), the composition described in Table 1 was changed to synthesize the polyester resin (a-11). The measurement results of the physical properties of the resin are shown in Table 1.

Manufacture of aqueous dispersion of polyester resin (b-1)

Into a three-necked separation flask equipped with a thermometer, a condenser, and a stirring blade, 300 parts by mass of a polyester resin (a-1) and 100 parts by mass of n-butyl sarbuta were placed, and dissolved at 130 °C. Then, after cooling to 90 ° C, 600 parts by mass of warm water was added over 30 minutes to obtain a solid concentration of 30% by mass. Aqueous dispersion of polyester resin. The results of measurement of the resin physical properties of the obtained aqueous dispersion of the polyester resin are shown in Table 2.

In the same manner as in the production example of the aqueous polyester resin dispersion (b-1), the polyester resin (a-2) to (a-9) were used, and the composition described in Table 2 was changed to produce an aqueous dispersion of the polyester resin. (b-2)~(b-9). The types of solvents are those described in Table 2. The physical properties of the resin were measured in the same manner as the aqueous polyester resin dispersion (b-1). The results are shown in Table 2.

Manufacture of aqueous dispersion of polyester resin (b-10)

100 parts by mass of the polyester resin (a-10), 40 parts by mass of n-butyl sarbuta, and 2.7 parts by mass of triethylamine were charged, and then stirred at 80 ° C for 1 hour to dissolve. Then, 193 parts by mass of ion-exchanged water was slowly added to obtain an aqueous polyester resin dispersion (b-10). The measurement results of the physical properties of the resin are shown in Table 2.

Manufacture of aqueous dispersion of polyester resin (b-11)

In the same manner as in the production example of the aqueous polyester resin dispersion (b-10), a polyester resin (a-11) was used to produce an aqueous polyester resin dispersion (b-11). The measurement results of the physical properties of the resin are shown in Table 2.

As the curing agent (C), a carbodiimide-based curing agent, that is, CARBODILITE (registered trademark) SV-02 manufactured by Nisshinbo Co., Ltd. is used.

As the anti-caking agent (D), a special ester compound, that is, NOPCO (registered trademark) LB-550 manufactured by SAN NOPCO Co., Ltd. was used.

Example 1

40 parts by mass of the aqueous polyester resin dispersion (b-3), 40 parts by mass of the aqueous polyester resin dispersion (b-9), and 20 parts by mass of the aqueous dispersion of the polyester resin (b-5), CARBODILITESV-022 Parts by mass and NOPCOLB-5502 parts by mass were mixed to prepare a coating liquid. The coating liquid was applied to a non-corona surface of a polyester film (E5107, manufactured by Toyobo Co., Ltd., thickness: 25 μm) as a substrate 1 by a hand coater, and dried at 120 ° C for 3 minutes, thereby obtaining a film having a thickness of about 8 μm. A laminate of a film (coating film). The glass transition temperature of the polyester resin contained in the film after absolute drying was 15 °C. The laminate and the substrate 2 (KOKUYO leaflet (NOTE-A836AH)) were laminated at a roll temperature of 120 ° C, a pressing force of 4 N, and a speed of 1 m/min to obtain a sample. The sample was cut into a size of 1 × 1 cm, and the adhesion, solvent resistance (butanone resistance, acetone resistance, ethyl acetate resistance, and toluene resistance), soap water resistance, and water resistance were evaluated. The evaluation results are shown in Table 3. In addition, the coating liquid was applied to a non-corona surface of a polypropylene film (P2161, thickness: 50 μm, manufactured by Toyobo Co., Ltd.) by a hand coater, and dried at 120 ° C for 1 minute to obtain a film having a thickness of about 8 μm (coating film). The layered body. The laminate was evaluated for the elastic modulus at 120 ° C using the laminate, and the modulus of elasticity was 383 kPa. Further, the coating liquid was applied to a non-corona surface of a polyester film (E5107, manufactured by Toyobo Co., Ltd., thickness: 25 μm) by a hand coater at 120 ° C. Thereafter, it was dried for 1 minute, whereby a laminate having a film (coated film) of about 8 μm was obtained. The laminate was evaluated for viscosity. The evaluation results are also shown in Table 3.

Example 2~11

In the same manner as in Example 1, the blending component and the film thickness shown in Table 3 were changed, and the same evaluation was carried out. The evaluation results are also shown in Table 3.

Comparative example 1~4

In the same manner as in Example 1, the same evaluation was carried out with different blending components. The evaluation results are shown together in Table 3.

It is clear from Table 3 that the present invention can provide an adhesive composition which, despite the use of the aqueous dispersion of the polyester resin, has good adhesion to various substrates such as cloth, paper, or plastic film, in the coating liquid. The storage stability is excellent, and it is excellent in solvent resistance, soap water resistance, and water resistance with respect to various solvents.

[Industrial Availability]

The present invention is easy to form a polyester resin adhesive composition which has long-term storage stability in a state of being applied to the substrate 1, and is excellent in adhesion, solvent resistance, soap water resistance, and water resistance, so that it is industrially Great contribution.

Claims (7)

A polyester resin aqueous dispersion composition comprising a polyester resin (A), a polyester resin (B) and a hardener (C), wherein the total amount of the carboxylic acid component is 100 moles in the polyester resin (A) In the case of %, the copolymerization amount of the aromatic dicarboxylic acid component is 56.8 mol% or more, and when the total amount of the diol component is 100 mol%, the copolymerization amount of the aliphatic diol component is 100 mol. %; and satisfy any of the following [1] to [3], and satisfy the following [4]; [1] polyester resin (A) has an acid value of 10 to 400 eq/t, and a glass transition temperature of 5 Polyester resin of ~50 ° C; polyester resin (B) is an amorphous polyester resin having a glass transition temperature of 25 ° C or less; glass transition temperature of polyester resin (A) is higher than that of polyester resin (B) Conversion temperature; [2] polyester resin (A) is a mixture of an amorphous polyester resin (A1) having a glass transition temperature of 50 ° C or higher and a crystalline polyester resin (A2) having a glass transition temperature of 0 ° C or less, The weighted average of the glass transition temperatures of (A1) and (A2) is 5 to 50 ° C, the weighted average of the acid value is 10 to 400 eq/t, and the polyester resin (B) is a glass transition temperature of 25 ° C or less. Crystalline polyester resin, polyester resin (A1) and The weighted average value of the glass transition temperature of the polyester resin (A2) is higher than the glass transition temperature of the polyester resin (B); [3] a film having a film thickness of 8 μm is formed from the aqueous dispersion composition of the polyester resin, so that the film is absolutely After drying, the glass transition temperature of the polyester resin (A) or the polyester resin (B) contained therein is at least one of 5 to 50 ° C; [4] a film thickness of 8 μm is formed from the aqueous dispersion composition of the polyester resin. In the case of a film, the film has an elastic modulus at 120 ° C of 1 MPa to 1 kPa. The aqueous polyester resin dispersion composition according to claim 1, wherein the curing agent (C) is a carbodiimide-based curing agent. The polyester resin aqueous dispersion composition according to claim 1 or 2, wherein the polyester resin (B) is contained in an amount of 10 to 100 parts by mass based on 100 parts by mass of the polyester resin (A), and a curing agent (C) ) 0.5 to 40 parts by mass. An adhesive composition comprising the aqueous polyester resin dispersion composition according to any one of claims 1 to 3. The adhesive composition of claim 4 is for bonding a film to a film or paper. A laminate obtained by laminating an adhesive composition as disclosed in claim 4 or 5. A method for producing a laminate, comprising applying a polyester resin aqueous dispersion composition containing the polyester resin and the curing agent (C) according to any one of the following [1] to [3] to the substrate 1, After forming a film having a film thickness of 8 μm and an elastic modulus of 120 MPa of 1 MPa to 1 kPa, the substrate 2 is bonded; [1] the polyester resin (A) has an acid value of 10 to 400 eq/t, and the glass transition temperature is a polyester resin of 5 to 50 ° C; a polyester resin (B) is an amorphous polyester resin having a glass transition temperature of 25 ° C or less; a glass transition temperature of the polyester resin (A) is higher than that of the polyester resin (B) Glass transition temperature; [2] Polyester resin (A) is a mixture of amorphous polyester resin (A1) having a glass transition temperature of 50 ° C or higher and a crystalline polyester resin (A2) having a glass transition temperature of 0 ° C or less (A1) and (A2) have a weighted average of glass transition temperatures of 5 to 50 ° C, a weighted average of acid values of 10 to 400 eq/t, and a polyester resin (B) glass transition temperature of 25 ° C or less. The weighted average value of the glass transition temperature of the amorphous polyester resin, the polyester resin (A1) and the polyester resin (A2) is higher than the glass transition temperature of the polyester resin (B); [3] After the film is absolutely dried, the glass transition temperature of the polyester resin (A) or the polyester resin (B) contained therein is at least one of 5 to 50 ° C; wherein the polyester resin (A) When the total amount of the carboxylic acid component is 100 mol%, the copolymerization amount of the aromatic dicarboxylic acid component is 56.8 mol% or more, and when the total amount of the diol component is 100 mol%, the aliphatic di The amount of copolymerization of the alcohol component was 100 mol%.